ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES
20220399510 · 2022-12-15
Assignee
Inventors
- Jui-Yi TSAI (Newtown, PA, US)
- Alexey Borisovich DYATKIN (Ambler, PA, US)
- Walter Yeager (Yardley, PA, US)
- Pierre-Luc T. Boudreault (Pennington, NJ)
Cpc classification
C09K2211/185
CHEMISTRY; METALLURGY
C07B59/004
CHEMISTRY; METALLURGY
H10K2101/30
ELECTRICITY
C07B2200/05
CHEMISTRY; METALLURGY
International classification
Abstract
A compound including a first ligand L.sub.A of Formula I,
##STR00001##
is described. In Formula I, each of X.sup.1 to X.sup.9 is independently C or N; one of Z.sup.1 and Z.sup.2 is C and the other is N; each of K.sup.1 and K.sup.2 is independently a direct bond, O, or S; at least one of K.sup.1 and K.sup.2 is a direct bond; at least one R.sup.B is not hydrogen; R.sup.3 is selected from alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl; L.sub.A is coordinated to a metal M; at least one of the following is true: (i) at least one R.sup.B comprises a 5- or 6-membered, (ii) two adjacent R.sup.B are joined to form a fused 5- or 6-membered ring, or (iii) R.sup.B comprises a carbocyclic or heterocyclic ring substituted with at least one electron withdrawing group. Devices, consumer products, and formulations including the compound are also described.
Claims
1. A compound comprising a first ligand L.sub.A of Formula I: ##STR00307## wherein: each of X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, and X.sup.9 is independently C or N; one of Z.sup.1 and Z.sup.2 is C and the other is N; K.sup.1 and K.sup.2 are each independently selected from the group consisting of a direct bond, O, and S; at least one of K.sup.1 and K.sup.2 is a direct bond; R.sup.A and R.sup.C each independently represents mono, up to maximum allowed substitutions, or no substitution; R.sup.B represents mono, or up to maximum allowed substitutions; each of R.sup.1, R.sup.2, R.sup.A, R.sup.B, and R.sup.C is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; each of X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, and X.sup.9 that has an R.sup.A, R.sup.B, or R.sup.C attached thereto is C; at least one of R.sup.1 and R.sup.2 is selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl; R.sup.3 is selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl; at least one of the following is true: (i) at least one R.sup.B comprises a 5-membered or 6-membered heterocycle, (ii) two adjacent R.sup.B are joined to form a fused 5-membered or 6-membered carbocyclic or heterocyclic ring, which can be further substituted, or (iii) R.sup.B comprises a carbocyclic or heterocyclic ring substituted with at least one electron withdrawing group; L.sub.A is coordinated to a metal M selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au; L.sub.A may be joined with other ligand to comprise a tridentate, tetradentate, pentadentate, and hexadentate ligand; and any two of R.sup.1, R.sup.2, R.sup.3, R.sup.A, R.sup.B, and R.sup.C can be joined to form a ring.
2. The compound of claim 1, wherein each of R.sup.1, R.sup.2, R.sup.A, R.sup.B, and R.sup.C is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
3. The compound of claim 1, wherein each of R.sup.1 and R.sup.2 is selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl; and/or wherein at least one of X.sup.1 to X.sup.9 is N; and/or wherein Z.sup.1 is N and Z.sup.2 is C or wherein Z.sup.1 is C and Z.sup.2 is N.
4. The compound of claim 1, wherein at least one R.sup.B comprises a 5-membered or 6-membered heterocycle; or wherein at least one R.sup.B comprises at least two 5-membered or 6-membered heterocyclic or carbocyclic rings; or wherein at least one R.sup.B comprises at least three 5-membered or 6-membered heterocyclic or carbocyclic rings.
5. The compound of claim 1, wherein two adjacent R.sup.B are joined to form a fused 5-membered or 6-membered carbocyclic or heterocyclic ring, which can be further substituted with a chemical group selected from the group consisting of: ##STR00308## ##STR00309## ##STR00310## ##STR00311## ##STR00312## ##STR00313## ##STR00314## ##STR00315## ##STR00316## ##STR00317## ##STR00318## ##STR00319## or wherein the fused 5-membered or 6-membered carbocyclic or heterocyclic ring is further fused by a 5-membered or 6-membered carbocyclic or heterocyclic ring.
6. The compound of claim 1, wherein R.sup.B comprises a 5-membered or 6-membered carbocyclic or heterocyclic aromatic ring substituted with at least one electron withdrawing group, wherein the electron withdrawing group is selected from the group consisting of CN, CF.sub.3, COCH.sub.3, CHO, COCF.sub.3, COOMe, COOCF.sub.3, NO.sub.2, SF.sub.3, SiF.sub.3, PF.sub.4, SF.sub.5, OCF.sub.3, SCF.sub.3, SeCF.sub.3, SOCF.sub.3, SeOCF.sub.3, SO.sub.2F, SO.sub.2CF.sub.3, SeO.sub.2CF.sub.3, OSO.sub.2CF.sub.3, OSeO.sub.2CF.sub.3, OCN, SCN, SeCN, NC, .sup.+N(R).sub.3, (R).sub.2CCN, (R).sub.2CCF.sub.3, CNC(CF.sub.3).sub.2, ##STR00320## wherein each R is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
7. The compound of claim 1, wherein two R.sup.C are joined to form a polycyclic fused ring structure that includes Ring C.
8. The compound of claim 1, wherein the ligand L.sub.A is selected from the group consisting of: ##STR00321## ##STR00322## ##STR00323## ##STR00324## ##STR00325## ##STR00326## ##STR00327## ##STR00328## ##STR00329## ##STR00330## wherein X for each structure is independently NR, O, S, Se, C═O, S═O, and SO.sub.2; R.sup.D independently represent mono, up to maximum allowed substitutions, or no substitution; and each R.sup.D is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
9. The compound of claim 1, wherein the ligand L.sub.A is selected from the group consisting of: ##STR00331## ##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336## ##STR00337## ##STR00338## ##STR00339## ##STR00340## ##STR00341## ##STR00342## ##STR00343## wherein X.sup.10 is independently C or N; wherein R.sup.C′ represents mono, up to maximum allowed substitutions, or no substitution; each R.sup.C′ and R.sup.D is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
10. The compound of claim 1, wherein the ligand L.sub.A is selected from the group consisting of: ##STR00344## ##STR00345## ##STR00346## ##STR00347## ##STR00348## ##STR00349## ##STR00350## ##STR00351## ##STR00352## ##STR00353## ##STR00354## ##STR00355## ##STR00356## ##STR00357## ##STR00358## ##STR00359## ##STR00360## ##STR00361## ##STR00362## ##STR00363## ##STR00364## ##STR00365##
11. The compound of claim 1, wherein the compound has a formula of M(L.sub.A).sub.p(L.sub.B).sub.q(L.sub.C).sub.r wherein L.sub.B and L.sub.C are each a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M.
12. The compound of claim 11, wherein the compound has a formula selected from the group consisting of Ir(L.sub.A).sub.3, Ir(L.sub.A)(L.sub.B).sub.2, Ir(L.sub.A).sub.2(L.sub.B), Ir(L.sub.A).sub.2(L.sub.C), and Ir(L.sub.A)(L.sub.B)(L.sub.C), and wherein L.sub.A, L.sub.B, and L.sub.C are different from each other; or the compound has a formula of Pt(L.sub.A)(L.sub.B), wherein L.sub.A and L.sub.B can be same or different.
13. The compound of claim 11, wherein L.sub.B and L.sub.C are each independently selected from the group consisting of: ##STR00366## ##STR00367## ##STR00368## wherein: T is selected from the group consisting of B, Al, Ga, and In; each of Y.sup.1 to Y.sup.13 is independently selected from the group consisting of carbon and nitrogen; Y′ is selected from the group consisting of BR.sub.e, NR.sub.e, PR.sub.e, O, S, Se, C═O, S═O, SO.sub.2, CR.sub.eR.sub.f, SiR.sub.eR.sub.f, and GeR.sub.eR.sub.f; R.sub.e and R.sub.f can be fused or joined to form a ring; each R.sub.a, R.sub.b, R.sub.c, and R.sub.d independently represent zero, mono, or up to a maximum allowed number of substitutions to its associated ring; each of R.sub.a1, R.sub.b1, R.sub.c1, R.sub.d1, R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f is independently a hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; the general substituents defined herein; and any two adjacent R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f can be fused or joined to form a ring or form a multidentate ligand.
14. The compound of claim 12, wherein the compound has a structure of formula Ir(L.sub.A).sub.3, formula Ir(L.sub.A)(L.sub.Bk).sub.2, formula Ir(L.sub.A).sub.2(L.sub.Bk), formula Ir(L.sub.A).sub.2(L.sub.Cj-I), or formula Ir(L.sub.A).sub.2(L.sub.Cj-II), wherein each L.sub.A is selected from the group consisting of: ##STR00369## ##STR00370## ##STR00371## ##STR00372## ##STR00373## ##STR00374## ##STR00375## ##STR00376## ##STR00377## wherein X for each structure is independently NR, O, S, Se, C═O, S═O, and SO.sub.2; R.sup.D independently represent mono, up to maximum allowed substitutions, or no substitution; and each R.sup.D is independently a hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; or each L.sub.A is selected from the group consisting of: ##STR00378## ##STR00379## ##STR00380## ##STR00381## ##STR00382## ##STR00383## wherein X.sup.10 is independently C or N; wherein R.sup.C′ represents mono, up to maximum allowed substitutions, or no substitution; and wherein each R.sup.C′ and R.sup.D is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; or each L.sub.A is selected from the group consisting of: ##STR00384## ##STR00385## ##STR00386## ##STR00387## ##STR00388## ##STR00389## ##STR00390## ##STR00391## ##STR00392## ##STR00393## ##STR00394## ##STR00395## ##STR00396## ##STR00397## ##STR00398## ##STR00399## ##STR00400## ##STR00401## ##STR00402## ##STR00403## ##STR00404## ##STR00405## ##STR00406## ##STR00407## wherein k is an integer from 1 to 324; j is an integer from 1 to 1416; and each of L.sub.B1 to L.sub.B324 has a defined as follows: ##STR00408## ##STR00409## ##STR00410## ##STR00411## ##STR00412## ##STR00413## ##STR00414## ##STR00415## ##STR00416## ##STR00417## ##STR00418## ##STR00419## ##STR00420## ##STR00421## ##STR00422## ##STR00423## ##STR00424## ##STR00425## ##STR00426## ##STR00427## ##STR00428## ##STR00429## ##STR00430## ##STR00431## ##STR00432## ##STR00433## ##STR00434## ##STR00435## ##STR00436## ##STR00437## ##STR00438## ##STR00439## ##STR00440## ##STR00441## ##STR00442## ##STR00443## ##STR00444## ##STR00445## ##STR00446## ##STR00447## ##STR00448## ##STR00449## ##STR00450## wherein each L.sub.Cj-I has a structure based on formula ##STR00451## and each L.sub.Cj-II has a structure based on formula ##STR00452## wherein for each L.sub.Cj in L.sub.Cj-I and L.sub.Cj-II, R.sup.201 and R.sup.202 are each independently defined as follows: TABLE-US-00004 L.sub.Cj R.sup.201 R.sup.202 L.sub.Cj R.sup.201 R.sup.202 L.sub.Cj R.sup.201 R.sup.202 L.sub.Cj R.sup.201 R.sup.202 L.sub.C1 R.sup.D1 R.sup.D1 L.sub.C193 R.sup.D1 R.sup.D3 L.sub.C385 R.sup.D17 R.sup.D40 L.sub.C577 R.sup.D143 R.sup.D120 L.sub.C2 R.sup.D2 R.sup.D2 L.sub.C194 R.sup.D1 R.sup.D4 L.sub.C386 R.sup.D17 R.sup.D41 L.sub.C578 R.sup.D143 R.sup.D133 L.sub.C3 R.sup.D3 R.sup.D3 L.sub.C195 R.sup.D1 R.sup.D5 L.sub.C387 R.sup.D17 R.sup.D42 L.sub.C579 R.sup.D143 R.sup.D134 L.sub.C4 R.sup.D4 R.sup.D4 L.sub.C196 R.sup.D1 R.sup.D9 L.sub.C388 R.sup.D17 R.sup.D43 L.sub.C580 R.sup.D143 R.sup.D135 L.sub.C5 R.sup.D5 R.sup.D5 L.sub.C197 R.sup.D1 R.sup.D10 L.sub.C389 R.sup.D17 R.sup.D48 L.sub.C581 R.sup.D143 R.sup.D136 L.sub.C6 R.sup.D6 R.sup.D6 L.sub.C198 R.sup.D1 R.sup.D17 L.sub.C390 R.sup.D17 R.sup.D49 L.sub.C582 R.sup.D143 R.sup.D144 L.sub.C7 R.sup.D7 R.sup.D7 L.sub.C199 R.sup.D1 R.sup.D18 L.sub.C391 R.sup.D17 R.sup.D50 L.sub.C583 R.sup.D143 R.sup.D145 L.sub.C8 R.sup.D8 R.sup.D8 L.sub.C200 R.sup.D1 R.sup.D20 L.sub.C392 R.sup.D17 R.sup.D54 L.sub.C584 R.sup.D143 R.sup.D146 L.sub.C9 R.sup.D9 R.sup.D9 L.sub.C201 R.sup.D1 R.sup.D22 L.sub.C393 R.sup.D17 R.sup.D55 L.sub.C585 R.sup.D143 R.sup.D147 L.sub.C10 R.sup.D10 R.sup.D10 L.sub.C202 R.sup.D1 R.sup.D37 L.sub.C394 R.sup.D17 R.sup.D58 L.sub.C586 R.sup.D143 R.sup.D149 L.sub.C11 R.sup.D11 R.sup.D11 L.sub.C203 R.sup.D1 R.sup.D40 L.sub.C395 R.sup.D17 R.sup.D59 L.sub.C587 R.sup.D143 R.sup.D151 L.sub.C12 R.sup.D12 R.sup.D12 L.sub.C204 R.sup.D1 R.sup.D41 L.sub.C396 R.sup.D17 R.sup.D78 L.sub.C588 R.sup.D143 R.sup.D154 L.sub.C13 R.sup.D13 R.sup.D13 L.sub.C205 R.sup.D1 R.sup.D42 L.sub.C397 R.sup.D17 R.sup.D79 L.sub.C589 R.sup.D143 R.sup.D155 L.sub.C14 R.sup.D14 R.sup.D14 L.sub.C206 R.sup.D1 R.sup.D43 L.sub.C398 R.sup.D17 R.sup.D81 L.sub.C590 R.sup.D143 R.sup.D161 L.sub.C15 R.sup.D15 R.sup.D15 L.sub.C207 R.sup.D1 R.sup.D48 L.sub.C399 R.sup.D17 R.sup.D87 L.sub.C591 R.sup.D143 R.sup.D175 L.sub.C16 R.sup.D16 R.sup.D16 L.sub.C208 R.sup.D1 R.sup.D49 L.sub.C400 R.sup.D17 R.sup.D88 L.sub.C592 R.sup.D144 R.sup.D3 L.sub.C17 R.sup.D17 R.sup.D17 L.sub.C209 R.sup.D1 R.sup.D50 L.sub.C401 R.sup.D17 R.sup.D89 L.sub.C593 R.sup.D144 R.sup.D5 L.sub.C18 R.sup.D18 R.sup.D18 L.sub.C210 R.sup.D1 R.sup.D54 L.sub.C402 R.sup.D17 R.sup.D93 L.sub.C594 R.sup.D144 R.sup.D17 L.sub.C19 R.sup.D19 R.sup.D19 L.sub.C211 R.sup.D1 R.sup.D55 L.sub.C403 R.sup.D17 R.sup.D116 L.sub.C595 R.sup.D144 R.sup.D18 L.sub.C20 R.sup.D20 R.sup.D20 L.sub.C212 R.sup.D1 R.sup.D58 L.sub.C404 R.sup.D17 R.sup.D117 L.sub.C596 R.sup.D144 R.sup.D20 L.sub.C21 R.sup.D21 R.sup.D21 L.sub.C213 R.sup.D1 R.sup.D59 L.sub.C405 R.sup.D17 R.sup.D118 L.sub.C597 R.sup.D144 R.sup.D22 L.sub.C22 R.sup.D22 R.sup.D22 L.sub.C214 R.sup.D1 R.sup.D78 L.sub.C406 R.sup.D17 R.sup.D119 L.sub.C598 R.sup.D144 R.sup.D37 L.sub.C23 R.sup.D23 R.sup.D23 L.sub.C215 R.sup.D1 R.sup.D79 L.sub.C407 R.sup.D17 R.sup.D120 L.sub.C599 R.sup.D144 R.sup.D40 L.sub.C24 R.sup.D24 R.sup.D24 L.sub.C216 R.sup.D1 R.sup.D81 L.sub.C408 R.sup.D17 R.sup.D133 L.sub.C600 R.sup.D144 R.sup.D41 L.sub.C25 R.sup.D25 R.sup.D25 L.sub.C217 R.sup.D1 R.sup.D87 L.sub.C409 R.sup.D17 R.sup.D134 L.sub.C601 R.sup.D144 R.sup.D42 L.sub.C26 R.sup.D26 R.sup.D26 L.sub.C218 R.sup.D1 R.sup.D88 L.sub.C410 R.sup.D17 R.sup.D135 L.sub.C602 R.sup.D144 R.sup.D43 L.sub.C27 R.sup.D27 R.sup.D27 L.sub.C219 R.sup.D1 R.sup.D89 L.sub.C411 R.sup.D17 R.sup.D136 L.sub.C603 R.sup.D144 R.sup.D48 L.sub.C28 R.sup.D28 R.sup.D28 L.sub.C220 R.sup.D1 R.sup.D93 L.sub.C412 R.sup.D17 R.sup.D143 L.sub.C604 R.sup.D144 R.sup.D49 L.sub.C29 R.sup.D29 R.sup.D29 L.sub.C221 R.sup.D1 R.sup.D116 L.sub.C413 R.sup.D17 R.sup.D144 L.sub.C605 R.sup.D144 R.sup.D54 L.sub.C30 R.sup.D30 R.sup.D30 L.sub.C222 R.sup.D1 R.sup.D117 L.sub.C414 R.sup.D17 R.sup.D145 L.sub.C606 R.sup.D144 R.sup.D58 L.sub.C31 R.sup.D31 R.sup.D31 L.sub.C223 R.sup.D1 R.sup.D118 L.sub.C415 R.sup.D17 R.sup.D146 L.sub.C607 R.sup.D144 R.sup.D59 L.sub.C32 R.sup.D32 R.sup.D32 L.sub.C224 R.sup.D1 R.sup.D119 L.sub.C416 R.sup.D17 R.sup.D147 L.sub.C608 R.sup.D144 R.sup.D78 L.sub.C33 R.sup.D33 R.sup.D33 L.sub.C225 R.sup.D1 R.sup.D120 L.sub.C417 R.sup.D17 R.sup.D149 L.sub.C609 R.sup.D144 R.sup.D79 L.sub.C34 R.sup.D34 R.sup.D34 L.sub.C226 R.sup.D1 R.sup.D133 L.sub.C418 R.sup.D17 R.sup.D151 L.sub.C610 R.sup.D144 R.sup.D81 L.sub.C35 R.sup.D35 R.sup.D35 L.sub.C227 R.sup.D1 R.sup.D134 L.sub.C419 R.sup.D17 R.sup.D154 L.sub.C611 R.sup.D144 R.sup.D87 L.sub.C36 R.sup.D36 R.sup.D36 L.sub.C228 R.sup.D1 R.sup.D135 L.sub.C420 R.sup.D17 R.sup.D155 L.sub.C612 R.sup.D144 R.sup.D88 L.sub.C37 R.sup.D37 R.sup.D37 L.sub.C229 R.sup.D1 R.sup.D136 L.sub.C421 R.sup.D17 R.sup.D161 L.sub.C613 R.sup.D144 R.sup.D89 L.sub.C38 R.sup.D38 R.sup.D38 L.sub.C230 R.sup.D1 R.sup.D143 L.sub.C422 R.sup.D17 R.sup.D175 L.sub.C614 R.sup.D144 R.sup.D93 L.sub.C39 R.sup.D39 R.sup.D39 L.sub.C231 R.sup.D1 R.sup.D144 L.sub.C423 R.sup.D50 R.sup.D3 L.sub.C615 R.sup.D144 R.sup.D116 L.sub.C40 R.sup.D40 R.sup.D40 L.sub.C232 R.sup.D1 R.sup.D145 L.sub.C424 R.sup.D50 R.sup.D5 L.sub.C616 R.sup.D144 R.sup.D117 L.sub.C41 R.sup.D41 R.sup.D41 L.sub.C233 R.sup.D1 R.sup.D146 L.sub.C425 R.sup.D50 R.sup.D18 L.sub.C617 R.sup.D144 R.sup.D118 L.sub.C42 R.sup.D42 R.sup.D42 L.sub.C234 R.sup.D1 R.sup.D147 L.sub.C426 R.sup.D50 R.sup.D20 L.sub.C618 R.sup.D144 R.sup.D119 L.sub.C43 R.sup.D43 R.sup.D43 L.sub.C235 R.sup.D1 R.sup.D149 L.sub.C427 R.sup.D50 R.sup.D22 L.sub.C619 R.sup.D144 R.sup.D120 L.sub.C44 R.sup.D44 R.sup.D44 L.sub.C236 R.sup.D1 R.sup.D151 L.sub.C428 R.sup.D50 R.sup.D37 L.sub.C620 R.sup.D144 R.sup.D133 L.sub.C45 R.sup.D45 R.sup.D45 L.sub.C237 R.sup.D1 R.sup.D154 L.sub.C429 R.sup.D50 R.sup.D40 L.sub.C621 R.sup.D144 R.sup.D134 L.sub.C46 R.sup.D46 R.sup.D46 L.sub.C238 R.sup.D1 R.sup.D155 L.sub.C430 R.sup.D50 R.sup.D41 L.sub.C622 R.sup.D144 R.sup.D135 L.sub.C47 R.sup.D47 R.sup.D47 L.sub.C239 R.sup.D1 R.sup.D161 L.sub.C431 R.sup.D50 R.sup.D42 L.sub.C623 R.sup.D144 R.sup.D136 L.sub.C48 R.sup.D48 R.sup.D48 L.sub.C240 R.sup.D1 R.sup.D175 L.sub.C432 R.sup.D50 R.sup.D43 L.sub.C624 R.sup.D144 R.sup.D145 L.sub.C49 R.sup.D49 R.sup.D49 L.sub.C241 R.sup.D4 R.sup.D3 L.sub.C433 R.sup.D50 R.sup.D48 L.sub.C625 R.sup.D144 R.sup.D146 L.sub.C50 R.sup.D50 R.sup.D50 L.sub.C242 R.sup.D4 R.sup.D5 L.sub.C434 R.sup.D50 R.sup.D49 L.sub.C626 R.sup.D144 R.sup.D147 L.sub.C51 R.sup.D51 R.sup.D51 L.sub.C243 R.sup.D4 R.sup.D9 L.sub.C435 R.sup.D50 R.sup.D54 L.sub.C627 R.sup.D144 R.sup.D149 L.sub.C52 R.sup.D52 R.sup.D52 L.sub.C244 R.sup.D4 R.sup.D10 L.sub.C436 R.sup.D50 R.sup.D55 L.sub.C628 R.sup.D144 R.sup.D151 L.sub.C53 R.sup.D53 R.sup.D53 L.sub.C245 R.sup.D4 R.sup.D17 L.sub.C437 R.sup.D50 R.sup.D58 L.sub.C629 R.sup.D144 R.sup.D154 L.sub.C54 R.sup.D54 R.sup.D54 L.sub.C246 R.sup.D4 R.sup.D18 L.sub.C438 R.sup.D50 R.sup.D59 L.sub.C630 R.sup.D144 R.sup.D155 L.sub.C55 R.sup.D55 R.sup.D55 L.sub.C247 R.sup.D4 R.sup.D20 L.sub.C439 R.sup.D50 R.sup.D78 L.sub.C631 R.sup.D144 R.sup.D161 L.sub.C56 R.sup.D56 R.sup.D56 L.sub.C248 R.sup.D4 R.sup.D22 L.sub.C440 R.sup.D50 R.sup.D79 L.sub.C632 R.sup.D144 R.sup.D175 L.sub.C57 R.sup.D57 R.sup.D57 L.sub.C249 R.sup.D4 R.sup.D37 L.sub.C441 R.sup.D50 R.sup.D81 L.sub.C633 R.sup.D145 R.sup.D3 L.sub.C58 R.sup.D58 R.sup.D58 L.sub.C250 R.sup.D4 R.sup.D40 L.sub.C442 R.sup.D50 R.sup.D87 L.sub.C634 R.sup.D145 R.sup.D5 L.sub.C59 R.sup.D59 R.sup.D59 L.sub.C251 R.sup.D4 R.sup.D41 L.sub.C443 R.sup.D50 R.sup.D88 L.sub.C635 R.sup.D145 R.sup.D17 L.sub.C60 R.sup.D60 R.sup.D60 L.sub.C252 R.sup.D4 R.sup.D42 L.sub.C444 R.sup.D50 R.sup.D89 L.sub.C636 R.sup.D145 R.sup.D18 L.sub.C61 R.sup.D61 R.sup.D61 L.sub.C253 R.sup.D4 R.sup.D43 L.sub.C445 R.sup.D50 R.sup.D93 L.sub.C637 R.sup.D145 R.sup.D20 L.sub.C62 R.sup.D62 R.sup.D62 L.sub.C254 R.sup.D4 R.sup.D48 L.sub.C446 R.sup.D50 R.sup.D116 L.sub.C638 R.sup.D145 R.sup.D22 L.sub.C63 R.sup.D63 R.sup.D63 L.sub.C255 R.sup.D4 R.sup.D49 L.sub.C447 R.sup.D50 R.sup.D117 L.sub.C639 R.sup.D145 R.sup.D37 L.sub.C64 R.sup.D64 R.sup.D64 L.sub.C256 R.sup.D4 R.sup.D50 L.sub.C448 R.sup.D50 R.sup.D118 L.sub.C640 R.sup.D145 R.sup.D40 L.sub.C65 R.sup.D65 R.sup.D65 L.sub.C257 R.sup.D4 R.sup.D54 L.sub.C449 R.sup.D50 R.sup.D119 L.sub.C641 R.sup.D145 R.sup.D41 L.sub.C66 R.sup.D66 R.sup.D66 L.sub.C258 R.sup.D4 R.sup.D55 L.sub.C450 R.sup.D50 R.sup.D120 L.sub.C642 R.sup.D145 R.sup.D42 L.sub.C67 R.sup.D67 R.sup.D67 L.sub.C259 R.sup.D4 R.sup.D58 L.sub.C451 R.sup.D50 R.sup.D133 L.sub.C643 R.sup.D145 R.sup.D43 L.sub.C68 R.sup.D68 R.sup.D68 L.sub.C260 R.sup.D4 R.sup.D59 L.sub.C452 R.sup.D50 R.sup.D134 L.sub.C644 R.sup.D145 R.sup.D48 L.sub.C69 R.sup.D69 R.sup.D69 L.sub.C261 R.sup.D4 R.sup.D78 L.sub.C453 R.sup.D50 R.sup.D135 L.sub.C645 R.sup.D145 R.sup.D49 L.sub.C70 R.sup.D70 R.sup.D70 L.sub.C262 R.sup.D4 R.sup.D79 L.sub.C454 R.sup.D50 R.sup.D136 L.sub.C646 R.sup.D145 R.sup.D54 L.sub.C71 R.sup.D71 R.sup.D71 L.sub.C263 R.sup.D4 R.sup.D81 L.sub.C455 R.sup.D50 R.sup.D143 L.sub.C647 R.sup.D145 R.sup.D58 L.sub.C72 R.sup.D72 R.sup.D72 L.sub.C264 R.sup.D4 R.sup.D87 L.sub.C456 R.sup.D50 R.sup.D144 L.sub.C648 R.sup.D145 R.sup.D59 L.sub.C73 R.sup.D73 R.sup.D73 L.sub.C265 R.sup.D4 R.sup.D88 L.sub.C457 R.sup.D50 R.sup.D145 L.sub.C649 R.sup.D145 R.sup.D78 L.sub.C74 R.sup.D74 R.sup.D74 L.sub.C266 R.sup.D4 R.sup.D89 L.sub.C458 R.sup.D50 R.sup.D146 L.sub.C650 R.sup.D145 R.sup.D79 L.sub.C75 R.sup.D75 R.sup.D75 L.sub.C267 R.sup.D4 R.sup.D93 L.sub.C459 R.sup.D50 R.sup.D147 L.sub.C651 R.sup.D145 R.sup.D81 L.sub.C76 R.sup.D76 R.sup.D76 L.sub.C268 R.sup.D4 R.sup.D116 L.sub.C460 R.sup.D50 R.sup.D149 L.sub.C652 R.sup.D145 R.sup.D87 L.sub.C77 R.sup.D77 R.sup.D77 L.sub.C269 R.sup.D4 R.sup.D117 L.sub.C461 R.sup.D50 R.sup.D151 L.sub.C653 R.sup.D145 R.sup.D88 L.sub.C78 R.sup.D78 R.sup.D78 L.sub.C270 R.sup.D4 R.sup.D118 L.sub.C462 R.sup.D50 R.sup.D154 L.sub.C654 R.sup.D145 R.sup.D89 L.sub.C79 R.sup.D79 R.sup.D79 L.sub.C271 R.sup.D4 R.sup.D119 L.sub.C463 R.sup.D50 R.sup.D155 L.sub.C655 R.sup.D145 R.sup.D93 L.sub.C80 R.sup.D80 R.sup.D80 L.sub.C272 R.sup.D4 R.sup.D120 L.sub.C464 R.sup.D50 R.sup.D161 L.sub.C656 R.sup.D145 R.sup.D116 L.sub.C81 R.sup.D81 R.sup.D81 L.sub.C273 R.sup.D4 R.sup.D133 L.sub.C465 R.sup.D50 R.sup.D175 L.sub.C657 R.sup.D145 R.sup.D117 L.sub.C82 R.sup.D82 R.sup.D82 L.sub.C274 R.sup.D4 R.sup.D134 L.sub.C466 R.sup.D55 R.sup.D3 L.sub.C658 R.sup.D145 R.sup.D118 L.sub.C83 R.sup.D83 R.sup.D83 L.sub.C275 R.sup.D4 R.sup.D135 L.sub.C467 R.sup.D55 R.sup.D5 L.sub.C659 R.sup.D145 R.sup.D119 L.sub.C84 R.sup.D84 R.sup.D84 L.sub.C276 R.sup.D4 R.sup.D136 L.sub.C468 R.sup.D55 R.sup.D18 L.sub.C660 R.sup.D145 R.sup.D120 L.sub.C85 R.sup.D85 R.sup.D85 L.sub.C277 R.sup.D4 R.sup.D143 L.sub.C469 R.sup.D55 R.sup.D20 L.sub.C661 R.sup.D145 R.sup.D133 L.sub.C86 R.sup.D86 R.sup.D86 L.sub.C278 R.sup.D4 R.sup.D144 L.sub.C470 R.sup.D55 R.sup.D22 L.sub.C662 R.sup.D145 R.sup.D134 L.sub.C87 R.sup.D87 R.sup.D87 L.sub.C279 R.sup.D4 R.sup.D145 L.sub.C471 R.sup.D55 R.sup.D37 L.sub.C663 R.sup.D145 R.sup.C135 L.sub.C88 R.sup.D88 R.sup.D88 L.sub.C280 R.sup.D4 R.sup.D146 L.sub.C472 R.sup.D55 R.sup.D40 L.sub.C664 R.sup.D145 R.sup.D136 L.sub.C89 R.sup.D89 R.sup.D89 L.sub.C281 R.sup.D4 R.sup.D147 L.sub.C473 R.sup.D55 R.sup.D41 L.sub.C665 R.sup.D145 R.sup.D146 L.sub.C90 R.sup.D90 R.sup.D90 L.sub.C282 R.sup.D4 R.sup.D149 L.sub.C474 R.sup.D55 R.sup.D42 L.sub.C666 R.sup.D145 R.sup.D147 L.sub.C91 R.sup.D91 R.sup.D91 L.sub.C283 R.sup.D4 R.sup.D151 L.sub.C475 R.sup.D55 R.sup.D43 L.sub.C667 R.sup.D145 R.sup.D149 L.sub.C92 R.sup.D92 R.sup.D92 L.sub.C284 R.sup.D4 R.sup.D154 L.sub.C476 R.sup.D55 R.sup.D48 L.sub.C668 R.sup.D145 R.sup.D151 L.sub.C93 R.sup.D93 R.sup.D93 L.sub.C285 R.sup.D4 R.sup.D155 L.sub.C477 R.sup.D55 R.sup.D49 L.sub.C669 R.sup.D145 R.sup.D154 L.sub.C94 R.sup.D94 R.sup.D94 L.sub.C286 R.sup.D4 R.sup.D161 L.sub.C478 R.sup.D55 R.sup.D54 L.sub.C670 R.sup.D145 R.sup.D155 L.sub.C95 R.sup.D95 R.sup.D95 L.sub.C287 R.sup.D4 R.sup.D175 L.sub.C479 R.sup.D55 R.sup.D58 L.sub.C671 R.sup.D145 R.sup.D161 L.sub.C96 R.sup.D96 R.sup.D96 L.sub.C288 R.sup.D9 R.sup.D3 L.sub.C480 R.sup.D55 R.sup.D59 L.sub.C672 R.sup.D145 R.sup.D175 L.sub.C97 R.sup.D97 R.sup.D97 L.sub.C289 R.sup.D9 R.sup.D5 L.sub.C481 R.sup.D55 R.sup.D78 L.sub.C673 R.sup.D146 R.sup.D3 L.sub.C98 R.sup.D98 R.sup.D98 L.sub.C290 R.sup.D9 R.sup.D10 L.sub.C482 R.sup.D55 R.sup.D79 L.sub.C674 R.sup.D146 R.sup.D5 L.sub.C99 R.sup.D99 R.sup.D99 L.sub.C291 R.sup.D9 R.sup.D17 L.sub.C483 R.sup.D55 R.sup.D81 L.sub.C675 R.sup.D146 R.sup.D17 L.sub.C100 R.sup.D100 R.sup.D100 L.sub.C292 R.sup.D9 R.sup.D18 L.sub.C484 R.sup.D55 R.sup.D87 L.sub.C676 R.sup.D146 R.sup.D18 L.sub.C101 R.sup.D101 R.sup.D101 L.sub.C293 R.sup.D9 R.sup.D20 L.sub.C485 R.sup.D55 R.sup.D88 L.sub.C677 R.sup.D146 R.sup.D20 L.sub.C102 R.sup.D102 R.sup.D102 L.sub.C294 R.sup.D9 R.sup.D22 L.sub.C486 R.sup.D55 R.sup.D89 L.sub.C678 R.sup.D146 R.sup.D22 L.sub.C103 R.sup.D103 R.sup.D103 L.sub.C295 R.sup.D9 R.sup.D37 L.sub.C487 R.sup.D55 R.sup.D93 L.sub.C679 R.sup.D146 R.sup.D37 L.sub.C104 R.sup.D104 R.sup.D104 L.sub.C296 R.sup.D9 R.sup.D40 L.sub.C488 R.sup.D55 R.sup.D116 L.sub.C680 R.sup.D146 R.sup.D40 L.sub.C105 R.sup.D105 R.sup.D105 L.sub.C297 R.sup.D9 R.sup.D41 L.sub.C489 R.sup.D55 R.sup.D117 L.sub.C681 R.sup.D146 R.sup.D41 L.sub.C106 R.sup.D106 R.sup.D106 L.sub.C298 R.sup.D9 R.sup.D42 L.sub.C490 R.sup.D55 R.sup.D118 L.sub.C682 R.sup.D146 R.sup.D42 L.sub.C107 R.sup.D107 R.sup.D107 L.sub.C299 R.sup.D9 R.sup.D43 L.sub.C491 R.sup.D55 R.sup.D119 L.sub.C683 R.sup.D146 R.sup.D43 L.sub.C108 R.sup.D108 R.sup.D108 L.sub.C300 R.sup.D9 R.sup.D48 L.sub.C492 R.sup.D55 R.sup.D120 L.sub.C684 R.sup.D146 R.sup.D48 L.sub.C109 R.sup.D109 R.sup.D109 L.sub.C301 R.sup.D9 R.sup.D49 L.sub.C493 R.sup.D55 R.sup.D133 L.sub.C685 R.sup.D146 R.sup.D49 L.sub.C110 R.sup.D110 R.sup.D110 L.sub.C302 R.sup.D9 R.sup.D50 L.sub.C494 R.sup.D55 R.sup.D134 L.sub.C686 R.sup.D146 R.sup.D54 L.sub.C111 R.sup.D111 R.sup.D111 L.sub.C303 R.sup.D9 R.sup.D54 L.sub.C495 R.sup.D55 R.sup.D135 L.sub.C687 R.sup.D146 R.sup.D58 L.sub.C112 R.sup.D112 R.sup.D112 L.sub.C304 R.sup.D9 R.sup.D55 L.sub.C496 R.sup.D55 R.sup.D136 L.sub.C688 R.sup.D146 R.sup.D59 L.sub.C113 R.sup.D113 R.sup.D113 L.sub.C305 R.sup.D9 R.sup.D58 L.sub.C497 R.sup.D55 R.sup.D143 L.sub.C689 R.sup.D146 R.sup.D78 L.sub.C114 R.sup.D114 R.sup.D114 L.sub.C306 R.sup.D9 R.sup.D59 L.sub.C498 R.sup.D55 R.sup.D144 L.sub.C690 R.sup.D146 R.sup.D79 L.sub.C115 R.sup.D115 R.sup.D115 L.sub.C307 R.sup.D9 R.sup.D78 L.sub.C499 R.sup.D55 R.sup.D145 L.sub.C691 R.sup.D146 R.sup.D81 L.sub.C116 R.sup.D116 R.sup.D116 L.sub.C308 R.sup.D9 R.sup.D79 L.sub.C500 R.sup.D55 R.sup.D146 L.sub.C692 R.sup.D146 R.sup.D87 L.sub.C117 R.sup.D117 R.sup.D117 L.sub.C309 R.sup.D9 R.sup.D81 L.sub.C501 R.sup.D55 R.sup.D147 L.sub.C693 R.sup.D146 R.sup.D88 L.sub.C118 R.sup.D118 R.sup.D118 L.sub.C310 R.sup.D9 R.sup.D87 L.sub.C502 R.sup.D55 R.sup.D149 L.sub.C694 R.sup.D146 R.sup.D89 L.sub.C119 R.sup.D119 R.sup.D119 L.sub.C311 R.sup.D9 R.sup.D88 L.sub.C503 R.sup.D55 R.sup.D151 L.sub.C695 R.sup.D146 R.sup.D93 L.sub.C120 R.sup.D120 R.sup.D120 L.sub.C312 R.sup.D9 R.sup.D89 L.sub.C504 R.sup.D55 R.sup.D154 L.sub.C696 R.sup.D146 R.sup.D117 L.sub.C121 R.sup.D121 R.sup.D121 L.sub.C313 R.sup.D9 R.sup.D93 L.sub.C505 R.sup.D55 R.sup.D155 L.sub.C697 R.sup.D146 R.sup.D118 L.sub.C122 R.sup.D122 R.sup.D122 L.sub.C314 R.sup.D9 R.sup.D116 L.sub.C506 R.sup.D55 R.sup.D161 L.sub.C698 R.sup.D146 R.sup.D119 L.sub.C123 R.sup.D123 R.sup.D123 L.sub.C315 R.sup.D9 R.sup.D117 L.sub.C507 R.sup.D55 R.sup.D175 L.sub.C699 R.sup.D146 R.sup.D120 L.sub.C124 R.sup.D124 R.sup.D124 L.sub.C316 R.sup.D9 R.sup.D118 L.sub.C508 R.sup.D116 R.sup.D3 L.sub.C700 R.sup.D146 R.sup.D133 L.sub.C125 R.sup.D125 R.sup.D125 L.sub.C317 R.sup.D9 R.sup.D119 L.sub.C509 R.sup.D116 R.sup.D5 L.sub.C701 R.sup.D146 R.sup.D134 L.sub.C126 R.sup.D126 R.sup.D126 L.sub.C318 R.sup.D9 R.sup.D120 L.sub.C510 R.sup.D116 R.sup.D17 L.sub.C702 R.sup.D146 R.sup.D135 L.sub.C127 R.sup.D127 R.sup.D127 L.sub.C319 R.sup.D9 R.sup.D133 L.sub.C511 R.sup.D116 R.sup.D18 L.sub.C703 R.sup.D146 R.sup.D136 L.sub.C128 R.sup.D128 R.sup.D128 L.sub.C320 R.sup.D9 R.sup.D134 L.sub.C512 R.sup.D116 R.sup.D20 L.sub.C704 R.sup.D146 R.sup.D146 L.sub.C129 R.sup.D129 R.sup.D129 L.sub.C321 R.sup.D9 R.sup.D135 L.sub.C513 R.sup.D116 R.sup.D22 L.sub.C705 R.sup.D146 R.sup.D147 L.sub.C130 R.sup.D130 R.sup.D130 L.sub.C322 R.sup.D9 R.sup.D136 L.sub.C514 R.sup.D116 R.sup.D37 L.sub.C706 R.sup.D146 R.sup.D149 L.sub.C131 R.sup.D131 R.sup.D131 L.sub.C323 R.sup.D9 R.sup.D143 L.sub.C515 R.sup.D116 R.sup.D40 L.sub.C707 R.sup.D146 R.sup.D151 L.sub.C132 R.sup.D132 R.sup.D132 L.sub.C324 R.sup.D9 R.sup.D144 L.sub.C516 R.sup.D116 R.sup.D41 L.sub.C708 R.sup.D146 R.sup.D154 L.sub.C133 R.sup.D133 R.sup.D133 L.sub.C325 R.sup.D9 R.sup.D145 L.sub.C517 R.sup.D116 R.sup.D42 L.sub.C709 R.sup.D146 R.sup.D155 L.sub.C134 R.sup.D134 R.sup.D134 L.sub.C326 R.sup.D9 R.sup.D146 L.sub.C518 R.sup.D116 R.sup.D43 L.sub.C710 R.sup.D146 R.sup.D161 L.sub.C135 R.sup.D135 R.sup.D135 L.sub.C327 R.sup.D9 R.sup.D147 L.sub.C519 R.sup.D116 R.sup.D48 L.sub.C711 R.sup.D146 R.sup.D175 L.sub.C136 R.sup.D136 R.sup.D136 L.sub.C328 R.sup.D9 R.sup.D149 L.sub.C520 R.sup.D116 R.sup.D49 L.sub.C712 R.sup.D133 R.sup.D3 L.sub.C137 R.sup.D137 R.sup.D137 L.sub.C329 R.sup.D9 R.sup.D151 L.sub.C521 R.sup.D116 R.sup.D54 L.sub.C713 R.sup.D133 R.sup.D5 L.sub.C138 R.sup.D138 R.sup.D138 L.sub.C330 R.sup.D9 R.sup.D154 L.sub.C522 R.sup.D116 R.sup.D58 L.sub.C714 R.sup.D133 R.sup.D3 L.sub.C139 R.sup.D139 R.sup.D139 L.sub.C331 R.sup.D9 R.sup.D155 L.sub.C523 R.sup.D116 R.sup.D59 L.sub.C715 R.sup.D133 R.sup.D18 L.sub.C140 R.sup.D140 R.sup.D140 L.sub.C332 R.sup.D9 R.sup.D161 L.sub.C524 R.sup.D116 R.sup.D78 L.sub.C716 R.sup.D133 R.sup.D20 L.sub.C141 R.sup.D141 R.sup.D141 L.sub.C333 R.sup.D9 R.sup.D175 L.sub.C525 R.sup.D116 R.sup.D79 L.sub.C717 R.sup.D133 R.sup.D22 L.sub.C142 R.sup.D142 R.sup.D142 L.sub.C334 R.sup.D10 R.sup.D3 L.sub.C526 R.sup.D116 R.sup.D81 L.sub.C718 R.sup.D133 R.sup.D37 L.sub.C143 R.sup.D143 R.sup.D143 L.sub.C335 R.sup.D10 R.sup.D5 L.sub.C527 R.sup.D116 R.sup.D87 L.sub.C719 R.sup.D133 R.sup.D40 L.sub.C144 R.sup.D144 R.sup.D144 L.sub.C336 R.sup.D10 R.sup.D17 L.sub.C528 R.sup.D116 R.sup.D88 L.sub.C720 R.sup.D133 R.sup.D41 L.sub.C145 R.sup.D145 R.sup.D145 L.sub.C337 R.sup.D10 R.sup.D18 L.sub.C529 R.sup.D116 R.sup.D89 L.sub.C721 R.sup.D133 R.sup.D42 L.sub.C146 R.sup.D146 R.sup.D146 L.sub.C338 R.sup.D10 R.sup.D20 L.sub.C530 R.sup.D116 R.sup.D93 L.sub.C722 R.sup.D133 R.sup.D43 L.sub.C147 R.sup.D147 R.sup.D147 L.sub.C339 R.sup.D10 R.sup.D22 L.sub.C531 R.sup.D116 R.sup.D117 L.sub.C723 R.sup.D133 R.sup.D48 L.sub.C148 R.sup.D148 R.sup.D148 L.sub.C340 R.sup.D10 R.sup.D37 L.sub.C532 R.sup.D116 R.sup.D118 L.sub.C724 R.sup.D133 R.sup.D49 L.sub.C149 R.sup.D149 R.sup.D149 L.sub.C341 R.sup.D10 R.sup.D40 L.sub.C533 R.sup.D116 R.sup.D119 L.sub.C725 R.sup.D133 R.sup.D54 L.sub.C150 R.sup.D150 R.sup.D150 L.sub.C342 R.sup.D10 R.sup.D41 L.sub.C534 R.sup.D116 R.sup.D120 L.sub.C726 R.sup.D133 R.sup.D58 L.sub.C151 R.sup.D151 R.sup.D151 L.sub.C343 R.sup.D10 R.sup.D42 L.sub.C535 R.sup.D116 R.sup.D133 L.sub.C727 R.sup.D133 R.sup.D59 L.sub.C152 R.sup.D152 R.sup.D152 L.sub.C344 R.sup.D10 R.sup.D43 L.sub.C536 R.sup.D116 R.sup.D134 L.sub.C728 R.sup.D133 R.sup.D78 L.sub.C153 R.sup.D153 R.sup.D153 L.sub.C345 R.sup.D10 R.sup.D48 L.sub.C537 R.sup.D116 R.sup.D135 L.sub.C729 R.sup.D133 R.sup.D79 L.sub.C154 R.sup.D154 R.sup.D154 L.sub.C346 R.sup.D10 R.sup.D49 L.sub.C538 R.sup.D116 R.sup.D136 L.sub.C730 R.sup.D133 R.sup.D81 L.sub.C155 R.sup.D155 R.sup.D155 L.sub.C347 R.sup.D10 R.sup.D50 L.sub.C539 R.sup.D116 R.sup.D143 L.sub.C731 R.sup.D133 R.sup.D87 L.sub.C156 R.sup.D156 R.sup.D156 L.sub.C348 R.sup.D10 R.sup.D54 L.sub.C540 R.sup.D116 R.sup.D144 L.sub.C732 R.sup.D133 R.sup.D88 L.sub.C157 R.sup.D157 R.sup.D157 L.sub.C349 R.sup.D10 R.sup.D55 L.sub.C541 R.sup.D116 R.sup.D145 L.sub.C733 R.sup.D133 R.sup.D89 L.sub.C158 R.sup.D158 R.sup.D158 L.sub.C350 R.sup.D10 R.sup.D58 L.sub.C542 R.sup.D116 R.sup.D146 L.sub.C734 R.sup.D133 R.sup.D93 L.sub.C159 R.sup.D159 R.sup.D159 L.sub.C351 R.sup.D10 R.sup.D59 L.sub.C543 R.sup.D116 R.sup.D147 L.sub.C735 R.sup.D133 R.sup.D117 L.sub.C160 R.sup.D160 R.sup.D160 L.sub.C352 R.sup.D10 R.sup.D78 L.sub.C544 R.sup.D116 R.sup.D149 L.sub.C736 R.sup.D133 R.sup.D118 L.sub.C161 R.sup.D161 R.sup.D161 L.sub.C353 R.sup.D10 R.sup.D79 L.sub.C545 R.sup.D116 R.sup.D151 L.sub.C737 R.sup.D133 R.sup.D119 L.sub.C162 R.sup.D162 R.sup.D162 L.sub.C354 R.sup.D10 R.sup.D81 L.sub.C546 R.sup.D116 R.sup.D154 L.sub.C738 R.sup.D133 R.sup.D120 L.sub.C163 R.sup.D163 R.sup.D163 L.sub.C355 R.sup.D10 R.sup.D87 L.sub.C547 R.sup.D116 R.sup.D155 L.sub.C739 R.sup.D133 R.sup.D133 L.sub.C164 R.sup.D164 R.sup.D164 L.sub.C356 R.sup.D10 R.sup.D88 L.sub.C548 R.sup.D116 R.sup.D161 L.sub.C740 R.sup.D133 R.sup.D134 L.sub.C165 R.sup.D165 R.sup.D165 L.sub.C357 R.sup.D10 R.sup.D89 L.sub.C549 R.sup.D116 R.sup.D175 L.sub.C741 R.sup.D133 R.sup.D135 L.sub.C166 R.sup.D166 R.sup.D166 L.sub.C358 R.sup.D10 R.sup.D93 L.sub.C550 R.sup.D143 R.sup.D3 L.sub.C742 R.sup.D133 R.sup.D136 L.sub.C167 R.sup.D167 R.sup.D167 L.sub.C359 R.sup.D10 R.sup.D116 L.sub.C551 R.sup.D143 R.sup.D5 L.sub.C743 R.sup.D133 R.sup.D146 L.sub.C168 R.sup.D168 R.sup.D168 L.sub.C360 R.sup.D10 R.sup.D117 L.sub.C552 R.sup.D143 R.sup.D17 L.sub.C744 R.sup.D133 R.sup.D147 L.sub.C169 R.sup.D169 R.sup.D169 L.sub.C361 R.sup.D10 R.sup.D118 L.sub.C553 R.sup.D143 R.sup.D18 L.sub.C745 R.sup.D133 R.sup.D149 L.sub.C170 R.sup.D170 R.sup.D170 L.sub.C362 R.sup.D10 R.sup.D119 L.sub.C554 R.sup.D143 R.sup.D20 L.sub.C746 R.sup.D133 R.sup.D151 L.sub.C171 R.sup.D171 R.sup.D171 L.sub.C363 R.sup.D10 R.sup.D120 L.sub.C555 R.sup.D143 R.sup.D22 L.sub.C747 R.sup.D133 R.sup.D154 L.sub.C172 R.sup.D172 R.sup.D172 L.sub.C364 R.sup.D10 R.sup.D133 L.sub.C556 R.sup.D143 R.sup.D37 L.sub.C748 R.sup.D133 R.sup.D155 L.sub.C173 R.sup.D173 R.sup.D173 L.sub.C365 R.sup.D10 R.sup.D134 L.sub.C557 R.sup.D143 R.sup.D40 L.sub.C749 R.sup.D133 R.sup.D161 L.sub.C174 R.sup.D174 R.sup.D174 L.sub.C366 R.sup.D10 R.sup.D135 L.sub.C558 R.sup.D143 R.sup.D41 L.sub.C750 R.sup.D133 R.sup.D175 L.sub.C175 R.sup.D175 R.sup.D175 L.sub.C367 R.sup.D10 R.sup.D136 L.sub.C559 R.sup.D143 R.sup.D42 L.sub.C751 R.sup.D175 R.sup.D3 L.sub.C176 R.sup.D176 R.sup.D176 L.sub.C368 R.sup.D10 R.sup.D143 L.sub.C560 R.sup.D143 R.sup.D43 L.sub.C752 R.sup.D175 R.sup.D5 L.sub.C177 R.sup.D177 R.sup.D177 L.sub.C369 R.sup.D10 R.sup.D144 L.sub.C561 R.sup.D143 R.sup.D48 L.sub.C753 R.sup.D175 R.sup.D18 L.sub.C178 R.sup.D178 R.sup.D178 L.sub.C370 R.sup.D10 R.sup.D145 L.sub.C562 R.sup.D143 R.sup.D49 L.sub.C754 R.sup.D175 R.sup.D20 L.sub.C179 R.sup.D179 R.sup.D179 L.sub.C371 R.sup.D10 R.sup.D146 L.sub.C563 R.sup.D143 R.sup.D54 L.sub.C755 R.sup.D175 R.sup.D22 L.sub.C180 R.sup.D180 R.sup.D180 L.sub.C372 R.sup.D10 R.sup.D147 L.sub.C564 R.sup.D143 R.sup.D58 L.sub.C756 R.sup.D175 R.sup.D37 L.sub.C181 R.sup.D181 R.sup.D181 L.sub.C373 R.sup.D10 R.sup.D149 L.sub.C565 R.sup.D143 R.sup.D59 L.sub.C757 R.sup.D175 R.sup.D40 L.sub.C182 R.sup.D182 R.sup.D182 L.sub.C374 R.sup.D10 R.sup.D151 L.sub.C566 R.sup.D143 R.sup.D78 L.sub.C758 R.sup.D175 R.sup.D41 L.sub.C183 R.sup.D183 R.sup.D183 L.sub.C375 R.sup.D10 R.sup.D154 L.sub.C567 R.sup.D143 R.sup.D79 L.sub.C759 R.sup.D175 R.sup.D42 L.sub.C184 R.sup.D184 R.sup.D184 L.sub.C376 R.sup.D10 R.sup.D155 L.sub.C568 R.sup.D143 R.sup.D81 L.sub.C760 R.sup.D175 R.sup.D43 L.sub.C185 R.sup.D185 R.sup.D185 L.sub.C377 R.sup.D10 R.sup.D161 L.sub.C569 R.sup.D143 R.sup.D87 L.sub.C761 R.sup.D175 R.sup.D48 L.sub.C186 R.sup.D186 R.sup.D186 L.sub.C378 R.sup.D10 R.sup.D175 L.sub.C570 R.sup.D143 R.sup.D88 L.sub.C762 R.sup.D175 R.sup.D49 L.sub.C187 R.sup.D187 R.sup.D187 L.sub.C379 R.sup.D17 R.sup.D3 L.sub.C571 R.sup.D143 R.sup.D89 L.sub.C763 R.sup.D175 R.sup.D54 L.sub.C188 R.sup.D188 R.sup.D188 L.sub.C380 R.sup.D17 R.sup.D5 L.sub.C572 R.sup.D143 R.sup.D93 L.sub.C764 R.sup.D175 R.sup.D58 L.sub.C189 R.sup.D189 R.sup.D189 L.sub.C381 R.sup.D17 R.sup.D18 L.sub.C573 R.sup.D143 R.sup.D116 L.sub.C765 R.sup.D175 R.sup.D59 L.sub.C190 R.sup.D190 R.sup.D190 L.sub.C382 R.sup.D17 R.sup.D20 L.sub.C574 R.sup.D143 R.sup.D117 L.sub.C766 R.sup.D175 R.sup.D78 L.sub.C191 R.sup.D191 R.sup.D191 L.sub.C383 R.sup.D17 R.sup.D22 L.sub.C575 R.sup.D143 R.sup.D118 L.sub.C767 R.sup.D175 R.sup.D79 L.sub.C192 R.sup.D192 R.sup.D192 L.sub.C384 R.sup.D17 R.sup.D37 L.sub.C576 R.sup.D143 R.sup.D119 L.sub.C768 R.sup.D175 R.sup.D81 L.sub.C769 R.sup.D193 R.sup.D193 L.sub.C877 R.sup.D1 R.sup.D193 L.sub.C985 R.sup.D4 R.sup.D193 L.sub.C1093 R.sup.D9 R.sup.D193 L.sub.C770 R.sup.D194 R.sup.D194 L.sub.C878 R.sup.D1 R.sup.D194 L.sub.C986 R.sup.D4 R.sup.D194 L.sub.C1094 R.sup.D9 R.sup.D194 L.sub.C771 R.sup.D195 R.sup.D195 L.sub.C879 R.sup.D1 R.sup.D195 L.sub.C987 R.sup.D4 R.sup.D195 L.sub.C1095 R.sup.D9 R.sup.D195 L.sub.C772 R.sup.D196 R.sup.D196 L.sub.C880 R.sup.D1 R.sup.D196 L.sub.C988 R.sup.D4 R.sup.D196 L.sub.C1096 R.sup.D9 R.sup.D196 L.sub.C773 R.sup.D197 R.sup.D197 L.sub.C881 R.sup.D1 R.sup.D197 L.sub.C989 R.sup.D4 R.sup.D197 L.sub.C1097 R.sup.D9 R.sup.D197 L.sub.C774 R.sup.D198 R.sup.D198 L.sub.C882 R.sup.D1 R.sup.D198 L.sub.C990 R.sup.D4 R.sup.D198 L.sub.C1098 R.sup.D9 R.sup.D198 L.sub.C775 R.sup.D199 R.sup.D199 L.sub.C883 R.sup.D1 R.sup.D199 L.sub.C991 R.sup.D4 R.sup.D199 L.sub.C1099 R.sup.D9 R.sup.D199 L.sub.C776 R.sup.D200 R.sup.D200 L.sub.C884 R.sup.D1 R.sup.D200 L.sub.C992 R.sup.D4 R.sup.D200 L.sub.C1100 R.sup.D9 R.sup.D200 L.sub.C777 R.sup.D201 R.sup.D201 L.sub.C885 R.sup.D1 R.sup.D201 L.sub.C993 R.sup.D4 R.sup.D201 L.sub.C1101 R.sup.D9 R.sup.D201 L.sub.C778 R.sup.D202 R.sup.D202 L.sub.C886 R.sup.D1 R.sup.D202 L.sub.C994 R.sup.D4 R.sup.D202 L.sub.C1102 R.sup.D9 R.sup.D202 L.sub.C779 R.sup.D203 R.sup.D203 L.sub.C887 R.sup.D1 R.sup.D203 L.sub.C995 R.sup.D4 R.sup.D203 L.sub.C1103 R.sup.D9 R.sup.D203 L.sub.C780 R.sup.D204 R.sup.D204 L.sub.C888 R.sup.D1 R.sup.D204 L.sub.C996 R.sup.D4 R.sup.D204 L.sub.C1104 R.sup.D9 R.sup.D204 L.sub.C781 R.sup.D205 R.sup.D205 L.sub.C889 R.sup.D1 R.sup.D205 L.sub.C997 R.sup.D4 R.sup.D205 L.sub.C1105 R.sup.D9 R.sup.D205 L.sub.C782 R.sup.D206 R.sup.D206 L.sub.C890 R.sup.D1 R.sup.D206 L.sub.C998 R.sup.D4 R.sup.D206 L.sub.C1106 R.sup.D9 R.sup.D206 L.sub.C783 R.sup.D207 R.sup.D207 L.sub.C891 R.sup.D1 R.sup.D207 L.sub.C999 R.sup.D4 R.sup.D207 L.sub.C1107 R.sup.D9 R.sup.D207 L.sub.C784 R.sup.D208 R.sup.D208 L.sub.C892 R.sup.D1 R.sup.D208 L.sub.C1000 R.sup.D4 R.sup.D208 L.sub.C1108 R.sup.D9 R.sup.D208 L.sub.C785 R.sup.D209 R.sup.D209 L.sub.C893 R.sup.D1 R.sup.D209 L.sub.C1001 R.sup.D4 R.sup.D209 L.sub.C1109 R.sup.D9 R.sup.D209 L.sub.C786 R.sup.D210 R.sup.D210 L.sub.C894 R.sup.D1 R.sup.D210 L.sub.C1002 R.sup.D4 R.sup.D210 L.sub.C1110 R.sup.D9 R.sup.D210 L.sub.C787 R.sup.D211 R.sup.D211 L.sub.C895 R.sup.D1 R.sup.D211 L.sub.C1003 R.sup.D4 R.sup.D211 L.sub.C1111 R.sup.D9 R.sup.D211 L.sub.C788 R.sup.D212 R.sup.D212 L.sub.C896 R.sup.D1 R.sup.D212 L.sub.C1004 R.sup.D4 R.sup.D212 L.sub.C1112 R.sup.D9 R.sup.D212 L.sub.C789 R.sup.D213 R.sup.D213 L.sub.C897 R.sup.D1 R.sup.D213 L.sub.C1005 R.sup.D4 R.sup.D213 L.sub.C1113 R.sup.D9 R.sup.D213 L.sub.C790 R.sup.D214 R.sup.D214 L.sub.C898 R.sup.D1 R.sup.D214 L.sub.C1006 R.sup.D4 R.sup.D214 L.sub.C1114 R.sup.D9 R.sup.D214 L.sub.C791 R.sup.D215 R.sup.D215 L.sub.C899 R.sup.D1 R.sup.D215 L.sub.C1007 R.sup.D4 R.sup.D215 L.sub.C1115 R.sup.D9 R.sup.D215 L.sub.C792 R.sup.D216 R.sup.D216 L.sub.C900 R.sup.D1 R.sup.D216 L.sub.C1008 R.sup.D4 R.sup.D216 L.sub.C1116 R.sup.D9 R.sup.D216 L.sub.C793 R.sup.D217 R.sup.D217 L.sub.C901 R.sup.D1 R.sup.D217 L.sub.C1009 R.sup.D4 R.sup.D217 L.sub.C1117 R.sup.D9 R.sup.D217 L.sub.C794 R.sup.D218 R.sup.D218 L.sub.C902 R.sup.D1 R.sup.D218 L.sub.C1010 R.sup.D4 R.sup.D218 L.sub.C1118 R.sup.D9 R.sup.D218 L.sub.C795 R.sup.D219 R.sup.D219 L.sub.C903 R.sup.D1 R.sup.D219 L.sub.C1011 R.sup.D4 R.sup.D219 L.sub.C1119 R.sup.D9 R.sup.D219 L.sub.C796 R.sup.D220 R.sup.D220 L.sub.C904 R.sup.D1 R.sup.D220 L.sub.C1012 R.sup.D4 R.sup.D220 L.sub.C1120 R.sup.D9 R.sup.D220 L.sub.C797 R.sup.D221 R.sup.D221 L.sub.C905 R.sup.D1 R.sup.D221 L.sub.C1013 R.sup.D4 R.sup.D221 L.sub.C1121 R.sup.D9 R.sup.D221 L.sub.C798 R.sup.D222 R.sup.D222 L.sub.C906 R.sup.D1 R.sup.D222 L.sub.C1014 R.sup.D4 R.sup.D222 L.sub.C1122 R.sup.D9 R.sup.D222 L.sub.C799 R.sup.D223 R.sup.D223 L.sub.C907 R.sup.D1 R.sup.D223 L.sub.C1015 R.sup.D4 R.sup.D223 L.sub.C1123 R.sup.D9 R.sup.D223 L.sub.C800 R.sup.D224 R.sup.D224 L.sub.C908 R.sup.D1 R.sup.D224 L.sub.C1016 R.sup.D4 R.sup.D224 L.sub.C1124 R.sup.D9 R.sup.D224 L.sub.C801 R.sup.D225 R.sup.D225 L.sub.C909 R.sup.D1 R.sup.D225 L.sub.C1017 R.sup.D4 R.sup.D225 L.sub.C1125 R.sup.D9 R.sup.D225 L.sub.C802 R.sup.D226 R.sup.D226 L.sub.C910 R.sup.D1 R.sup.D226 L.sub.C1018 R.sup.D4 R.sup.D226 L.sub.C1126 R.sup.D9 R.sup.D226 L.sub.C803 R.sup.D227 R.sup.D227 L.sub.C911 R.sup.D1 R.sup.D227 L.sub.C1019 R.sup.D4 R.sup.D227 L.sub.C1127 R.sup.D9 R.sup.D227 L.sub.C804 R.sup.D228 R.sup.D228 L.sub.C912 R.sup.D1 R.sup.D228 L.sub.C1020 R.sup.D4 R.sup.D228 L.sub.C1128 R.sup.D9 R.sup.D228 L.sub.C805 R.sup.D229 R.sup.D229 L.sub.C913 R.sup.D1 R.sup.D229 L.sub.C1021 R.sup.D4 R.sup.D229 L.sub.C1129 R.sup.D9 R.sup.D229 L.sub.C806 R.sup.D230 R.sup.D230 L.sub.C914 R.sup.D1 R.sup.D230 L.sub.C1022 R.sup.D4 R.sup.D230 L.sub.C1130 R.sup.D9 R.sup.D230 L.sub.C807 R.sup.D231 R.sup.D231 L.sub.C915 R.sup.D1 R.sup.D231 L.sub.C1023 R.sup.D4 R.sup.D231 L.sub.C1131 R.sup.D9 R.sup.D231 L.sub.C808 R.sup.D232 R.sup.D232 L.sub.C916 R.sup.D1 R.sup.D232 L.sub.C1024 R.sup.D4 R.sup.D232 L.sub.C1132 R.sup.D9 R.sup.D232 L.sub.C809 R.sup.D233 R.sup.D233 L.sub.C917 R.sup.D1 R.sup.D233 L.sub.C1025 R.sup.D4 R.sup.D233 L.sub.C1133 R.sup.D9 R.sup.D233 L.sub.C810 R.sup.D234 R.sup.D234 L.sub.C918 R.sup.D1 R.sup.D234 L.sub.C1026 R.sup.D4 R.sup.D234 L.sub.C1134 R.sup.D9 R.sup.D234 L.sub.C811 R.sup.D235 R.sup.D235 L.sub.C919 R.sup.D1 R.sup.D235 L.sub.C1027 R.sup.D4 R.sup.D235 L.sub.C1135 R.sup.D9 R.sup.D235 L.sub.C812 R.sup.D236 R.sup.D236 L.sub.C920 R.sup.D1 R.sup.D236 L.sub.C1028 R.sup.D4 R.sup.D236 L.sub.C1136 R.sup.D9 R.sup.D236 L.sub.C813 R.sup.D237 R.sup.D237 L.sub.C921 R.sup.D1 R.sup.D237 L.sub.C1029 R.sup.D4 R.sup.D237 L.sub.C1137 R.sup.D9 R.sup.D237 L.sub.C814 R.sup.D238 R.sup.D238 L.sub.C922 R.sup.D1 R.sup.D238 L.sub.C1030 R.sup.D4 R.sup.D238 L.sub.C1138 R.sup.D9 R.sup.D238 L.sub.C815 R.sup.D239 R.sup.D239 L.sub.C923 R.sup.D1 R.sup.D239 L.sub.C1031 R.sup.D4 R.sup.D239 L.sub.C1139 R.sup.D9 R.sup.D239 L.sub.C816 R.sup.D240 R.sup.D240 L.sub.C924 R.sup.D1 R.sup.D240 L.sub.C1032 R.sup.D4 R.sup.D240 L.sub.C1140 R.sup.D9 R.sup.D240 L.sub.C817 R.sup.D241 R.sup.D241 L.sub.C925 R.sup.D1 R.sup.D241 L.sub.C1033 R.sup.D4 R.sup.D241 L.sub.C1141 R.sup.D9 R.sup.D241 L.sub.C818 R.sup.D242 R.sup.D242 L.sub.C926 R.sup.D1 R.sup.D242 L.sub.C1034 R.sup.D4 R.sup.D242 L.sub.C1142 R.sup.D9 R.sup.D242 L.sub.C819 R.sup.D243 R.sup.D243 L.sub.C927 R.sup.D1 R.sup.D243 L.sub.C1035 R.sup.D4 R.sup.D243 L.sub.C1143 R.sup.D9 R.sup.D243 L.sub.C820 R.sup.D244 R.sup.D244 L.sub.C928 R.sup.D1 R.sup.D244 L.sub.C1036 R.sup.D4 R.sup.D244 L.sub.C1144 R.sup.D9 R.sup.D244 L.sub.C821 R.sup.D245 R.sup.D245 L.sub.C929 R.sup.D1 R.sup.D245 L.sub.C1037 R.sup.D4 R.sup.D245 L.sub.C1145 R.sup.D9 R.sup.D245 L.sub.C822 R.sup.D246 R.sup.D246 L.sub.C930 R.sup.D1 R.sup.D246 L.sub.C1038 R.sup.D4 R.sup.D246 L.sub.C1146 R.sup.D9 R.sup.D246 L.sub.C823 R.sup.D17 R.sup.D193 L.sub.C931 R.sup.D50 R.sup.D193 L.sub.C1039 R.sup.D145 R.sup.D193 L.sub.C1147 R.sup.D168 R.sup.D193 L.sub.C824 R.sup.D17 R.sup.D194 L.sub.C932 R.sup.D50 R.sup.D194 L.sub.C1040 R.sup.D145 R.sup.D194 L.sub.C1148 R.sup.D168 R.sup.D194 L.sub.C825 R.sup.D17 R.sup.D195 L.sub.C933 R.sup.D50 R.sup.D195 L.sub.C1041 R.sup.D145 R.sup.D195 L.sub.C1149 R.sup.D168 R.sup.D195 L.sub.C826 R.sup.D17 R.sup.D196 L.sub.C934 R.sup.D50 R.sup.D196 L.sub.C1042 R.sup.D145 R.sup.D196 L.sub.C1150 R.sup.D168 R.sup.D196 L.sub.C827 R.sup.D17 R.sup.D197 L.sub.C935 R.sup.D50 R.sup.D197 L.sub.C1043 R.sup.D145 R.sup.D197 L.sub.C1151 R.sup.D168 R.sup.D197 L.sub.C828 R.sup.D17 R.sup.D198 L.sub.C936 R.sup.D50 R.sup.D198 L.sub.C1044 R.sup.D145 R.sup.D198 L.sub.C1152 R.sup.D168 R.sup.D198 L.sub.C829 R.sup.D17 R.sup.D199 L.sub.C937 R.sup.D50 R.sup.D199 L.sub.C1045 R.sup.D145 R.sup.D199 L.sub.C1153 R.sup.D168 R.sup.D199 L.sub.C830 R.sup.D17 R.sup.D200 L.sub.C938 R.sup.D50 R.sup.D200 L.sub.C1046 R.sup.D145 R.sup.D200 L.sub.C1154 R.sup.D168 R.sup.D200 L.sub.C831 R.sup.D17 R.sup.D201 L.sub.C939 R.sup.D50 R.sup.D201 L.sub.C1047 R.sup.D145 R.sup.D201 L.sub.C1155 R.sup.D168 R.sup.D201 L.sub.C832 R.sup.D17 R.sup.D202 L.sub.C940 R.sup.D50 R.sup.D202 L.sub.C1048 R.sup.D145 R.sup.D202 L.sub.C1156 R.sup.D168 R.sup.D202 L.sub.C833 R.sup.D17 R.sup.D203 L.sub.C941 R.sup.D50 R.sup.D203 L.sub.C1049 R.sup.D145 R.sup.D203 L.sub.C1157 R.sup.D168 R.sup.D203 L.sub.C834 R.sup.D17 R.sup.D204 L.sub.C942 R.sup.D50 R.sup.D204 L.sub.C1050 R.sup.D145 R.sup.D204 L.sub.C1158 R.sup.D168 R.sup.D204 L.sub.C835 R.sup.D17 R.sup.D205 L.sub.C943 R.sup.D50 R.sup.D205 L.sub.C1051 R.sup.D145 R.sup.D205 L.sub.C1159 R.sup.D168 R.sup.D205 L.sub.C836 R.sup.D17 R.sup.D206 L.sub.C944 R.sup.D50 R.sup.D206 L.sub.C1052 R.sup.D145 R.sup.D206 L.sub.C1160 R.sup.D168 R.sup.D206 L.sub.C837 R.sup.D17 R.sup.D207 L.sub.C945 R.sup.D50 R.sup.D207 L.sub.C1053 R.sup.D145 R.sup.D207 L.sub.C1161 R.sup.D168 R.sup.D207 L.sub.C838 R.sup.D17 R.sup.D208 L.sub.C946 R.sup.D50 R.sup.D208 L.sub.C1054 R.sup.D145 R.sup.D208 L.sub.C1162 R.sup.D168 R.sup.D208 L.sub.C839 R.sup.D17 R.sup.D209 L.sub.C947 R.sup.D50 R.sup.D209 L.sub.C1055 R.sup.D145 R.sup.D209 L.sub.C1163 R.sup.D168 R.sup.D209 L.sub.C840 R.sup.D17 R.sup.D210 L.sub.C948 R.sup.D50 R.sup.D210 L.sub.C1056 R.sup.D145 R.sup.D210 L.sub.C1164 R.sup.D168 R.sup.D210 L.sub.C841 R.sup.D17 R.sup.D211 L.sub.C949 R.sup.D50 R.sup.D211 L.sub.C1057 R.sup.D145 R.sup.D211 L.sub.C1165 R.sup.D168 R.sup.D211 L.sub.C842 R.sup.D17 R.sup.D212 L.sub.C950 R.sup.D50 R.sup.D212 L.sub.C1058 R.sup.D145 R.sup.D212 L.sub.C1166 R.sup.D168 R.sup.D212 L.sub.C843 R.sup.D17 R.sup.D213 L.sub.C951 R.sup.D50 R.sup.D213 L.sub.C1059 R.sup.D145 R.sup.D213 L.sub.C1167 R.sup.D168 R.sup.D213 L.sub.C844 R.sup.D17 R.sup.D214 L.sub.C952 R.sup.D50 R.sup.D214 L.sub.C1060 R.sup.D145 R.sup.D214 L.sub.C1168 R.sup.D168 R.sup.D214 L.sub.C845 R.sup.D17 R.sup.D215 L.sub.C953 R.sup.D50 R.sup.D215 L.sub.C1061 R.sup.D145 R.sup.D215 L.sub.C1169 R.sup.D168 R.sup.D215 L.sub.C846 R.sup.D17 R.sup.D216 L.sub.C954 R.sup.D50 R.sup.D216 L.sub.C1062 R.sup.D145 R.sup.D216 L.sub.C1170 R.sup.D168 R.sup.D216 L.sub.C847 R.sup.D17 R.sup.D217 L.sub.C955 R.sup.D50 R.sup.D217 L.sub.C1063 R.sup.D145 R.sup.D217 L.sub.C1171 R.sup.D168 R.sup.D217 L.sub.C848 R.sup.D17 R.sup.D218 L.sub.C956 R.sup.D50 R.sup.D218 L.sub.C1064 R.sup.D145 R.sup.D218 L.sub.C1172 R.sup.D168 R.sup.D218 L.sub.C849 R.sup.D17 R.sup.D219 L.sub.C957 R.sup.D50 R.sup.D219 L.sub.C1065 R.sup.D145 R.sup.D219 L.sub.C1173 R.sup.D168 R.sup.D219 L.sub.C850 R.sup.D17 R.sup.D220 L.sub.C958 R.sup.D50 R.sup.D220 L.sub.C1066 R.sup.D145 R.sup.D220 L.sub.C1174 R.sup.D168 R.sup.D220 L.sub.C851 R.sup.D17 R.sup.D221 L.sub.C959 R.sup.D50 R.sup.D221 L.sub.C1067 R.sup.D145 R.sup.D221 L.sub.C1175 R.sup.D168 R.sup.D221 L.sub.C852 R.sup.D17 R.sup.D222 L.sub.C960 R.sup.D50 R.sup.D222 L.sub.C1068 R.sup.D145 R.sup.D222 L.sub.C1176 R.sup.D168 R.sup.D222 L.sub.C853 R.sup.D17 R.sup.D223 L.sub.C961 R.sup.D50 R.sup.D223 L.sub.C1069 R.sup.D145 R.sup.D223 L.sub.C1177 R.sup.D168 R.sup.D223 L.sub.C854 R.sup.D17 R.sup.D224 L.sub.C962 R.sup.D50 R.sup.D224 L.sub.C1070 R.sup.D145 R.sup.D224 L.sub.C1178 R.sup.D168 R.sup.D224 L.sub.C855 R.sup.D17 R.sup.D225 L.sub.C963 R.sup.D50 R.sup.D225 L.sub.C1071 R.sup.D145 R.sup.D225 L.sub.C1179 R.sup.D168 R.sup.D225 L.sub.C856 R.sup.D17 R.sup.D226 L.sub.C964 R.sup.D50 R.sup.D226 L.sub.C1072 R.sup.D145 R.sup.D226 L.sub.C1180 R.sup.D168 R.sup.D226 L.sub.C857 R.sup.D17 R.sup.D227 L.sub.C965 R.sup.D50 R.sup.D227 L.sub.C1073 R.sup.D145 R.sup.D227 L.sub.C1181 R.sup.D168 R.sup.D227 L.sub.C858 R.sup.D17 R.sup.D228 L.sub.C966 R.sup.D50 R.sup.D228 L.sub.C1074 R.sup.D145 R.sup.D228 L.sub.C1182 R.sup.D168 R.sup.D228 L.sub.C859 R.sup.D17 R.sup.D229 L.sub.C967 R.sup.D50 R.sup.D229 L.sub.C1075 R.sup.D145 R.sup.D229 L.sub.C1183 R.sup.D168 R.sup.D229 L.sub.C860 R.sup.D17 R.sup.D230 L.sub.C968 R.sup.D50 R.sup.D230 L.sub.C1076 R.sup.D145 R.sup.D230 L.sub.C1184 R.sup.D168 R.sup.D230 L.sub.C861 R.sup.D17 R.sup.D231 L.sub.C969 R.sup.D50 R.sup.D231 L.sub.C1077 R.sup.D145 R.sup.D231 L.sub.C1185 R.sup.D168 R.sup.D231 L.sub.C862 R.sup.D17 R.sup.D232 L.sub.C970 R.sup.D50 R.sup.D232 L.sub.C1078 R.sup.D145 R.sup.D232 L.sub.C1186 R.sup.D168 R.sup.D232 L.sub.C863 R.sup.D17 R.sup.D233 L.sub.C971 R.sup.D50 R.sup.D233 L.sub.C1079 R.sup.D145 R.sup.D233 L.sub.C1187 R.sup.D168 R.sup.D233 L.sub.C864 R.sup.D17 R.sup.D234 L.sub.C972 R.sup.D50 R.sup.D234 L.sub.C1080 R.sup.D145 R.sup.D234 L.sub.C1188 R.sup.D168 R.sup.D234 L.sub.C865 R.sup.D17 R.sup.D235 L.sub.C973 R.sup.D50 R.sup.D235 L.sub.C1081 R.sup.D145 R.sup.D235 L.sub.C1189 R.sup.D168 R.sup.D235 L.sub.C866 R.sup.D17 R.sup.D236 L.sub.C974 R.sup.D50 R.sup.D236 L.sub.C1082 R.sup.D145 R.sup.D236 L.sub.C1190 R.sup.D168 R.sup.D236 L.sub.C867 R.sup.D17 R.sup.D237 L.sub.C975 R.sup.D50 R.sup.D237 L.sub.C1083 R.sup.D145 R.sup.D237 L.sub.C1191 R.sup.D168 R.sup.D237 L.sub.C868 R.sup.D17 R.sup.D238 L.sub.C976 R.sup.D50 R.sup.D238 L.sub.C1084 R.sup.D145 R.sup.D238 L.sub.C1192 R.sup.D168 R.sup.D238 L.sub.C869 R.sup.D17 R.sup.D239 L.sub.C977 R.sup.D50 R.sup.D239 L.sub.C1085 R.sup.D145 R.sup.D239 L.sub.C1193 R.sup.D168 R.sup.D239 L.sub.C870 R.sup.D17 R.sup.D240 L.sub.C978 R.sup.D50 R.sup.D240 L.sub.C1086 R.sup.D145 R.sup.D240 L.sub.C1194 R.sup.D168 R.sup.D240 L.sub.C871 R.sup.D17 R.sup.D241 L.sub.C979 R.sup.D50 R.sup.D241 L.sub.C1087 R.sup.D145 R.sup.D241 L.sub.C1195 R.sup.D168 R.sup.D241 L.sub.C872 R.sup.D17 R.sup.D242 L.sub.C980 R.sup.D50 R.sup.D242 L.sub.C1088 R.sup.D145 R.sup.D242 L.sub.C1196 R.sup.D168 R.sup.D242 L.sub.C873 R.sup.D17 R.sup.D243 L.sub.C981 R.sup.D50 R.sup.D243 L.sub.C1089 R.sup.D145 R.sup.D243 L.sub.C1197 R.sup.D168 R.sup.D243 L.sub.C874 R.sup.D17 R.sup.D244 L.sub.C982 R.sup.D50 R.sup.D244 L.sub.C1090 R.sup.D145 R.sup.D244 L.sub.C1198 R.sup.D168 R.sup.D244 L.sub.C875 R.sup.D17 R.sup.D245 L.sub.C983 R.sup.D50 R.sup.D245 L.sub.C1091 R.sup.D145 R.sup.D245 L.sub.C1199 R.sup.D168 R.sup.D245 L.sub.C876 R.sup.D17 R.sup.D246 L.sub.C984 R.sup.D50 R.sup.D246 L.sub.C1092 R.sup.D145 R.sup.D246 L.sub.C1200 R.sup.D168 R.sup.D246 L.sub.C1201 R.sup.D10 R.sup.D193 L.sub.C1255 R.sup.D55 R.sup.D193 L.sub.C1309 R.sup.D37 R.sup.D193 L.sub.C1363 R.sup.D143 R.sup.D193 L.sub.C1202 R.sup.D10 R.sup.D194 L.sub.C1256 R.sup.D55 R.sup.D194 L.sub.C1310 R.sup.D37 R.sup.D194 L.sub.C1364 R.sup.D143 R.sup.D194 L.sub.C1203 R.sup.D10 R.sup.D195 L.sub.C1257 R.sup.D55 R.sup.D195 L.sub.C1311 R.sup.D37 R.sup.D195 L.sub.C1365 R.sup.D143 R.sup.D195 L.sub.C1204 R.sup.D10 R.sup.D196 L.sub.C1258 R.sup.D55 R.sup.D196 L.sub.C1312 R.sup.D37 R.sup.D196 L.sub.C1366 R.sup.D143 R.sup.D196 L.sub.C1205 R.sup.D10 R.sup.D197 L.sub.C1259 R.sup.D55 R.sup.D197 L.sub.C1313 R.sup.D37 R.sup.D197 L.sub.C1367 R.sup.D143 R.sup.D197 L.sub.C1206 R.sup.D10 R.sup.D198 L.sub.C1260 R.sup.D55 R.sup.D198 L.sub.C1314 R.sup.D37 R.sup.D198 L.sub.C1368 R.sup.D143 R.sup.D198 L.sub.C1207 R.sup.D10 R.sup.D199 L.sub.C1261 R.sup.D55 R.sup.D199 L.sub.C1315 R.sup.D37 R.sup.D199 L.sub.C1369 R.sup.D143 R.sup.D199 L.sub.C1208 R.sup.D10 R.sup.D200 L.sub.C1262 R.sup.D55 R.sup.D200 L.sub.C1316 R.sup.D37 R.sup.D200 L.sub.C1370 R.sup.D143 R.sup.D200 L.sub.C1209 R.sup.D10 R.sup.D201 L.sub.C1263 R.sup.D55 R.sup.D201 L.sub.C1317 R.sup.D37 R.sup.D201 L.sub.C1371 R.sup.D143 R.sup.D201 L.sub.C1210 R.sup.D10 R.sup.D202 L.sub.C1264 R.sup.D55 R.sup.D202 L.sub.C1318 R.sup.D37 R.sup.D202 L.sub.C1372 R.sup.D143 R.sup.D202 L.sub.C1211 R.sup.D10 R.sup.D203 L.sub.C1265 R.sup.D55 R.sup.D203 L.sub.C1319 R.sup.D37 R.sup.D203 L.sub.C1373 R.sup.D143 R.sup.D203 L.sub.C1212 R.sup.D10 R.sup.D204 L.sub.C1266 R.sup.D55 R.sup.D204 L.sub.C1320 R.sup.D37 R.sup.D204 L.sub.C1374 R.sup.D143 R.sup.D204 L.sub.C1213 R.sup.D10 R.sup.D205 L.sub.C1267 R.sup.D55 R.sup.D205 L.sub.C1321 R.sup.D37 R.sup.D205 L.sub.C1375 R.sup.D143 R.sup.D205 L.sub.C1214 R.sup.D10 R.sup.D206 L.sub.C1268 R.sup.D55 R.sup.D206 L.sub.C1322 R.sup.D37 R.sup.D206 L.sub.C1376 R.sup.D143 R.sup.D206 L.sub.C1215 R.sup.D10 R.sup.D207 L.sub.C1269 R.sup.D55 R.sup.D207 L.sub.C1323 R.sup.D37 R.sup.D207 L.sub.C1377 R.sup.D143 R.sup.D207 L.sub.C1216 R.sup.D10 R.sup.D208 L.sub.C1270 R.sup.D55 R.sup.D208 L.sub.C1324 R.sup.D37 R.sup.D208 L.sub.C1378 R.sup.D143 R.sup.D208 L.sub.C1217 R.sup.D10 R.sup.D209 L.sub.C1271 R.sup.D55 R.sup.D209 L.sub.C1325 R.sup.D37 R.sup.D209 L.sub.C1379 R.sup.D143 R.sup.D209 L.sub.C1218 R.sup.D10 R.sup.D210 L.sub.C1272 R.sup.D55 R.sup.D210 L.sub.C1326 R.sup.D37 R.sup.D210 L.sub.C1380 R.sup.D143 R.sup.D210 L.sub.C1219 R.sup.D10 R.sup.D211 L.sub.C1273 R.sup.D55 R.sup.D211 L.sub.C1327 R.sup.D37 R.sup.D211 L.sub.C1381 R.sup.D143 R.sup.D211 L.sub.C1220 R.sup.D10 R.sup.D212 L.sub.C1274 R.sup.D55 R.sup.D212 L.sub.C1328 R.sup.D37 R.sup.D212 L.sub.C1382 R.sup.D143 R.sup.D212 L.sub.C1221 R.sup.D10 R.sup.D213 L.sub.C1275 R.sup.D55 R.sup.D213 L.sub.C1329 R.sup.D37 R.sup.D213 L.sub.C1383 R.sup.D143 R.sup.D213 L.sub.C1222 R.sup.D10 R.sup.D214 L.sub.C1276 R.sup.D55 R.sup.D214 L.sub.C1330 R.sup.D37 R.sup.D214 L.sub.C1384 R.sup.D143 R.sup.D214 L.sub.C1223 R.sup.D10 R.sup.D215 L.sub.C1277 R.sup.D55 R.sup.D215 L.sub.C1331 R.sup.D37 R.sup.D215 L.sub.C1385 R.sup.D143 R.sup.D215 L.sub.C1224 R.sup.D10 R.sup.D216 L.sub.C1278 R.sup.D55 R.sup.D216 L.sub.C1332 R.sup.D37 R.sup.D216 L.sub.C1386 R.sup.D143 R.sup.D216 L.sub.C1225 R.sup.D10 R.sup.D217 L.sub.C1279 R.sup.D55 R.sup.D217 L.sub.C1333 R.sup.D37 R.sup.D217 L.sub.C1387 R.sup.D143 R.sup.D217 L.sub.C1226 R.sup.D10 R.sup.D218 L.sub.C1280 R.sup.D55 R.sup.D218 L.sub.C1334 R.sup.D37 R.sup.D218 L.sub.C1388 R.sup.D143 R.sup.D218 L.sub.C1227 R.sup.D10 R.sup.D219 L.sub.C1281 R.sup.D55 R.sup.D219 L.sub.C1335 R.sup.D37 R.sup.D219 L.sub.C1389 R.sup.D143 R.sup.D219 L.sub.C1228 R.sup.D10 R.sup.D220 L.sub.C1282 R.sup.D55 R.sup.D220 L.sub.C1336 R.sup.D37 R.sup.D220 L.sub.C1390 R.sup.D143 R.sup.D220 L.sub.C1229 R.sup.D10 R.sup.D221 L.sub.C1283 R.sup.D55 R.sup.D221 L.sub.C1337 R.sup.D37 R.sup.D221 L.sub.C1391 R.sup.D143 R.sup.D221 L.sub.C1230 R.sup.D10 R.sup.D222 L.sub.C1284 R.sup.D55 R.sup.D222 L.sub.C1338 R.sup.D37 R.sup.D222 L.sub.C1392 R.sup.D143 R.sup.D222 L.sub.C1231 R.sup.D10 R.sup.D223 L.sub.C1285 R.sup.D55 R.sup.D223 L.sub.C1339 R.sup.D37 R.sup.D223 L.sub.C1393 R.sup.D143 R.sup.D223 L.sub.C1232 R.sup.D10 R.sup.D224 L.sub.C1286 R.sup.D55 R.sup.D224 L.sub.C1340 R.sup.D37 R.sup.D224 L.sub.C1394 R.sup.D143 R.sup.D224 L.sub.C1233 R.sup.D10 R.sup.D225 L.sub.C1287 R.sup.D55 R.sup.D225 L.sub.C1341 R.sup.D37 R.sup.D225 L.sub.C1395 R.sup.D143 R.sup.D225 L.sub.C1234 R.sup.D10 R.sup.D226 L.sub.C1288 R.sup.D55 R.sup.D226 L.sub.C1342 R.sup.D37 R.sup.D226 L.sub.C1396 R.sup.D143 R.sup.D226 L.sub.C1235 R.sup.D10 R.sup.D227 L.sub.C1289 R.sup.D55 R.sup.D227 L.sub.C1343 R.sup.D37 R.sup.D227 L.sub.C1397 R.sup.D143 R.sup.D227 L.sub.C1236 R.sup.D10 R.sup.D228 L.sub.C1290 R.sup.D55 R.sup.D228 L.sub.C1344 R.sup.D37 R.sup.D228 L.sub.C1398 R.sup.D143 R.sup.D228 L.sub.C1237 R.sup.D10 R.sup.D229 L.sub.C1291 R.sup.D55 R.sup.D229 L.sub.C1345 R.sup.D37 R.sup.D229 L.sub.C1399 R.sup.D143 R.sup.D229 L.sub.C1238 R.sup.D10 R.sup.D230 L.sub.C1292 R.sup.D55 R.sup.D230 L.sub.C1346 R.sup.D37 R.sup.D230 L.sub.C1400 R.sup.D143 R.sup.D230 L.sub.C1239 R.sup.D10 R.sup.D231 L.sub.C1293 R.sup.D55 R.sup.D231 L.sub.C1347 R.sup.D37 R.sup.D231 L.sub.C1401 R.sup.D143 R.sup.D231 L.sub.C1240 R.sup.D10 R.sup.D232 L.sub.C1294 R.sup.D55 R.sup.D232 L.sub.C1348 R.sup.D37 R.sup.D232 L.sub.C1402 R.sup.D143 R.sup.D232 L.sub.C1241 R.sup.D10 R.sup.D233 L.sub.C1295 R.sup.D55 R.sup.D233 L.sub.C1349 R.sup.D37 R.sup.D233 L.sub.C1403 R.sup.D143 R.sup.D233 L.sub.C1242 R.sup.D10 R.sup.D234 L.sub.C1296 R.sup.D55 R.sup.D234 L.sub.C1350 R.sup.D37 R.sup.D234 L.sub.C1404 R.sup.D143 R.sup.D234 L.sub.C1243 R.sup.D10 R.sup.D235 L.sub.C1297 R.sup.D55 R.sup.D235 L.sub.C1351 R.sup.D37 R.sup.D235 L.sub.C1405 R.sup.D143 R.sup.D235 L.sub.C1244 R.sup.D10 R.sup.D236 L.sub.C1298 R.sup.D55 R.sup.D236 L.sub.C1352 R.sup.D37 R.sup.D236 L.sub.C1406 R.sup.D143 R.sup.D236 L.sub.C1245 R.sup.D10 R.sup.D237 L.sub.C1299 R.sup.D55 R.sup.D237 L.sub.C1353 R.sup.D37 R.sup.D237 L.sub.C1407 R.sup.D143 R.sup.D237 L.sub.C1246 R.sup.D10 R.sup.D238 L.sub.C1300 R.sup.D55 R.sup.D238 L.sub.C1354 R.sup.D37 R.sup.D238 L.sub.C1408 R.sup.D143 R.sup.D238 L.sub.C1247 R.sup.D10 R.sup.D239 L.sub.C1301 R.sup.D55 R.sup.D239 L.sub.C1355 R.sup.D37 R.sup.D239 L.sub.C1409 R.sup.D143 R.sup.D239 L.sub.C1248 R.sup.D10 R.sup.D240 L.sub.C1302 R.sup.D55 R.sup.D240 L.sub.C1356 R.sup.D37 R.sup.D240 L.sub.C1410 R.sup.D143 R.sup.D240 L.sub.C1249 R.sup.D10 R.sup.D241 L.sub.C1303 R.sup.D55 R.sup.D241 L.sub.C1357 R.sup.D37 R.sup.D241 L.sub.C1411 R.sup.D143 R.sup.D241 L.sub.C1250 R.sup.D10 R.sup.D242 L.sub.C1304 R.sup.D55 R.sup.D242 L.sub.C1358 R.sup.D37 R.sup.D242 L.sub.C1412 R.sup.D143 R.sup.D242 L.sub.C1251 R.sup.D10 R.sup.D243 L.sub.C1305 R.sup.D55 R.sup.D243 L.sub.C1359 R.sup.D37 R.sup.D243 L.sub.C1413 R.sup.D143 R.sup.D243 L.sub.C1252 R.sup.D10 R.sup.D244 L.sub.C1306 R.sup.D55 R.sup.D244 L.sub.C1360 R.sup.D37 R.sup.D244 L.sub.C1414 R.sup.D143 R.sup.D244 L.sub.C1253 R.sup.D10 R.sup.D245 L.sub.C1307 R.sup.D55 R.sup.D245 L.sub.C1361 R.sup.D37 R.sup.D245 L.sub.C1415 R.sup.D143 R.sup.D245 L.sub.C1254 R.sup.D10 R.sup.D246 L.sub.C1308 R.sup.D55 R.sup.D246 L.sub.C1362 R.sup.D37 R.sup.D246 L.sub.C1416 R.sup.D143 R.sup.D246 wherein R.sup.D1 to R.sup.D246 have the following structures: ##STR00453## ##STR00454## ##STR00455## ##STR00456## ##STR00457## ##STR00458## ##STR00459## ##STR00460## ##STR00461## ##STR00462## ##STR00463## ##STR00464## ##STR00465## ##STR00466## ##STR00467## ##STR00468## ##STR00469## ##STR00470## ##STR00471## ##STR00472## ##STR00473## ##STR00474## ##STR00475## ##STR00476## ##STR00477## ##STR00478## ##STR00479## ##STR00480##
15. The compound of claim 12, wherein the compound is selected from the group consisting of: ##STR00481## ##STR00482## ##STR00483## ##STR00484## ##STR00485## ##STR00486## ##STR00487## ##STR00488## ##STR00489## ##STR00490##
16. The compound of claim 11, wherein the compound has the Formula II: ##STR00491## wherein: M.sup.1 is Pd or Pt; moieties E and F are each independently a 5-membered or 6-membered carbocyclic or heterocyclic ring; Z.sup.3 and Z.sup.4 are each independently C or N; K.sup.1, K.sup.2, K.sup.3, and K.sup.4 are each independently selected from the group consisting of a direct bond, O, and S, wherein at least two of K.sup.1, K.sup.2, K.sup.3, and K.sup.4 are direct bonds; L.sup.1, L.sup.2, and L.sup.3 are each independently selected from the group consisting of a single bond, absent a bond, O, Se, S, SO, SO.sub.2, C═CR′R″, C═NR′, C═O, CR′R″, SiR′R″, BR′, P(O)R′, and NR′, wherein at least one of L.sup.1 and L.sup.2 is present; X.sup.3′ and X.sup.4′ are each independently C or N; R.sup.E and R.sup.F each independently represent mono, up to a maximum allowed substitution, or no substitution; each of R′, R″, R.sup.E, and R.sup.F is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof; and two substituents can be joined or fused together to form a ring where chemically feasible.
17. An organic light emitting device (OLED) comprising: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound comprising a first ligand L.sub.A of Formula I: ##STR00492## wherein: each of X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, and X.sup.9 is independently C or N; one of Z.sup.1 and Z.sup.2 is C and the other is N; K.sup.1 and K.sup.2 are each independently selected from the group consisting of a direct bond, O, and S; at least one of K.sup.1 and K.sup.2 is a direct bond; R.sup.A and R.sup.C each independently represents mono, up to maximum allowed substitutions, or no substitution; R.sup.B represents mono, or up to maximum allowed substitutions; each of R.sup.1, R.sup.2, R.sup.A, R.sup.B, and R.sup.C is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; each of X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, and X.sup.9 that has an R.sup.A, R.sup.B, or R.sup.C attached thereto is C; at least one of R.sup.1 and R.sup.2 is selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl; R.sup.3 is selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl; at least one of the following is true: (i) at least one R.sup.B comprises a 5-membered or 6-membered heterocycle, (ii) two adjacent R.sup.B are joined to form a fused 5-membered or 6-membered carbocyclic or heterocyclic ring, which can be further substituted, or (iii) R.sup.B comprises a carbocyclic or heterocyclic ring substituted with at least one electron withdrawing group; L.sub.A is coordinated to a metal M selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au; L.sub.A may be joined with other ligand to comprise a tridentate, tetradentate, pentadentate, and hexadentate ligand; and any two of R.sup.1, R.sup.2, R.sup.3, R.sup.A, R.sup.B, and R.sup.C can be joined to form a ring.
18. The OLED of claim 17, wherein the organic layer further comprises a host, wherein host comprises at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).
19. The OLED of claim 18, wherein the host is selected from the group consisting of the HOST Group defined herein.
20. A consumer product comprising an organic light-emitting device comprising: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound comprising a first ligand L.sub.A of Formula I: ##STR00493## wherein: each of X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, and X.sup.9 is independently C or N; one of Z.sup.1 and Z.sup.2 is C and the other is N; K.sup.1 and K.sup.2 are each independently selected from the group consisting of a direct bond, O, and S; at least one of K.sup.1 and K.sup.2 is a direct bond; R.sup.A and R.sup.C each independently represents mono, up to maximum allowed substitutions, or no substitution; R.sup.B represents mono, or up to maximum allowed substitutions; each of R.sup.1, R.sup.2, R.sup.A, R.sup.B, and R.sup.C is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; each of X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, and X.sup.9 that has an R.sup.A, R.sup.B, or R.sup.C attached thereto is C; at least one of R.sup.1 and R.sup.2 is selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl; R.sup.3 is selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl; at least one of the following is true: (i) at least one R.sup.B comprises a 5-membered or 6-membered heterocycle, (ii) two adjacent R.sup.B are joined to form a fused 5-membered or 6-membered carbocyclic or heterocyclic ring, which can be further substituted, or (iii) R.sup.B comprises a carbocyclic or heterocyclic ring substituted with at least one electron withdrawing group; L.sub.A is coordinated to a metal M selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au; L.sub.A may be joined with other ligand to comprise a tridentate, tetradentate, pentadentate, and hexadentate ligand; and any two of R.sup.1, R.sup.2, R.sup.3, R.sup.A, R.sup.B, and R.sup.C can be joined to form a ring.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0027]
[0028]
DETAILED DESCRIPTION
A. Terminology
[0029] Unless otherwise specified, the below terms used herein are defined as follows:
[0030] As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
[0031] As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
[0032] As used herein, “solution processable” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
[0033] A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
[0034] As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
[0035] As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
[0036] The terms “halo,” “halogen,” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.
[0037] The term “acyl” refers to a substituted carbonyl radical (C(O)—R.sub.s).
[0038] The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—R.sub.s or —C(O)—O—R.sub.s) radical.
[0039] The term “ether” refers to an —OR.sub.s radical.
[0040] The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SR.sub.s radical.
[0041] The term “selenyl” refers to a —SeR.sub.s radical.
[0042] The term “sulfinyl” refers to a —S(O)—R.sub.s radical.
[0043] The term “sulfonyl” refers to a —SO.sub.2—R.sub.s radical.
[0044] The term “phosphino” refers to a —P(R.sub.s).sub.3 radical, wherein each R.sub.s can be same or different.
[0045] The term “silyl” refers to a —Si(R.sub.s).sub.3 radical, wherein each R.sub.s can be same or different.
[0046] The term “germyl” refers to a —Ge(R.sub.s).sub.3 radical, wherein each R.sub.s can be same or different.
[0047] The term “boryl” refers to a —B(R.sub.s).sub.2 radical or its Lewis adduct —B(R.sub.s).sub.3 radical, wherein R.sub.s can be same or different.
[0048] In each of the above, R.sub.s can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof. Preferred R.sub.s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.
[0049] The term “alkyl” refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.
[0050] The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.
[0051] The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or a cycloalkyl radical, respectively, having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably, O, S or N. Additionally, the heteroalkyl or heterocycloalkyl group may be optionally substituted.
[0052] The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. The term “heteroalkenyl” as used herein refers to an alkenyl radical having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted.
[0053] The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.
[0054] The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted.
[0055] The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.
[0056] The term “aryl” refers to and includes both single-ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is an aromatic hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.
[0057] The term “heteroaryl” refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.
[0058] Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and the respective aza-analogs of each thereof are of particular interest.
[0059] The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted, or independently substituted, with one or more general substituents.
[0060] In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.
[0061] In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.
[0062] In some instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, and combinations thereof.
[0063] In yet other instances, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
[0064] The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R.sup.1 represents mono-substitution, then one R.sup.1 must be other than H (i.e., a substitution). Similarly, when R.sup.1 represents di-substitution, then two of R.sup.1 must be other than H. Similarly, when R.sup.1 represents zero or no substitution, R.sup.1, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.
[0065] As used herein, “combinations thereof” indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.
[0066] The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective aromatic ring can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
[0067] As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.
[0068] It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
[0069] In some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2′ positions in a biphenyl, or 1, 8 position in a naphthalene, as long as they can form a stable fused ring system.
B. The Compounds of the Present Disclosure
[0070] In one aspect, the present disclosure provides a compound comprising a first ligand L.sub.A of Formula I:
##STR00003##
In Formula I:
[0071] each of X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, and X.sup.9 is independently C or N;
[0072] one of Z.sup.1 and Z.sup.2 is C and the other is N;
[0073] K.sup.1 and K.sup.2 are each independently selected from the group consisting of a direct bond, O, and S;
[0074] at least one of K.sup.1 and K.sup.2 is a direct bond;
[0075] R.sup.A and R.sup.C each independently represents mono, up to maximum allowed substitutions, or no substitution;
[0076] R.sup.B represents mono, or up to maximum allowed substitutions;
[0077] each of R.sup.1, R.sup.2, R.sup.A, R.sup.B, and R.sup.C is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein;
[0078] each of X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, and X.sup.9 that has an R.sup.A, R.sup.B, or R.sup.C attached thereto is C;
[0079] at least one of R.sup.1 and R.sup.2 is selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl;
[0080] R.sup.3 is selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl;
[0081] at least one of the following is true: [0082] (i) at least one R.sup.B comprises a 5-membered or 6-membered heterocycle, [0083] (ii) two adjacent R.sup.B are joined to form a fused 5-membered or 6-membered carbocyclic or heterocyclic ring, which can be further substituted, or [0084] (iii) R.sup.B comprises a carbocyclic or heterocyclic ring substituted with at least one electron withdrawing group;
[0085] L.sub.A is coordinated to a metal M selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au;
[0086] L.sub.A may be joined with other ligand to comprise a tridentate, tetradentate, pentadentate, and hexadentate ligand; and
[0087] any two of R.sup.1, R.sup.2, R.sup.3, R.sup.A, R.sup.B, and R.sup.C can be joined to form a ring.
[0088] In some embodiments, the maximum number of N atoms that can connect to each other within a ring is two.
[0089] In some embodiments, each of K.sup.1 and K.sup.2 can be a direct bond. In some embodiments, one of K.sup.1 and K.sup.2 can be O, and the other can be a direct bond. It should be understood that K.sup.1 or K.sup.2 can be O or S only when Z.sup.1 or Z.sup.2 to which K.sup.1 or K.sup.2 is attached is C. In other words, when K.sup.1 is S or O, Z.sup.1 is C, and when K.sup.2 is S or O, Z.sup.2 is C.
[0090] In some embodiments, each of R.sup.1, R.sup.2, R.sup.A, R.sup.B, and R.sup.C is independently a hydrogen or a substituent selected from the group consisting of the preferred general substituents. In some embodiments, each of R.sup.1, R.sup.2, R.sup.A, R.sup.B, and R.sup.C is independently a hydrogen or a substituent selected from the group consisting of the more preferred general substituents. In some embodiments, each of R.sup.1, R.sup.2, R.sup.A, R.sup.B, and R.sup.C is independently a hydrogen or a substituent selected from the group consisting of the most preferred general substituents.
[0091] In some embodiments, each of R.sup.1 and R.sup.2 is selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl.
[0092] In some embodiments, at least one of X.sup.1 to X.sup.9 is N. In some embodiments, at least one of X.sup.1 and X.sup.2 is N. In some embodiments, at least one of X.sup.3 to X.sup.5 is N. In some embodiments, at least one of X.sup.6 to X.sup.9 is N.
[0093] In some embodiments, Z.sup.1 is N and Z.sup.2 is C. In some embodiments, Z.sup.1 is C and Z.sup.2 is N.
[0094] In some embodiments, at least one R.sup.B comprises a 5-membered or 6-membered heterocycle. In some embodiments, at least one R.sup.B comprises a 5-membered heterocycle. In some embodiments, at least one R.sup.B comprises a 6-membered heterocycle. In some embodiments, at least one R.sup.B comprises a 6-membered heteroaryl ring. In some embodiments, exactly one R.sup.B comprises a 5-membered or 6-membered heterocycle.
[0095] In some embodiments, at least one R.sup.B comprises at least two 5-membered or 6-membered heterocyclic or carbocyclic rings. In some embodiments, at least one R.sup.B comprises at least three 5-membered or 6-membered heterocyclic or carbocyclic rings.
[0096] In some embodiments, two adjacent R.sup.B are joined to form a fused 5-membered or 6-membered carbocyclic or heterocyclic ring, which can be further substituted. In some such embodiments, the fused 5-membered or 6-membered carbocyclic or heterocyclic ring is an aromatic ring. In some such embodiments, the two adjacent R.sup.B are joined to form a 5-membered carbocyclic or heterocyclic ring. In some such embodiments, the two adjacent R.sup.B are joined to form a 6-membered carbocyclic or heterocyclic ring.
[0097] In some embodiments, the fused 5-membered or 6-membered carbocyclic or heterocyclic ring formed by two adjacent R.sup.B is further substituted with a chemical group selected from the group consisting of structures in the following LIST 1:
##STR00004## ##STR00005## ##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013##
[0098] In some embodiments, the fused 5-membered or 6-membered carbocyclic or heterocyclic ring formed by two adjacent R.sup.B is further fused by a 5-membered or 6-membered carbocyclic or heterocyclic ring. In some embodiments, R.sup.B comprises a 5-membered or 6-membered carbocyclic or heterocyclic aromatic ring substituted with at least one electron withdrawing group. In some such embodiments, the electron withdrawing group is selected from the group consisting of CN, CF.sub.3, COCH.sub.3, CHO, COCF.sub.3, COOMe, COOCF.sub.3, NO.sub.2, SF.sub.3, SiF.sub.3, PF.sub.4, SF.sub.5, OCF.sub.3, SCF.sub.3, SeCF.sub.3, SOCF.sub.3, SeOCF.sub.3, SO.sub.2F, SO.sub.2CF.sub.3, SeO.sub.2CF.sub.3, OSO.sub.2CF.sub.3, OSeO.sub.2CF.sub.3, OCN, SCN, SeCN, NC, .sup.+N(R).sub.3, (R).sub.2CCN, (R).sub.2CCF.sub.3, CNC(CF.sub.3).sub.2,
##STR00014##
[0099] where each R is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
[0100] In some embodiments, R.sup.B comprises a 5-membered or 6-membered carbocyclic or heterocyclic aromatic ring substituted with at least one electron withdrawing group selected from the group consisting of perfluoroalkyl, perfluorocycloalkyl, perfluorovinyl, CN, SCN, SF.sub.5, and SCF.sub.3.
[0101] In some embodiments, two R.sup.C are joined to form a polycyclic fused ring structure that includes Ring C. In the discussion that follows, Ring C is the first 6-membered ring. In some such embodiments, the polycyclic fused ring structure includes two 5-membered and/or 6-membered carbocyclic or heterocyclic rings, or at least three 5-membered and/or 6-membered carbocyclic or heterocyclic rings, or at least four 5-membered and/or 6-membered carbocyclic or heterocyclic rings, or at least five 5-membered and/or 6-membered carbocyclic or heterocyclic rings, or at least six 5-membered and/or 6-membered carbocyclic or heterocyclic rings.
[0102] In some embodiments, the polycyclic ring structure comprises 5-membered and/or 6-membered aromatic rings.
[0103] In some embodiments, the polycyclic ring structure has two fused rings and comprises two 6-membered rings or one 6-membered ring and one 5-membered ring.
[0104] In some embodiments, the polycyclic ring structure has three fused rings and comprises two 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to Ring C and the second 6-membered ring is fused to the 5-membered ring.
[0105] In some embodiments, the polycyclic ring structure has four fused rings and comprises three 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to Ring C, the second 6-membered ring is fused to the 5-membered ring, and the third 6-membered ring is fused to the second 6-membered ring.
[0106] In some embodiments, the polycyclic ring structure has five fused rings and comprises four 6-membered rings and one 5-membered ring or three 6-membered rings and two 5-membered rings. In some embodiments comprising two 5-membered rings, the 5-membered rings are fused together. In some embodiments comprising two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments with one 5-membered ring, the 5-membered ring is fused to Ring C, the second 6-membered ring is fused to the 5-membered ring, the third 6-membered ring is fused to the second 6-membered ring, and the fourth 6-membered ring is fused to the third-6-membered ring.
[0107] In some embodiments, the polycyclic ring structure has six fused rings and comprises five 6-membered rings and one 5-membered ring or four 6-membered rings and two 5-membered rings. In some embodiments comprising two 5-membered rings, the 5-membered rings are fused together. In some embodiments comprising two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments with one 5-membered ring, the 5-membered ring is fused to Ring C, the second 6-membered ring is fused to the 5-membered ring, the third 6-membered ring is fused to the second 6-membered ring, the fourth 6-membered ring is fused to the third-6-membered ring, and the fifth 6-membered ring is fused to the fourth 6-membered ring.
[0108] In some embodiments the ligand L.sub.A is selected from the group consisting of the structures in the following LIST 2:
##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022##
[0109] wherein X for each structure is independently NR, O, S, Se, C═O, S═O, and SO.sub.2;
[0110] R.sup.D independently represent mono, up to maximum allowed substitutions, or no substitution; and
[0111] each R.sup.D is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein.
[0112] In some embodiments, the ligand L.sub.A is selected from the group consisting of the structures in the following LIST 3:
##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033##
[0113] wherein X.sup.10 is independently C or N;
[0114] wherein R.sup.C′ represents mono, up to maximum allowed substitutions, or no substitution; and
[0115] wherein each R.sup.C′ and R.sup.D is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein.
[0116] In some embodiments, the ligand L.sub.A is selected from the group consisting of the structures in the following LIST 4:
##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058##
[0117] In some embodiments, the compound has a formula of M(L.sub.A).sub.p(L.sub.B).sub.q(L.sub.C).sub.r wherein L.sub.B and L.sub.C are each a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M.
[0118] In some embodiments, M is Ir, L.sub.B is a substituted or unsubstituted phenylpyridine, and L.sub.C is a substituted or unsubstituted acetylacetonate.
[0119] In some embodiments, the compound has a formula selected from the group consisting of Ir(L.sub.A).sub.3, Ir(L.sub.A)(L.sub.B).sub.2, Ir(L.sub.A).sub.2(L.sub.B), Ir(L.sub.A).sub.2(L.sub.C), and Ir(L.sub.A)(L.sub.B)(L.sub.C); and wherein L.sub.A, L.sub.B, and L.sub.C are different from each other.
[0120] In some embodiments, the compound has a formula of Pt(L.sub.A)(L.sub.B); and wherein L.sub.A and L.sub.B can be same or different. In some such embodiments, L.sub.A and L.sub.B are connected to form a tetradentate ligand.
[0121] In some embodiments, L.sub.B and L.sub.C are each independently selected from the group consisting of the structures in the following LIST 5:
##STR00059## ##STR00060## ##STR00061## ##STR00062##
wherein:
[0122] T is selected from the group consisting of B, Al, Ga, and In;
[0123] each of Y.sup.1 to Y.sup.13 is independently selected from the group consisting of carbon and nitrogen;
[0124] Y′ is selected from the group consisting of BR.sub.e, BR.sub.eR.sub.f, NR.sub.e, PR.sub.e, P(O)R.sub.e, O, S, Se, C═O, C═S, C═Se, C═NR.sub.e, C═CR.sub.eR.sub.f, S═O, SO.sub.2, CR.sub.eR.sub.f, SiR.sub.eR.sub.f, and GeR.sub.eR.sub.f;
[0125] R.sub.e and R.sub.f can be fused or joined to form a ring;
[0126] each R.sub.a, R.sub.b, R.sub.c, and R.sub.d independently represent zero, mono, or up to a maximum allowed number of substitutions to its associated ring;
[0127] each of R.sub.a1, R.sub.b1, R.sub.c1, R.sub.d1, R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and
[0128] any two adjacent R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f can be fused or joined to form a ring or form a multidentate ligand.
[0129] In some embodiments, L.sub.B and L.sub.C are each independently selected from the group consisting of the structures of the following LIST 6:
##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069##
wherein:
[0130] R.sub.a′, R.sub.b′, and R.sub.c′ each independently represent zero, mono, or up to a maximum allowed substitutions;
[0131] each of R.sub.a1, R.sub.b1, R.sub.c1, R.sub.a, R.sub.b, R.sub.c, R.sub.N, R.sub.a′, R.sub.b′, and R.sub.c′ is independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and
[0132] two adjacent R.sub.a′, R.sub.b′, and R.sub.c′ can be fused or joined to form a ring or form a multidentate ligand.
[0133] In some embodiments, the compound has a structure of formula Ir(L.sub.A).sub.3, formula Ir(L.sub.A)(L.sub.Bk).sub.2, formula Ir(L.sub.A).sub.2(L.sub.Bk), formula Ir(L.sub.A).sub.2(L.sub.Cj-I), or formula Ir(L.sub.A).sub.2(L.sub.Cj-II),
[0134] wherein each L.sub.A is selected from any one of L.sub.A ligands described herein;
[0135] wherein k is an integer from 1 to 324; j is an integer from 1 to 1416; and each of L.sub.B1 to L.sub.B324 has a structure defined in the following LIST 7:
##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105##
##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127##
wherein each L.sub.Cj-I has a structure based on formula
##STR00128##
and
each L.sub.Cj-II has a structure based on formula
##STR00129##
wherein for each L.sub.Cj in L.sub.Cj-I and L.sub.Cj-II, R.sup.201 and R.sup.202 are each independently defined in the following LIST 8:
TABLE-US-00001 L.sub.Cj R.sup.201 R.sup.202 L.sub.Cj R.sup.201 R.sup.202 L.sub.Cj R.sup.201 R.sup.202 L.sub.Cj R.sup.201 R.sup.202 L.sub.C1 R.sup.D1 R.sup.D1 L.sub.C193 R.sup.D1 R.sup.D3 L.sub.C385 R.sup.D17 R.sup.D40 L.sub.C577 R.sup.D143 R.sup.D120 L.sub.C2 R.sup.D2 R.sup.D2 L.sub.C194 R.sup.D1 R.sup.D4 L.sub.C386 R.sup.D17 R.sup.D41 L.sub.C578 R.sup.D143 R.sup.D133 L.sub.C3 R.sup.D3 R.sup.D3 L.sub.C195 R.sup.D1 R.sup.D5 L.sub.C387 R.sup.D17 R.sup.D42 L.sub.C579 R.sup.D143 R.sup.D134 L.sub.C4 R.sup.D4 R.sup.D4 L.sub.C196 R.sup.D1 R.sup.D9 L.sub.C388 R.sup.D17 R.sup.D43 L.sub.C580 R.sup.D143 R.sup.D135 L.sub.C5 R.sup.D5 R.sup.D5 L.sub.C197 R.sup.D1 R.sup.D10 L.sub.C389 R.sup.D17 R.sup.D48 L.sub.C581 R.sup.D143 R.sup.D136 L.sub.C6 R.sup.D6 R.sup.D6 L.sub.C198 R.sup.D1 R.sup.D17 L.sub.C390 R.sup.D17 R.sup.D49 L.sub.C582 R.sup.D143 R.sup.D144 L.sub.C7 R.sup.D7 R.sup.D7 L.sub.C199 R.sup.D1 R.sup.D18 L.sub.C391 R.sup.D17 R.sup.D50 L.sub.C583 R.sup.D143 R.sup.D145 L.sub.C8 R.sup.D8 R.sup.D8 L.sub.C200 R.sup.D1 R.sup.D20 L.sub.C392 R.sup.D17 R.sup.D54 L.sub.C584 R.sup.D143 R.sup.D146 L.sub.C9 R.sup.D9 R.sup.D9 L.sub.C201 R.sup.D1 R.sup.D22 L.sub.C393 R.sup.D17 R.sup.D55 L.sub.C585 R.sup.D143 R.sup.D147 L.sub.C10 R.sup.D10 R.sup.D10 L.sub.C202 R.sup.D1 R.sup.D37 L.sub.C394 R.sup.D17 R.sup.D58 L.sub.C586 R.sup.D143 R.sup.D149 L.sub.C11 R.sup.D11 R.sup.D11 L.sub.C203 R.sup.D1 R.sup.D40 L.sub.C395 R.sup.D17 R.sup.D59 L.sub.C587 R.sup.D143 R.sup.D151 L.sub.C12 R.sup.D12 R.sup.D12 L.sub.C204 R.sup.D1 R.sup.D41 L.sub.C396 R.sup.D17 R.sup.D78 L.sub.C588 R.sup.D143 R.sup.D154 L.sub.C13 R.sup.D13 R.sup.D13 L.sub.C205 R.sup.D1 R.sup.D42 L.sub.C397 R.sup.D17 R.sup.D79 L.sub.C589 R.sup.D143 R.sup.D155 L.sub.C14 R.sup.D14 R.sup.D14 L.sub.C206 R.sup.D1 R.sup.D43 L.sub.C398 R.sup.D17 R.sup.D81 L.sub.C590 R.sup.D143 R.sup.D161 L.sub.C15 R.sup.D15 R.sup.D15 L.sub.C207 R.sup.D1 R.sup.D48 L.sub.C399 R.sup.D17 R.sup.D87 L.sub.C591 R.sup.D143 R.sup.D175 L.sub.C16 R.sup.D16 R.sup.D16 L.sub.C208 R.sup.D1 R.sup.D49 L.sub.C400 R.sup.D17 R.sup.D88 L.sub.C592 R.sup.D144 R.sup.D3 L.sub.C17 R.sup.D17 R.sup.D17 L.sub.C209 R.sup.D1 R.sup.D50 L.sub.C401 R.sup.D17 R.sup.D89 L.sub.C593 R.sup.D144 R.sup.D5 L.sub.C18 R.sup.D18 R.sup.D18 L.sub.C210 R.sup.D1 R.sup.D54 L.sub.C402 R.sup.D17 R.sup.D93 L.sub.C594 R.sup.D144 R.sup.D17 L.sub.C19 R.sup.D19 R.sup.D19 L.sub.C211 R.sup.D1 R.sup.D55 L.sub.C403 R.sup.D17 R.sup.D116 L.sub.C595 R.sup.D144 R.sup.D18 L.sub.C20 R.sup.D20 R.sup.D20 L.sub.C212 R.sup.D1 R.sup.D58 L.sub.C404 R.sup.D17 R.sup.D117 L.sub.C596 R.sup.D144 R.sup.D20 L.sub.C21 R.sup.D21 R.sup.D21 L.sub.C213 R.sup.D1 R.sup.D59 L.sub.C405 R.sup.D17 R.sup.D118 L.sub.C597 R.sup.D144 R.sup.D22 L.sub.C22 R.sup.D22 R.sup.D22 L.sub.C214 R.sup.D1 R.sup.D78 L.sub.C406 R.sup.D17 R.sup.D119 L.sub.C598 R.sup.D144 R.sup.D37 L.sub.C23 R.sup.D23 R.sup.D23 L.sub.C215 R.sup.D1 R.sup.D79 L.sub.C407 R.sup.D17 R.sup.D120 L.sub.C599 R.sup.D144 R.sup.D40 L.sub.C24 R.sup.D24 R.sup.D24 L.sub.C216 R.sup.D1 R.sup.D81 L.sub.C408 R.sup.D17 R.sup.D133 L.sub.C600 R.sup.D144 R.sup.D41 L.sub.C25 R.sup.D25 R.sup.D25 L.sub.C217 R.sup.D1 R.sup.D87 L.sub.C409 R.sup.D17 R.sup.D134 L.sub.C601 R.sup.D144 R.sup.D42 L.sub.C26 R.sup.D26 R.sup.D26 L.sub.C218 R.sup.D1 R.sup.D88 L.sub.C410 R.sup.D17 R.sup.D135 L.sub.C602 R.sup.D144 R.sup.D43 L.sub.C27 R.sup.D27 R.sup.D27 L.sub.C219 R.sup.D1 R.sup.D89 L.sub.C411 R.sup.D17 R.sup.D136 L.sub.C603 R.sup.D144 R.sup.D48 L.sub.C28 R.sup.D28 R.sup.D28 L.sub.C220 R.sup.D1 R.sup.D93 L.sub.C412 R.sup.D17 R.sup.D143 L.sub.C604 R.sup.D144 R.sup.D49 L.sub.C29 R.sup.D29 R.sup.D29 L.sub.C221 R.sup.D1 R.sup.D116 L.sub.C413 R.sup.D17 R.sup.D144 L.sub.C605 R.sup.D144 R.sup.D54 L.sub.C30 R.sup.D30 R.sup.D30 L.sub.C222 R.sup.D1 R.sup.D117 L.sub.C414 R.sup.D17 R.sup.D145 L.sub.C606 R.sup.D144 R.sup.D58 L.sub.C31 R.sup.D31 R.sup.D31 L.sub.C223 R.sup.D1 R.sup.D118 L.sub.C415 R.sup.D17 R.sup.D146 L.sub.C607 R.sup.D144 R.sup.D59 L.sub.C32 R.sup.D32 R.sup.D32 L.sub.C224 R.sup.D1 R.sup.D119 L.sub.C416 R.sup.D17 R.sup.D147 L.sub.C608 R.sup.D144 R.sup.D78 L.sub.C33 R.sup.D33 R.sup.D33 L.sub.C225 R.sup.D1 R.sup.D120 L.sub.C417 R.sup.D17 R.sup.D149 L.sub.C609 R.sup.D144 R.sup.D79 L.sub.C34 R.sup.D34 R.sup.D34 L.sub.C226 R.sup.D1 R.sup.D133 L.sub.C418 R.sup.D17 R.sup.D151 L.sub.C610 R.sup.D144 R.sup.D81 L.sub.C35 R.sup.D35 R.sup.D35 L.sub.C227 R.sup.D1 R.sup.D134 L.sub.C419 R.sup.D17 R.sup.D154 L.sub.C611 R.sup.D144 R.sup.D87 L.sub.C36 R.sup.D36 R.sup.D36 L.sub.C228 R.sup.D1 R.sup.D135 L.sub.C420 R.sup.D17 R.sup.D155 L.sub.C612 R.sup.D144 R.sup.D88 L.sub.C37 R.sup.D37 R.sup.D37 L.sub.C229 R.sup.D1 R.sup.D136 L.sub.C421 R.sup.D17 R.sup.D161 L.sub.C613 R.sup.D144 R.sup.D89 L.sub.C38 R.sup.D38 R.sup.D38 L.sub.C230 R.sup.D1 R.sup.D143 L.sub.C422 R.sup.D17 R.sup.D175 L.sub.C614 R.sup.D144 R.sup.D93 L.sub.C39 R.sup.D39 R.sup.D39 L.sub.C231 R.sup.D1 R.sup.D144 L.sub.C423 R.sup.D50 R.sup.D3 L.sub.C615 R.sup.D144 R.sup.D116 L.sub.C40 R.sup.D40 R.sup.D40 L.sub.C232 R.sup.D1 R.sup.D145 L.sub.C424 R.sup.D50 R.sup.D5 L.sub.C616 R.sup.D144 R.sup.D117 L.sub.C41 R.sup.D41 R.sup.D41 L.sub.C233 R.sup.D1 R.sup.D146 L.sub.C425 R.sup.D50 R.sup.D18 L.sub.C617 R.sup.D144 R.sup.D118 L.sub.C42 R.sup.D42 R.sup.D42 L.sub.C234 R.sup.D1 R.sup.D147 L.sub.C426 R.sup.D50 R.sup.D20 L.sub.C618 R.sup.D144 R.sup.D119 L.sub.C43 R.sup.D43 R.sup.D43 L.sub.C235 R.sup.D1 R.sup.D149 L.sub.C427 R.sup.D50 R.sup.D22 L.sub.C619 R.sup.D144 R.sup.D120 L.sub.C44 R.sup.D44 R.sup.D44 L.sub.C236 R.sup.D1 R.sup.D151 L.sub.C428 R.sup.D50 R.sup.D37 L.sub.C620 R.sup.D144 R.sup.D133 L.sub.C45 R.sup.D45 R.sup.D45 L.sub.C237 R.sup.D1 R.sup.D154 L.sub.C429 R.sup.D50 R.sup.D40 L.sub.C621 R.sup.D144 R.sup.D134 L.sub.C46 R.sup.D46 R.sup.D46 L.sub.C238 R.sup.D1 R.sup.D155 L.sub.C430 R.sup.D50 R.sup.D41 L.sub.C622 R.sup.D144 R.sup.D135 L.sub.C47 R.sup.D47 R.sup.D47 L.sub.C239 R.sup.D1 R.sup.D161 L.sub.C431 R.sup.D50 R.sup.D42 L.sub.C623 R.sup.D144 R.sup.D136 L.sub.C48 R.sup.D48 R.sup.D48 L.sub.C240 R.sup.D1 R.sup.D175 L.sub.C432 R.sup.D50 R.sup.D43 L.sub.C624 R.sup.D144 R.sup.D145 L.sub.C49 R.sup.D49 R.sup.D49 L.sub.C241 R.sup.D4 R.sup.D3 L.sub.C433 R.sup.D50 R.sup.D48 L.sub.C625 R.sup.D144 R.sup.D146 L.sub.C50 R.sup.D50 R.sup.D50 L.sub.C242 R.sup.D4 R.sup.D5 L.sub.C434 R.sup.D50 R.sup.D49 L.sub.C626 R.sup.D144 R.sup.D147 L.sub.C51 R.sup.D51 R.sup.D51 L.sub.C243 R.sup.D4 R.sup.D9 L.sub.C435 R.sup.D50 R.sup.D54 L.sub.C627 R.sup.D144 R.sup.D149 L.sub.C52 R.sup.D52 R.sup.D52 L.sub.C244 R.sup.D4 R.sup.D10 L.sub.C436 R.sup.D50 R.sup.D55 L.sub.C628 R.sup.D144 R.sup.D151 L.sub.C53 R.sup.D53 R.sup.D53 L.sub.C245 R.sup.D4 R.sup.D17 L.sub.C437 R.sup.D50 R.sup.D58 L.sub.C629 R.sup.D144 R.sup.D154 L.sub.C54 R.sup.D54 R.sup.D54 L.sub.C246 R.sup.D4 R.sup.D18 L.sub.C438 R.sup.D50 R.sup.D59 L.sub.C630 R.sup.D144 R.sup.D155 L.sub.C55 R.sup.D55 R.sup.D55 L.sub.C247 R.sup.D4 R.sup.D20 L.sub.C439 R.sup.D50 R.sup.D78 L.sub.C631 R.sup.D144 R.sup.D161 L.sub.C56 R.sup.D56 R.sup.D56 L.sub.C248 R.sup.D4 R.sup.D22 L.sub.C440 R.sup.D50 R.sup.D79 L.sub.C632 R.sup.D144 R.sup.D175 L.sub.C57 R.sup.D57 R.sup.D57 L.sub.C249 R.sup.D4 R.sup.D37 L.sub.C441 R.sup.D50 R.sup.D81 L.sub.C633 R.sup.D145 R.sup.D3 L.sub.C58 R.sup.D58 R.sup.D58 L.sub.C250 R.sup.D4 R.sup.D40 L.sub.C442 R.sup.D50 R.sup.D87 L.sub.C634 R.sup.D145 R.sup.D5 L.sub.C59 R.sup.D59 R.sup.D59 L.sub.C251 R.sup.D4 R.sup.D41 L.sub.C443 R.sup.D50 R.sup.D88 L.sub.C635 R.sup.D145 R.sup.D17 L.sub.C60 R.sup.D60 R.sup.D60 L.sub.C252 R.sup.D4 R.sup.D42 L.sub.C444 R.sup.D50 R.sup.D89 L.sub.C636 R.sup.D145 R.sup.D18 L.sub.C61 R.sup.D61 R.sup.D61 L.sub.C253 R.sup.D4 R.sup.D43 L.sub.C445 R.sup.D50 R.sup.D93 L.sub.C637 R.sup.D145 R.sup.D20 L.sub.C62 R.sup.D62 R.sup.D62 L.sub.C254 R.sup.D4 R.sup.D48 L.sub.C446 R.sup.D50 R.sup.D116 L.sub.C638 R.sup.D145 R.sup.D22 L.sub.C63 R.sup.D63 R.sup.D63 L.sub.C255 R.sup.D4 R.sup.D49 L.sub.C447 R.sup.D50 R.sup.D117 L.sub.C639 R.sup.D145 R.sup.D37 L.sub.C64 R.sup.D64 R.sup.D64 L.sub.C256 R.sup.D4 R.sup.D50 L.sub.C448 R.sup.D50 R.sup.D118 L.sub.C640 R.sup.D145 R.sup.D40 L.sub.C65 R.sup.D65 R.sup.D65 L.sub.C257 R.sup.D4 R.sup.D54 L.sub.C449 R.sup.D50 R.sup.D119 L.sub.C641 R.sup.D145 R.sup.D41 L.sub.C66 R.sup.D66 R.sup.D66 L.sub.C258 R.sup.D4 R.sup.D55 L.sub.C450 R.sup.D50 R.sup.D120 L.sub.C642 R.sup.D145 R.sup.D42 L.sub.C67 R.sup.D67 R.sup.D67 L.sub.C259 R.sup.D4 R.sup.D58 L.sub.C451 R.sup.D50 R.sup.D133 L.sub.C643 R.sup.D145 R.sup.D43 L.sub.C68 R.sup.D68 R.sup.D68 L.sub.C260 R.sup.D4 R.sup.D59 L.sub.C452 R.sup.D50 R.sup.D134 L.sub.C644 R.sup.D145 R.sup.D48 L.sub.C69 R.sup.D69 R.sup.D69 L.sub.C261 R.sup.D4 R.sup.D78 L.sub.C453 R.sup.D50 R.sup.D135 L.sub.C645 R.sup.D145 R.sup.D49 L.sub.C70 R.sup.D70 R.sup.D70 L.sub.C262 R.sup.D4 R.sup.D79 L.sub.C454 R.sup.D50 R.sup.D136 L.sub.C646 R.sup.D145 R.sup.D54 L.sub.C71 R.sup.D71 R.sup.D71 L.sub.C263 R.sup.D4 R.sup.D81 L.sub.C455 R.sup.D50 R.sup.D143 L.sub.C647 R.sup.D145 R.sup.D58 L.sub.C72 R.sup.D72 R.sup.D72 L.sub.C264 R.sup.D4 R.sup.D87 L.sub.C456 R.sup.D50 R.sup.D144 L.sub.C648 R.sup.D145 R.sup.D59 L.sub.C73 R.sup.D73 R.sup.D73 L.sub.C265 R.sup.D4 R.sup.D88 L.sub.C457 R.sup.D50 R.sup.D145 L.sub.C649 R.sup.D145 R.sup.D78 L.sub.C74 R.sup.D74 R.sup.D74 L.sub.C266 R.sup.D4 R.sup.D89 L.sub.C458 R.sup.D50 R.sup.D146 L.sub.C650 R.sup.D145 R.sup.D79 L.sub.C75 R.sup.D75 R.sup.D75 L.sub.C267 R.sup.D4 R.sup.D93 L.sub.C459 R.sup.D50 R.sup.D147 L.sub.C651 R.sup.D145 R.sup.D81 L.sub.C76 R.sup.D76 R.sup.D76 L.sub.C268 R.sup.D4 R.sup.D116 L.sub.C460 R.sup.D50 R.sup.D149 L.sub.C652 R.sup.D145 R.sup.D87 L.sub.C77 R.sup.D77 R.sup.D77 L.sub.C269 R.sup.D4 R.sup.D117 L.sub.C461 R.sup.D50 R.sup.D151 L.sub.C653 R.sup.D145 R.sup.D88 L.sub.C78 R.sup.D78 R.sup.D78 L.sub.C270 R.sup.D4 R.sup.D118 L.sub.C462 R.sup.D50 R.sup.D154 L.sub.C654 R.sup.D145 R.sup.D89 L.sub.C79 R.sup.D79 R.sup.D79 L.sub.C271 R.sup.D4 R.sup.D119 L.sub.C463 R.sup.D50 R.sup.D155 L.sub.C655 R.sup.D145 R.sup.D93 L.sub.C80 R.sup.D80 R.sup.D80 L.sub.C272 R.sup.D4 R.sup.D120 L.sub.C464 R.sup.D50 R.sup.D161 L.sub.C656 R.sup.D145 R.sup.D116 L.sub.C81 R.sup.D81 R.sup.D81 L.sub.C273 R.sup.D4 R.sup.D133 L.sub.C465 R.sup.D50 R.sup.D175 L.sub.C657 R.sup.D145 R.sup.D117 L.sub.C82 R.sup.D82 R.sup.D82 L.sub.C274 R.sup.D4 R.sup.D134 L.sub.C466 R.sup.D55 R.sup.D3 L.sub.C658 R.sup.D145 R.sup.D118 L.sub.C83 R.sup.D83 R.sup.D83 L.sub.C275 R.sup.D4 R.sup.D135 L.sub.C467 R.sup.D55 R.sup.D5 L.sub.C659 R.sup.D145 R.sup.D119 L.sub.C84 R.sup.D84 R.sup.D84 L.sub.C276 R.sup.D4 R.sup.D136 L.sub.C468 R.sup.D55 R.sup.D18 L.sub.C660 R.sup.D145 R.sup.D120 L.sub.C85 R.sup.D85 R.sup.D85 L.sub.C277 R.sup.D4 R.sup.D143 L.sub.C469 R.sup.D55 R.sup.D20 L.sub.C661 R.sup.D145 R.sup.D133 L.sub.C86 R.sup.D86 R.sup.D86 L.sub.C278 R.sup.D4 R.sup.D144 L.sub.C470 R.sup.D55 R.sup.D22 L.sub.C662 R.sup.D145 R.sup.D134 L.sub.C87 R.sup.D87 R.sup.D87 L.sub.C279 R.sup.D4 R.sup.D145 L.sub.C471 R.sup.D55 R.sup.D37 L.sub.C663 R.sup.D145 R.sup.C135 L.sub.C88 R.sup.D88 R.sup.D88 L.sub.C280 R.sup.D4 R.sup.D146 L.sub.C472 R.sup.D55 R.sup.D40 L.sub.C664 R.sup.D145 R.sup.D136 L.sub.C89 R.sup.D89 R.sup.D89 L.sub.C281 R.sup.D4 R.sup.D147 L.sub.C473 R.sup.D55 R.sup.D41 L.sub.C665 R.sup.D145 R.sup.D146 L.sub.C90 R.sup.D90 R.sup.D90 L.sub.C282 R.sup.D4 R.sup.D149 L.sub.C474 R.sup.D55 R.sup.D42 L.sub.C666 R.sup.D145 R.sup.D147 L.sub.C91 R.sup.D91 R.sup.D91 L.sub.C283 R.sup.D4 R.sup.D151 L.sub.C475 R.sup.D55 R.sup.D43 L.sub.C667 R.sup.D145 R.sup.D149 L.sub.C92 R.sup.D92 R.sup.D92 L.sub.C284 R.sup.D4 R.sup.D154 L.sub.C476 R.sup.D55 R.sup.D48 L.sub.C668 R.sup.D145 R.sup.D151 L.sub.C93 R.sup.D93 R.sup.D93 L.sub.C285 R.sup.D4 R.sup.D155 L.sub.C477 R.sup.D55 R.sup.D49 L.sub.C669 R.sup.D145 R.sup.D154 L.sub.C94 R.sup.D94 R.sup.D94 L.sub.C286 R.sup.D4 R.sup.D161 L.sub.C478 R.sup.D55 R.sup.D54 L.sub.C670 R.sup.D145 R.sup.D155 L.sub.C95 R.sup.D95 R.sup.D95 L.sub.C287 R.sup.D4 R.sup.D175 L.sub.C479 R.sup.D55 R.sup.D58 L.sub.C671 R.sup.D145 R.sup.D161 L.sub.C96 R.sup.D96 R.sup.D96 L.sub.C288 R.sup.D9 R.sup.D3 L.sub.C480 R.sup.D55 R.sup.D59 L.sub.C672 R.sup.D145 R.sup.D175 L.sub.C97 R.sup.D97 R.sup.D97 L.sub.C289 R.sup.D9 R.sup.D5 L.sub.C481 R.sup.D55 R.sup.D78 L.sub.C673 R.sup.D146 R.sup.D3 L.sub.C98 R.sup.D98 R.sup.D98 L.sub.C290 R.sup.D9 R.sup.D10 L.sub.C482 R.sup.D55 R.sup.D79 L.sub.C674 R.sup.D146 R.sup.D5 L.sub.C99 R.sup.D99 R.sup.D99 L.sub.C291 R.sup.D9 R.sup.D17 L.sub.C483 R.sup.D55 R.sup.D81 L.sub.C675 R.sup.D146 R.sup.D17 L.sub.C100 R.sup.D100 R.sup.D100 L.sub.C292 R.sup.D9 R.sup.D18 L.sub.C484 R.sup.D55 R.sup.D87 L.sub.C676 R.sup.D146 R.sup.D18 L.sub.C101 R.sup.D101 R.sup.D101 L.sub.C293 R.sup.D9 R.sup.D20 L.sub.C485 R.sup.D55 R.sup.D88 L.sub.C677 R.sup.D146 R.sup.D20 L.sub.C102 R.sup.D102 R.sup.D102 L.sub.C294 R.sup.D9 R.sup.D22 L.sub.C486 R.sup.D55 R.sup.D89 L.sub.C678 R.sup.D146 R.sup.D22 L.sub.C103 R.sup.D103 R.sup.D103 L.sub.C295 R.sup.D9 R.sup.D37 L.sub.C487 R.sup.D55 R.sup.D93 L.sub.C679 R.sup.D146 R.sup.D37 L.sub.C104 R.sup.D104 R.sup.D104 L.sub.C296 R.sup.D9 R.sup.D40 L.sub.C488 R.sup.D55 R.sup.D116 L.sub.C680 R.sup.D146 R.sup.D40 L.sub.C105 R.sup.D105 R.sup.D105 L.sub.C297 R.sup.D9 R.sup.D41 L.sub.C489 R.sup.D55 R.sup.D117 L.sub.C681 R.sup.D146 R.sup.D41 L.sub.C106 R.sup.D106 R.sup.D106 L.sub.C298 R.sup.D9 R.sup.D42 L.sub.C490 R.sup.D55 R.sup.D118 L.sub.C682 R.sup.D146 R.sup.D42 L.sub.C107 R.sup.D107 R.sup.D107 L.sub.C299 R.sup.D9 R.sup.D43 L.sub.C491 R.sup.D55 R.sup.D119 L.sub.C683 R.sup.D146 R.sup.D43 L.sub.C108 R.sup.D108 R.sup.D108 L.sub.C300 R.sup.D9 R.sup.D48 L.sub.C492 R.sup.D55 R.sup.D120 L.sub.C684 R.sup.D146 R.sup.D48 L.sub.C109 R.sup.D109 R.sup.D109 L.sub.C301 R.sup.D9 R.sup.D49 L.sub.C493 R.sup.D55 R.sup.D133 L.sub.C685 R.sup.D146 R.sup.D49 L.sub.C110 R.sup.D110 R.sup.D110 L.sub.C302 R.sup.D9 R.sup.D50 L.sub.C494 R.sup.D55 R.sup.D134 L.sub.C686 R.sup.D146 R.sup.D54 L.sub.C111 R.sup.D111 R.sup.D111 L.sub.C303 R.sup.D9 R.sup.D54 L.sub.C495 R.sup.D55 R.sup.D135 L.sub.C687 R.sup.D146 R.sup.D58 L.sub.C112 R.sup.D112 R.sup.D112 L.sub.C304 R.sup.D9 R.sup.D55 L.sub.C496 R.sup.D55 R.sup.D136 L.sub.C688 R.sup.D146 R.sup.D59 L.sub.C113 R.sup.D113 R.sup.D113 L.sub.C305 R.sup.D9 R.sup.D58 L.sub.C497 R.sup.D55 R.sup.D143 L.sub.C689 R.sup.D146 R.sup.D78 L.sub.C114 R.sup.D114 R.sup.D114 L.sub.C306 R.sup.D9 R.sup.D59 L.sub.C498 R.sup.D55 R.sup.D144 L.sub.C690 R.sup.D146 R.sup.D79 L.sub.C115 R.sup.D115 R.sup.D115 L.sub.C307 R.sup.D9 R.sup.D78 L.sub.C499 R.sup.D55 R.sup.D145 L.sub.C691 R.sup.D146 R.sup.D81 L.sub.C116 R.sup.D116 R.sup.D116 L.sub.C308 R.sup.D9 R.sup.D79 L.sub.C500 R.sup.D55 R.sup.D146 L.sub.C692 R.sup.D146 R.sup.D87 L.sub.C117 R.sup.D117 R.sup.D117 L.sub.C309 R.sup.D9 R.sup.D81 L.sub.C501 R.sup.D55 R.sup.D147 L.sub.C693 R.sup.D146 R.sup.D88 L.sub.C118 R.sup.D118 R.sup.D118 L.sub.C310 R.sup.D9 R.sup.D87 L.sub.C502 R.sup.D55 R.sup.D149 L.sub.C694 R.sup.D146 R.sup.D89 L.sub.C119 R.sup.D119 R.sup.D119 L.sub.C311 R.sup.D9 R.sup.D88 L.sub.C503 R.sup.D55 R.sup.D151 L.sub.C695 R.sup.D146 R.sup.D93 L.sub.C120 R.sup.D120 R.sup.D120 L.sub.C312 R.sup.D9 R.sup.D89 L.sub.C504 R.sup.D55 R.sup.D154 L.sub.C696 R.sup.D146 R.sup.D117 L.sub.C121 R.sup.D121 R.sup.D121 L.sub.C313 R.sup.D9 R.sup.D93 L.sub.C505 R.sup.D55 R.sup.D155 L.sub.C697 R.sup.D146 R.sup.D118 L.sub.C122 R.sup.D122 R.sup.D122 L.sub.C314 R.sup.D9 R.sup.D116 L.sub.C506 R.sup.D55 R.sup.D161 L.sub.C698 R.sup.D146 R.sup.D119 L.sub.C123 R.sup.D123 R.sup.D123 L.sub.C315 R.sup.D9 R.sup.D117 L.sub.C507 R.sup.D55 R.sup.D175 L.sub.C699 R.sup.D146 R.sup.D120 L.sub.C124 R.sup.D124 R.sup.D124 L.sub.C316 R.sup.D9 R.sup.D118 L.sub.C508 R.sup.D116 R.sup.D3 L.sub.C700 R.sup.D146 R.sup.D133 L.sub.C125 R.sup.D125 R.sup.D125 L.sub.C317 R.sup.D9 R.sup.D119 L.sub.C509 R.sup.D116 R.sup.D5 L.sub.C701 R.sup.D146 R.sup.D134 L.sub.C126 R.sup.D126 R.sup.D126 L.sub.C318 R.sup.D9 R.sup.D120 L.sub.C510 R.sup.D116 R.sup.D17 L.sub.C702 R.sup.D146 R.sup.D135 L.sub.C127 R.sup.D127 R.sup.D127 L.sub.C319 R.sup.D9 R.sup.D133 L.sub.C511 R.sup.D116 R.sup.D18 L.sub.C703 R.sup.D146 R.sup.D136 L.sub.C128 R.sup.D128 R.sup.D128 L.sub.C320 R.sup.D9 R.sup.D134 L.sub.C512 R.sup.D116 R.sup.D20 L.sub.C704 R.sup.D146 R.sup.D146 L.sub.C129 R.sup.D129 R.sup.D129 L.sub.C321 R.sup.D9 R.sup.D135 L.sub.C513 R.sup.D116 R.sup.D22 L.sub.C705 R.sup.D146 R.sup.D147 L.sub.C130 R.sup.D130 R.sup.D130 L.sub.C322 R.sup.D9 R.sup.D136 L.sub.C514 R.sup.D116 R.sup.D37 L.sub.C706 R.sup.D146 R.sup.D149 L.sub.C131 R.sup.D131 R.sup.D131 L.sub.C323 R.sup.D9 R.sup.D143 L.sub.C515 R.sup.D116 R.sup.D40 L.sub.C707 R.sup.D146 R.sup.D151 L.sub.C132 R.sup.D132 R.sup.D132 L.sub.C324 R.sup.D9 R.sup.D144 L.sub.C516 R.sup.D116 R.sup.D41 L.sub.C708 R.sup.D146 R.sup.D154 L.sub.C133 R.sup.D133 R.sup.D133 L.sub.C325 R.sup.D9 R.sup.D145 L.sub.C517 R.sup.D116 R.sup.D42 L.sub.C709 R.sup.D146 R.sup.D155 L.sub.C134 R.sup.D134 R.sup.D134 L.sub.C326 R.sup.D9 R.sup.D146 L.sub.C518 R.sup.D116 R.sup.D43 L.sub.C710 R.sup.D146 R.sup.D161 L.sub.C135 R.sup.D135 R.sup.D135 L.sub.C327 R.sup.D9 R.sup.D147 L.sub.C519 R.sup.D116 R.sup.D48 L.sub.C711 R.sup.D146 R.sup.D175 L.sub.C136 R.sup.D136 R.sup.D136 L.sub.C328 R.sup.D9 R.sup.D149 L.sub.C520 R.sup.D116 R.sup.D49 L.sub.C712 R.sup.D133 R.sup.D3 L.sub.C137 R.sup.D137 R.sup.D137 L.sub.C329 R.sup.D9 R.sup.D151 L.sub.C521 R.sup.D116 R.sup.D54 L.sub.C713 R.sup.D133 R.sup.D5 L.sub.C138 R.sup.D138 R.sup.D138 L.sub.C330 R.sup.D9 R.sup.D154 L.sub.C522 R.sup.D116 R.sup.D58 L.sub.C714 R.sup.D133 R.sup.D3 L.sub.C139 R.sup.D139 R.sup.D139 L.sub.C331 R.sup.D9 R.sup.D155 L.sub.C523 R.sup.D116 R.sup.D59 L.sub.C715 R.sup.D133 R.sup.D18 L.sub.C140 R.sup.D140 R.sup.D140 L.sub.C332 R.sup.D9 R.sup.D161 L.sub.C524 R.sup.D116 R.sup.D78 L.sub.C716 R.sup.D133 R.sup.D20 L.sub.C141 R.sup.D141 R.sup.D141 L.sub.C333 R.sup.D9 R.sup.D175 L.sub.C525 R.sup.D116 R.sup.D79 L.sub.C717 R.sup.D133 R.sup.D22 L.sub.C142 R.sup.D142 R.sup.D142 L.sub.C334 R.sup.D10 R.sup.D3 L.sub.C526 R.sup.D116 R.sup.D81 L.sub.C718 R.sup.D133 R.sup.D37 L.sub.C143 R.sup.D143 R.sup.D143 L.sub.C335 R.sup.D10 R.sup.D5 L.sub.C527 R.sup.D116 R.sup.D87 L.sub.C719 R.sup.D133 R.sup.D40 L.sub.C144 R.sup.D144 R.sup.D144 L.sub.C336 R.sup.D10 R.sup.D17 L.sub.C528 R.sup.D116 R.sup.D88 L.sub.C720 R.sup.D133 R.sup.D41 L.sub.C145 R.sup.D145 R.sup.D145 L.sub.C337 R.sup.D10 R.sup.D18 L.sub.C529 R.sup.D116 R.sup.D89 L.sub.C721 R.sup.D133 R.sup.D42 L.sub.C146 R.sup.D146 R.sup.D146 L.sub.C338 R.sup.D10 R.sup.D20 L.sub.C530 R.sup.D116 R.sup.D93 L.sub.C722 R.sup.D133 R.sup.D43 L.sub.C147 R.sup.D147 R.sup.D147 L.sub.C339 R.sup.D10 R.sup.D22 L.sub.C531 R.sup.D116 R.sup.D117 L.sub.C723 R.sup.D133 R.sup.D48 L.sub.C148 R.sup.D148 R.sup.D148 L.sub.C340 R.sup.D10 R.sup.D37 L.sub.C532 R.sup.D116 R.sup.D118 L.sub.C724 R.sup.D133 R.sup.D49 L.sub.C149 R.sup.D149 R.sup.D149 L.sub.C341 R.sup.D10 R.sup.D40 L.sub.C533 R.sup.D116 R.sup.D119 L.sub.C725 R.sup.D133 R.sup.D54 L.sub.C150 R.sup.D150 R.sup.D150 L.sub.C342 R.sup.D10 R.sup.D41 L.sub.C534 R.sup.D116 R.sup.D120 L.sub.C726 R.sup.D133 R.sup.D58 L.sub.C151 R.sup.D151 R.sup.D151 L.sub.C343 R.sup.D10 R.sup.D42 L.sub.C535 R.sup.D116 R.sup.D133 L.sub.C727 R.sup.D133 R.sup.D59 L.sub.C152 R.sup.D152 R.sup.D152 L.sub.C344 R.sup.D10 R.sup.D43 L.sub.C536 R.sup.D116 R.sup.D134 L.sub.C728 R.sup.D133 R.sup.D78 L.sub.C153 R.sup.D153 R.sup.D153 L.sub.C345 R.sup.D10 R.sup.D48 L.sub.C537 R.sup.D116 R.sup.D135 L.sub.C729 R.sup.D133 R.sup.D79 L.sub.C154 R.sup.D154 R.sup.D154 L.sub.C346 R.sup.D10 R.sup.D49 L.sub.C538 R.sup.D116 R.sup.D136 L.sub.C730 R.sup.D133 R.sup.D81 L.sub.C155 R.sup.D155 R.sup.D155 L.sub.C347 R.sup.D10 R.sup.D50 L.sub.C539 R.sup.D116 R.sup.D143 L.sub.C731 R.sup.D133 R.sup.D87 L.sub.C156 R.sup.D156 R.sup.D156 L.sub.C348 R.sup.D10 R.sup.D54 L.sub.C540 R.sup.D116 R.sup.D144 L.sub.C732 R.sup.D133 R.sup.D88 L.sub.C157 R.sup.D157 R.sup.D157 L.sub.C349 R.sup.D10 R.sup.D55 L.sub.C541 R.sup.D116 R.sup.D145 L.sub.C733 R.sup.D133 R.sup.D89 L.sub.C158 R.sup.D158 R.sup.D158 L.sub.C350 R.sup.D10 R.sup.D58 L.sub.C542 R.sup.D116 R.sup.D146 L.sub.C734 R.sup.D133 R.sup.D93 L.sub.C159 R.sup.D159 R.sup.D159 L.sub.C351 R.sup.D10 R.sup.D59 L.sub.C543 R.sup.D116 R.sup.D147 L.sub.C735 R.sup.D133 R.sup.D117 L.sub.C160 R.sup.D160 R.sup.D160 L.sub.C352 R.sup.D10 R.sup.D78 L.sub.C544 R.sup.D116 R.sup.D149 L.sub.C736 R.sup.D133 R.sup.D118 L.sub.C161 R.sup.D161 R.sup.D161 L.sub.C353 R.sup.D10 R.sup.D79 L.sub.C545 R.sup.D116 R.sup.D151 L.sub.C737 R.sup.D133 R.sup.D119 L.sub.C162 R.sup.D162 R.sup.D162 L.sub.C354 R.sup.D10 R.sup.D81 L.sub.C546 R.sup.D116 R.sup.D154 L.sub.C738 R.sup.D133 R.sup.D120 L.sub.C163 R.sup.D163 R.sup.D163 L.sub.C355 R.sup.D10 R.sup.D87 L.sub.C547 R.sup.D116 R.sup.D155 L.sub.C739 R.sup.D133 R.sup.D133 L.sub.C164 R.sup.D164 R.sup.D164 L.sub.C356 R.sup.D10 R.sup.D88 L.sub.C548 R.sup.D116 R.sup.D161 L.sub.C740 R.sup.D133 R.sup.D134 L.sub.C165 R.sup.D165 R.sup.D165 L.sub.C357 R.sup.D10 R.sup.D89 L.sub.C549 R.sup.D116 R.sup.D175 L.sub.C741 R.sup.D133 R.sup.D135 L.sub.C166 R.sup.D166 R.sup.D166 L.sub.C358 R.sup.D10 R.sup.D93 L.sub.C550 R.sup.D143 R.sup.D3 L.sub.C742 R.sup.D133 R.sup.D136 L.sub.C167 R.sup.D167 R.sup.D167 L.sub.C359 R.sup.D10 R.sup.D116 L.sub.C551 R.sup.D143 R.sup.D5 L.sub.C743 R.sup.D133 R.sup.D146 L.sub.C168 R.sup.D168 R.sup.D168 L.sub.C360 R.sup.D10 R.sup.D117 L.sub.C552 R.sup.D143 R.sup.D17 L.sub.C744 R.sup.D133 R.sup.D147 L.sub.C169 R.sup.D169 R.sup.D169 L.sub.C361 R.sup.D10 R.sup.D118 L.sub.C553 R.sup.D143 R.sup.D18 L.sub.C745 R.sup.D133 R.sup.D149 L.sub.C170 R.sup.D170 R.sup.D170 L.sub.C362 R.sup.D10 R.sup.D119 L.sub.C554 R.sup.D143 R.sup.D20 L.sub.C746 R.sup.D133 R.sup.D151 L.sub.C171 R.sup.D171 R.sup.D171 L.sub.C363 R.sup.D10 R.sup.D120 L.sub.C555 R.sup.D143 R.sup.D22 L.sub.C747 R.sup.D133 R.sup.D154 L.sub.C172 R.sup.D172 R.sup.D172 L.sub.C364 R.sup.D10 R.sup.D133 L.sub.C556 R.sup.D143 R.sup.D37 L.sub.C748 R.sup.D133 R.sup.D155 L.sub.C173 R.sup.D173 R.sup.D173 L.sub.C365 R.sup.D10 R.sup.D134 L.sub.C557 R.sup.D143 R.sup.D40 L.sub.C749 R.sup.D133 R.sup.D161 L.sub.C174 R.sup.D174 R.sup.D174 L.sub.C366 R.sup.D10 R.sup.D135 L.sub.C558 R.sup.D143 R.sup.D41 L.sub.C750 R.sup.D133 R.sup.D175 L.sub.C175 R.sup.D175 R.sup.D175 L.sub.C367 R.sup.D10 R.sup.D136 L.sub.C559 R.sup.D143 R.sup.D42 L.sub.C751 R.sup.D175 R.sup.D3 L.sub.C176 R.sup.D176 R.sup.D176 L.sub.C368 R.sup.D10 R.sup.D143 L.sub.C560 R.sup.D143 R.sup.D43 L.sub.C752 R.sup.D175 R.sup.D5 L.sub.C177 R.sup.D177 R.sup.D177 L.sub.C369 R.sup.D10 R.sup.D144 L.sub.C561 R.sup.D143 R.sup.D48 L.sub.C753 R.sup.D175 R.sup.D18 L.sub.C178 R.sup.D178 R.sup.D178 L.sub.C370 R.sup.D10 R.sup.D145 L.sub.C562 R.sup.D143 R.sup.D49 L.sub.C754 R.sup.D175 R.sup.D20 L.sub.C179 R.sup.D179 R.sup.D179 L.sub.C371 R.sup.D10 R.sup.D146 L.sub.C563 R.sup.D143 R.sup.D54 L.sub.C755 R.sup.D175 R.sup.D22 L.sub.C180 R.sup.D180 R.sup.D180 L.sub.C372 R.sup.D10 R.sup.D147 L.sub.C564 R.sup.D143 R.sup.D58 L.sub.C756 R.sup.D175 R.sup.D37 L.sub.C181 R.sup.D181 R.sup.D181 L.sub.C373 R.sup.D10 R.sup.D149 L.sub.C565 R.sup.D143 R.sup.D59 L.sub.C757 R.sup.D175 R.sup.D40 L.sub.C182 R.sup.D182 R.sup.D182 L.sub.C374 R.sup.D10 R.sup.D151 L.sub.C566 R.sup.D143 R.sup.D78 L.sub.C758 R.sup.D175 R.sup.D41 L.sub.C183 R.sup.D183 R.sup.D183 L.sub.C375 R.sup.D10 R.sup.D154 L.sub.C567 R.sup.D143 R.sup.D79 L.sub.C759 R.sup.D175 R.sup.D42 L.sub.C184 R.sup.D184 R.sup.D184 L.sub.C376 R.sup.D10 R.sup.D155 L.sub.C568 R.sup.D143 R.sup.D81 L.sub.C760 R.sup.D175 R.sup.D43 L.sub.C185 R.sup.D185 R.sup.D185 L.sub.C377 R.sup.D10 R.sup.D161 L.sub.C569 R.sup.D143 R.sup.D87 L.sub.C761 R.sup.D175 R.sup.D48 L.sub.C186 R.sup.D186 R.sup.D186 L.sub.C378 R.sup.D10 R.sup.D175 L.sub.C570 R.sup.D143 R.sup.D88 L.sub.C762 R.sup.D175 R.sup.D49 L.sub.C187 R.sup.D187 R.sup.D187 L.sub.C379 R.sup.D17 R.sup.D3 L.sub.C571 R.sup.D143 R.sup.D89 L.sub.C763 R.sup.D175 R.sup.D54 L.sub.C188 R.sup.D188 R.sup.D188 L.sub.C380 R.sup.D17 R.sup.D5 L.sub.C572 R.sup.D143 R.sup.D93 L.sub.C764 R.sup.D175 R.sup.D58 L.sub.C189 R.sup.D189 R.sup.D189 L.sub.C381 R.sup.D17 R.sup.D18 L.sub.C573 R.sup.D143 R.sup.D116 L.sub.C765 R.sup.D175 R.sup.D59 L.sub.C190 R.sup.D190 R.sup.D190 L.sub.C382 R.sup.D17 R.sup.D20 L.sub.C574 R.sup.D143 R.sup.D117 L.sub.C766 R.sup.D175 R.sup.D78 L.sub.C191 R.sup.D191 R.sup.D191 L.sub.C383 R.sup.D17 R.sup.D22 L.sub.C575 R.sup.D143 R.sup.D118 L.sub.C767 R.sup.D175 R.sup.D79 L.sub.C192 R.sup.D192 R.sup.D192 L.sub.C384 R.sup.D17 R.sup.D37 L.sub.C576 R.sup.D143 R.sup.D119 L.sub.C768 R.sup.D175 R.sup.D81 L.sub.C769 R.sup.D193 R.sup.D193 L.sub.C877 R.sup.D1 R.sup.D193 L.sub.C985 R.sup.D4 R.sup.D193 L.sub.C1093 R.sup.D9 R.sup.D193 L.sub.C770 R.sup.D194 R.sup.D194 L.sub.C878 R.sup.D1 R.sup.D194 L.sub.C986 R.sup.D4 R.sup.D194 L.sub.C1094 R.sup.D9 R.sup.D194 L.sub.C771 R.sup.D195 R.sup.D195 L.sub.C879 R.sup.D1 R.sup.D195 L.sub.C987 R.sup.D4 R.sup.D195 L.sub.C1095 R.sup.D9 R.sup.D195 L.sub.C772 R.sup.D196 R.sup.D196 L.sub.C880 R.sup.D1 R.sup.D196 L.sub.C988 R.sup.D4 R.sup.D196 L.sub.C1096 R.sup.D9 R.sup.D196 L.sub.C773 R.sup.D197 R.sup.D197 L.sub.C881 R.sup.D1 R.sup.D197 L.sub.C989 R.sup.D4 R.sup.D197 L.sub.C1097 R.sup.D9 R.sup.D197 L.sub.C774 R.sup.D198 R.sup.D198 L.sub.C882 R.sup.D1 R.sup.D198 L.sub.C990 R.sup.D4 R.sup.D198 L.sub.C1098 R.sup.D9 R.sup.D198 L.sub.C775 R.sup.D199 R.sup.D199 L.sub.C883 R.sup.D1 R.sup.D199 L.sub.C991 R.sup.D4 R.sup.D199 L.sub.C1099 R.sup.D9 R.sup.D199 L.sub.C776 R.sup.D200 R.sup.D200 L.sub.C884 R.sup.D1 R.sup.D200 L.sub.C992 R.sup.D4 R.sup.D200 L.sub.C1100 R.sup.D9 R.sup.D200 L.sub.C777 R.sup.D201 R.sup.D201 L.sub.C885 R.sup.D1 R.sup.D201 L.sub.C993 R.sup.D4 R.sup.D201 L.sub.C1101 R.sup.D9 R.sup.D201 L.sub.C778 R.sup.D202 R.sup.D202 L.sub.C886 R.sup.D1 R.sup.D202 L.sub.C994 R.sup.D4 R.sup.D202 L.sub.C1102 R.sup.D9 R.sup.D202 L.sub.C779 R.sup.D203 R.sup.D203 L.sub.C887 R.sup.D1 R.sup.D203 L.sub.C995 R.sup.D4 R.sup.D203 L.sub.C1103 R.sup.D9 R.sup.D203 L.sub.C780 R.sup.D204 R.sup.D204 L.sub.C888 R.sup.D1 R.sup.D204 L.sub.C996 R.sup.D4 R.sup.D204 L.sub.C1104 R.sup.D9 R.sup.D204 L.sub.C781 R.sup.D205 R.sup.D205 L.sub.C889 R.sup.D1 R.sup.D205 L.sub.C997 R.sup.D4 R.sup.D205 L.sub.C1105 R.sup.D9 R.sup.D205 L.sub.C782 R.sup.D206 R.sup.D206 L.sub.C890 R.sup.D1 R.sup.D206 L.sub.C998 R.sup.D4 R.sup.D206 L.sub.C1106 R.sup.D9 R.sup.D206 L.sub.C783 R.sup.D207 R.sup.D207 L.sub.C891 R.sup.D1 R.sup.D207 L.sub.C999 R.sup.D4 R.sup.D207 L.sub.C1107 R.sup.D9 R.sup.D207 L.sub.C784 R.sup.D208 R.sup.D208 L.sub.C892 R.sup.D1 R.sup.D208 L.sub.C1000 R.sup.D4 R.sup.D208 L.sub.C1108 R.sup.D9 R.sup.D208 L.sub.C785 R.sup.D209 R.sup.D209 L.sub.C893 R.sup.D1 R.sup.D209 L.sub.C1001 R.sup.D4 R.sup.D209 L.sub.C1109 R.sup.D9 R.sup.D209 L.sub.C786 R.sup.D210 R.sup.D210 L.sub.C894 R.sup.D1 R.sup.D210 L.sub.C1002 R.sup.D4 R.sup.D210 L.sub.C1110 R.sup.D9 R.sup.D210 L.sub.C787 R.sup.D211 R.sup.D211 L.sub.C895 R.sup.D1 R.sup.D211 L.sub.C1003 R.sup.D4 R.sup.D211 L.sub.C1111 R.sup.D9 R.sup.D211 L.sub.C788 R.sup.D212 R.sup.D212 L.sub.C896 R.sup.D1 R.sup.D212 L.sub.C1004 R.sup.D4 R.sup.D212 L.sub.C1112 R.sup.D9 R.sup.D212 L.sub.C789 R.sup.D213 R.sup.D213 L.sub.C897 R.sup.D1 R.sup.D213 L.sub.C1005 R.sup.D4 R.sup.D213 L.sub.C1113 R.sup.D9 R.sup.D213 L.sub.C790 R.sup.D214 R.sup.D214 L.sub.C898 R.sup.D1 R.sup.D214 L.sub.C1006 R.sup.D4 R.sup.D214 L.sub.C1114 R.sup.D9 R.sup.D214 L.sub.C791 R.sup.D215 R.sup.D215 L.sub.C899 R.sup.D1 R.sup.D215 L.sub.C1007 R.sup.D4 R.sup.D215 L.sub.C1115 R.sup.D9 R.sup.D215 L.sub.C792 R.sup.D216 R.sup.D216 L.sub.C900 R.sup.D1 R.sup.D216 L.sub.C1008 R.sup.D4 R.sup.D216 L.sub.C1116 R.sup.D9 R.sup.D216 L.sub.C793 R.sup.D217 R.sup.D217 L.sub.C901 R.sup.D1 R.sup.D217 L.sub.C1009 R.sup.D4 R.sup.D217 L.sub.C1117 R.sup.D9 R.sup.D217 L.sub.C794 R.sup.D218 R.sup.D218 L.sub.C902 R.sup.D1 R.sup.D218 L.sub.C1010 R.sup.D4 R.sup.D218 L.sub.C1118 R.sup.D9 R.sup.D218 L.sub.C795 R.sup.D219 R.sup.D219 L.sub.C903 R.sup.D1 R.sup.D219 L.sub.C1011 R.sup.D4 R.sup.D219 L.sub.C1119 R.sup.D9 R.sup.D219 L.sub.C796 R.sup.D220 R.sup.D220 L.sub.C904 R.sup.D1 R.sup.D220 L.sub.C1012 R.sup.D4 R.sup.D220 L.sub.C1120 R.sup.D9 R.sup.D220 L.sub.C797 R.sup.D221 R.sup.D221 L.sub.C905 R.sup.D1 R.sup.D221 L.sub.C1013 R.sup.D4 R.sup.D221 L.sub.C1121 R.sup.D9 R.sup.D221 L.sub.C798 R.sup.D222 R.sup.D222 L.sub.C906 R.sup.D1 R.sup.D222 L.sub.C1014 R.sup.D4 R.sup.D222 L.sub.C1122 R.sup.D9 R.sup.D222 L.sub.C799 R.sup.D223 R.sup.D223 L.sub.C907 R.sup.D1 R.sup.D223 L.sub.C1015 R.sup.D4 R.sup.D223 L.sub.C1123 R.sup.D9 R.sup.D223 L.sub.C800 R.sup.D224 R.sup.D224 L.sub.C908 R.sup.D1 R.sup.D224 L.sub.C1016 R.sup.D4 R.sup.D224 L.sub.C1124 R.sup.D9 R.sup.D224 L.sub.C801 R.sup.D225 R.sup.D225 L.sub.C909 R.sup.D1 R.sup.D225 L.sub.C1017 R.sup.D4 R.sup.D225 L.sub.C1125 R.sup.D9 R.sup.D225 L.sub.C802 R.sup.D226 R.sup.D226 L.sub.C910 R.sup.D1 R.sup.D226 L.sub.C1018 R.sup.D4 R.sup.D226 L.sub.C1126 R.sup.D9 R.sup.D226 L.sub.C803 R.sup.D227 R.sup.D227 L.sub.C911 R.sup.D1 R.sup.D227 L.sub.C1019 R.sup.D4 R.sup.D227 L.sub.C1127 R.sup.D9 R.sup.D227 L.sub.C804 R.sup.D228 R.sup.D228 L.sub.C912 R.sup.D1 R.sup.D228 L.sub.C1020 R.sup.D4 R.sup.D228 L.sub.C1128 R.sup.D9 R.sup.D228 L.sub.C805 R.sup.D229 R.sup.D229 L.sub.C913 R.sup.D1 R.sup.D229 L.sub.C1021 R.sup.D4 R.sup.D229 L.sub.C1129 R.sup.D9 R.sup.D229 L.sub.C806 R.sup.D230 R.sup.D230 L.sub.C914 R.sup.D1 R.sup.D230 L.sub.C1022 R.sup.D4 R.sup.D230 L.sub.C1130 R.sup.D9 R.sup.D230 L.sub.C807 R.sup.D231 R.sup.D231 L.sub.C915 R.sup.D1 R.sup.D231 L.sub.C1023 R.sup.D4 R.sup.D231 L.sub.C1131 R.sup.D9 R.sup.D231 L.sub.C808 R.sup.D232 R.sup.D232 L.sub.C916 R.sup.D1 R.sup.D232 L.sub.C1024 R.sup.D4 R.sup.D232 L.sub.C1132 R.sup.D9 R.sup.D232 L.sub.C809 R.sup.D233 R.sup.D233 L.sub.C917 R.sup.D1 R.sup.D233 L.sub.C1025 R.sup.D4 R.sup.D233 L.sub.C1133 R.sup.D9 R.sup.D233 L.sub.C810 R.sup.D234 R.sup.D234 L.sub.C918 R.sup.D1 R.sup.D234 L.sub.C1026 R.sup.D4 R.sup.D234 L.sub.C1134 R.sup.D9 R.sup.D234 L.sub.C811 R.sup.D235 R.sup.D235 L.sub.C919 R.sup.D1 R.sup.D235 L.sub.C1027 R.sup.D4 R.sup.D235 L.sub.C1135 R.sup.D9 R.sup.D235 L.sub.C812 R.sup.D236 R.sup.D236 L.sub.C920 R.sup.D1 R.sup.D236 L.sub.C1028 R.sup.D4 R.sup.D236 L.sub.C1136 R.sup.D9 R.sup.D236 L.sub.C813 R.sup.D237 R.sup.D237 L.sub.C921 R.sup.D1 R.sup.D237 L.sub.C1029 R.sup.D4 R.sup.D237 L.sub.C1137 R.sup.D9 R.sup.D237 L.sub.C814 R.sup.D238 R.sup.D238 L.sub.C922 R.sup.D1 R.sup.D238 L.sub.C1030 R.sup.D4 R.sup.D238 L.sub.C1138 R.sup.D9 R.sup.D238 L.sub.C815 R.sup.D239 R.sup.D239 L.sub.C923 R.sup.D1 R.sup.D239 L.sub.C1031 R.sup.D4 R.sup.D239 L.sub.C1139 R.sup.D9 R.sup.D239 L.sub.C816 R.sup.D240 R.sup.D240 L.sub.C924 R.sup.D1 R.sup.D240 L.sub.C1032 R.sup.D4 R.sup.D240 L.sub.C1140 R.sup.D9 R.sup.D240 L.sub.C817 R.sup.D241 R.sup.D241 L.sub.C925 R.sup.D1 R.sup.D241 L.sub.C1033 R.sup.D4 R.sup.D241 L.sub.C1141 R.sup.D9 R.sup.D241 L.sub.C818 R.sup.D242 R.sup.D242 L.sub.C926 R.sup.D1 R.sup.D242 L.sub.C1034 R.sup.D4 R.sup.D242 L.sub.C1142 R.sup.D9 R.sup.D242 L.sub.C819 R.sup.D243 R.sup.D243 L.sub.C927 R.sup.D1 R.sup.D243 L.sub.C1035 R.sup.D4 R.sup.D243 L.sub.C1143 R.sup.D9 R.sup.D243 L.sub.C820 R.sup.D244 R.sup.D244 L.sub.C928 R.sup.D1 R.sup.D244 L.sub.C1036 R.sup.D4 R.sup.D244 L.sub.C1144 R.sup.D9 R.sup.D244 L.sub.C821 R.sup.D245 R.sup.D245 L.sub.C929 R.sup.D1 R.sup.D245 L.sub.C1037 R.sup.D4 R.sup.D245 L.sub.C1145 R.sup.D9 R.sup.D245 L.sub.C822 R.sup.D246 R.sup.D246 L.sub.C930 R.sup.D1 R.sup.D246 L.sub.C1038 R.sup.D4 R.sup.D246 L.sub.C1146 R.sup.D9 R.sup.D246 L.sub.C823 R.sup.D17 R.sup.D193 L.sub.C931 R.sup.D50 R.sup.D193 L.sub.C1039 R.sup.D145 R.sup.D193 L.sub.C1147 R.sup.D168 R.sup.D193 L.sub.C824 R.sup.D17 R.sup.D194 L.sub.C932 R.sup.D50 R.sup.D194 L.sub.C1040 R.sup.D145 R.sup.D194 L.sub.C1148 R.sup.D168 R.sup.D194 L.sub.C825 R.sup.D17 R.sup.D195 L.sub.C933 R.sup.D50 R.sup.D195 L.sub.C1041 R.sup.D145 R.sup.D195 L.sub.C1149 R.sup.D168 R.sup.D195 L.sub.C826 R.sup.D17 R.sup.D196 L.sub.C934 R.sup.D50 R.sup.D196 L.sub.C1042 R.sup.D145 R.sup.D196 L.sub.C1150 R.sup.D168 R.sup.D196 L.sub.C827 R.sup.D17 R.sup.D197 L.sub.C935 R.sup.D50 R.sup.D197 L.sub.C1043 R.sup.D145 R.sup.D197 L.sub.C1151 R.sup.D168 R.sup.D197 L.sub.C828 R.sup.D17 R.sup.D198 L.sub.C936 R.sup.D50 R.sup.D198 L.sub.C1044 R.sup.D145 R.sup.D198 L.sub.C1152 R.sup.D168 R.sup.D198 L.sub.C829 R.sup.D17 R.sup.D199 L.sub.C937 R.sup.D50 R.sup.D199 L.sub.C1045 R.sup.D145 R.sup.D199 L.sub.C1153 R.sup.D168 R.sup.D199 L.sub.C830 R.sup.D17 R.sup.D200 L.sub.C938 R.sup.D50 R.sup.D200 L.sub.C1046 R.sup.D145 R.sup.D200 L.sub.C1154 R.sup.D168 R.sup.D200 L.sub.C831 R.sup.D17 R.sup.D201 L.sub.C939 R.sup.D50 R.sup.D201 L.sub.C1047 R.sup.D145 R.sup.D201 L.sub.C1155 R.sup.D168 R.sup.D201 L.sub.C832 R.sup.D17 R.sup.D202 L.sub.C940 R.sup.D50 R.sup.D202 L.sub.C1048 R.sup.D145 R.sup.D202 L.sub.C1156 R.sup.D168 R.sup.D202 L.sub.C833 R.sup.D17 R.sup.D203 L.sub.C941 R.sup.D50 R.sup.D203 L.sub.C1049 R.sup.D145 R.sup.D203 L.sub.C1157 R.sup.D168 R.sup.D203 L.sub.C834 R.sup.D17 R.sup.D204 L.sub.C942 R.sup.D50 R.sup.D204 L.sub.C1050 R.sup.D145 R.sup.D204 L.sub.C1158 R.sup.D168 R.sup.D204 L.sub.C835 R.sup.D17 R.sup.D205 L.sub.C943 R.sup.D50 R.sup.D205 L.sub.C1051 R.sup.D145 R.sup.D205 L.sub.C1159 R.sup.D168 R.sup.D205 L.sub.C836 R.sup.D17 R.sup.D206 L.sub.C944 R.sup.D50 R.sup.D206 L.sub.C1052 R.sup.D145 R.sup.D206 L.sub.C1160 R.sup.D168 R.sup.D206 L.sub.C837 R.sup.D17 R.sup.D207 L.sub.C945 R.sup.D50 R.sup.D207 L.sub.C1053 R.sup.D145 R.sup.D207 L.sub.C1161 R.sup.D168 R.sup.D207 L.sub.C838 R.sup.D17 R.sup.D208 L.sub.C946 R.sup.D50 R.sup.D208 L.sub.C1054 R.sup.D145 R.sup.D208 L.sub.C1162 R.sup.D168 R.sup.D208 L.sub.C839 R.sup.D17 R.sup.D209 L.sub.C947 R.sup.D50 R.sup.D209 L.sub.C1055 R.sup.D145 R.sup.D209 L.sub.C1163 R.sup.D168 R.sup.D209 L.sub.C840 R.sup.D17 R.sup.D210 L.sub.C948 R.sup.D50 R.sup.D210 L.sub.C1056 R.sup.D145 R.sup.D210 L.sub.C1164 R.sup.D168 R.sup.D210 L.sub.C841 R.sup.D17 R.sup.D211 L.sub.C949 R.sup.D50 R.sup.D211 L.sub.C1057 R.sup.D145 R.sup.D211 L.sub.C1165 R.sup.D168 R.sup.D211 L.sub.C842 R.sup.D17 R.sup.D212 L.sub.C950 R.sup.D50 R.sup.D212 L.sub.C1058 R.sup.D145 R.sup.D212 L.sub.C1166 R.sup.D168 R.sup.D212 L.sub.C843 R.sup.D17 R.sup.D213 L.sub.C951 R.sup.D50 R.sup.D213 L.sub.C1059 R.sup.D145 R.sup.D213 L.sub.C1167 R.sup.D168 R.sup.D213 L.sub.C844 R.sup.D17 R.sup.D214 L.sub.C952 R.sup.D50 R.sup.D214 L.sub.C1060 R.sup.D145 R.sup.D214 L.sub.C1168 R.sup.D168 R.sup.D214 L.sub.C845 R.sup.D17 R.sup.D215 L.sub.C953 R.sup.D50 R.sup.D215 L.sub.C1061 R.sup.D145 R.sup.D215 L.sub.C1169 R.sup.D168 R.sup.D215 L.sub.C846 R.sup.D17 R.sup.D216 L.sub.C954 R.sup.D50 R.sup.D216 L.sub.C1062 R.sup.D145 R.sup.D216 L.sub.C1170 R.sup.D168 R.sup.D216 L.sub.C847 R.sup.D17 R.sup.D217 L.sub.C955 R.sup.D50 R.sup.D217 L.sub.C1063 R.sup.D145 R.sup.D217 L.sub.C1171 R.sup.D168 R.sup.D217 L.sub.C848 R.sup.D17 R.sup.D218 L.sub.C956 R.sup.D50 R.sup.D218 L.sub.C1064 R.sup.D145 R.sup.D218 L.sub.C1172 R.sup.D168 R.sup.D218 L.sub.C849 R.sup.D17 R.sup.D219 L.sub.C957 R.sup.D50 R.sup.D219 L.sub.C1065 R.sup.D145 R.sup.D219 L.sub.C1173 R.sup.D168 R.sup.D219 L.sub.C850 R.sup.D17 R.sup.D220 L.sub.C958 R.sup.D50 R.sup.D220 L.sub.C1066 R.sup.D145 R.sup.D220 L.sub.C1174 R.sup.D168 R.sup.D220 L.sub.C851 R.sup.D17 R.sup.D221 L.sub.C959 R.sup.D50 R.sup.D221 L.sub.C1067 R.sup.D145 R.sup.D221 L.sub.C1175 R.sup.D168 R.sup.D221 L.sub.C852 R.sup.D17 R.sup.D222 L.sub.C960 R.sup.D50 R.sup.D222 L.sub.C1068 R.sup.D145 R.sup.D222 L.sub.C1176 R.sup.D168 R.sup.D222 L.sub.C853 R.sup.D17 R.sup.D223 L.sub.C961 R.sup.D50 R.sup.D223 L.sub.C1069 R.sup.D145 R.sup.D223 L.sub.C1177 R.sup.D168 R.sup.D223 L.sub.C854 R.sup.D17 R.sup.D224 L.sub.C962 R.sup.D50 R.sup.D224 L.sub.C1070 R.sup.D145 R.sup.D224 L.sub.C1178 R.sup.D168 R.sup.D224 L.sub.C855 R.sup.D17 R.sup.D225 L.sub.C963 R.sup.D50 R.sup.D225 L.sub.C1071 R.sup.D145 R.sup.D225 L.sub.C1179 R.sup.D168 R.sup.D225 L.sub.C856 R.sup.D17 R.sup.D226 L.sub.C964 R.sup.D50 R.sup.D226 L.sub.C1072 R.sup.D145 R.sup.D226 L.sub.C1180 R.sup.D168 R.sup.D226 L.sub.C857 R.sup.D17 R.sup.D227 L.sub.C965 R.sup.D50 R.sup.D227 L.sub.C1073 R.sup.D145 R.sup.D227 L.sub.C1181 R.sup.D168 R.sup.D227 L.sub.C858 R.sup.D17 R.sup.D228 L.sub.C966 R.sup.D50 R.sup.D228 L.sub.C1074 R.sup.D145 R.sup.D228 L.sub.C1182 R.sup.D168 R.sup.D228 L.sub.C859 R.sup.D17 R.sup.D229 L.sub.C967 R.sup.D50 R.sup.D229 L.sub.C1075 R.sup.D145 R.sup.D229 L.sub.C1183 R.sup.D168 R.sup.D229 L.sub.C860 R.sup.D17 R.sup.D230 L.sub.C968 R.sup.D50 R.sup.D230 L.sub.C1076 R.sup.D145 R.sup.D230 L.sub.C1184 R.sup.D168 R.sup.D230 L.sub.C861 R.sup.D17 R.sup.D231 L.sub.C969 R.sup.D50 R.sup.D231 L.sub.C1077 R.sup.D145 R.sup.D231 L.sub.C1185 R.sup.D168 R.sup.D231 L.sub.C862 R.sup.D17 R.sup.D232 L.sub.C970 R.sup.D50 R.sup.D232 L.sub.C1078 R.sup.D145 R.sup.D232 L.sub.C1186 R.sup.D168 R.sup.D232 L.sub.C863 R.sup.D17 R.sup.D233 L.sub.C971 R.sup.D50 R.sup.D233 L.sub.C1079 R.sup.D145 R.sup.D233 L.sub.C1187 R.sup.D168 R.sup.D233 L.sub.C864 R.sup.D17 R.sup.D234 L.sub.C972 R.sup.D50 R.sup.D234 L.sub.C1080 R.sup.D145 R.sup.D234 L.sub.C1188 R.sup.D168 R.sup.D234 L.sub.C865 R.sup.D17 R.sup.D235 L.sub.C973 R.sup.D50 R.sup.D235 L.sub.C1081 R.sup.D145 R.sup.D235 L.sub.C1189 R.sup.D168 R.sup.D235 L.sub.C866 R.sup.D17 R.sup.D236 L.sub.C974 R.sup.D50 R.sup.D236 L.sub.C1082 R.sup.D145 R.sup.D236 L.sub.C1190 R.sup.D168 R.sup.D236 L.sub.C867 R.sup.D17 R.sup.D237 L.sub.C975 R.sup.D50 R.sup.D237 L.sub.C1083 R.sup.D145 R.sup.D237 L.sub.C1191 R.sup.D168 R.sup.D237 L.sub.C868 R.sup.D17 R.sup.D238 L.sub.C976 R.sup.D50 R.sup.D238 L.sub.C1084 R.sup.D145 R.sup.D238 L.sub.C1192 R.sup.D168 R.sup.D238 L.sub.C869 R.sup.D17 R.sup.D239 L.sub.C977 R.sup.D50 R.sup.D239 L.sub.C1085 R.sup.D145 R.sup.D239 L.sub.C1193 R.sup.D168 R.sup.D239 L.sub.C870 R.sup.D17 R.sup.D240 L.sub.C978 R.sup.D50 R.sup.D240 L.sub.C1086 R.sup.D145 R.sup.D240 L.sub.C1194 R.sup.D168 R.sup.D240 L.sub.C871 R.sup.D17 R.sup.D241 L.sub.C979 R.sup.D50 R.sup.D241 L.sub.C1087 R.sup.D145 R.sup.D241 L.sub.C1195 R.sup.D168 R.sup.D241 L.sub.C872 R.sup.D17 R.sup.D242 L.sub.C980 R.sup.D50 R.sup.D242 L.sub.C1088 R.sup.D145 R.sup.D242 L.sub.C1196 R.sup.D168 R.sup.D242 L.sub.C873 R.sup.D17 R.sup.D243 L.sub.C981 R.sup.D50 R.sup.D243 L.sub.C1089 R.sup.D145 R.sup.D243 L.sub.C1197 R.sup.D168 R.sup.D243 L.sub.C874 R.sup.D17 R.sup.D244 L.sub.C982 R.sup.D50 R.sup.D244 L.sub.C1090 R.sup.D145 R.sup.D244 L.sub.C1198 R.sup.D168 R.sup.D244 L.sub.C875 R.sup.D17 R.sup.D245 L.sub.C983 R.sup.D50 R.sup.D245 L.sub.C1091 R.sup.D145 R.sup.D245 L.sub.C1199 R.sup.D168 R.sup.D245 L.sub.C876 R.sup.D17 R.sup.D246 L.sub.C984 R.sup.D50 R.sup.D246 L.sub.C1092 R.sup.D145 R.sup.D246 L.sub.C1200 R.sup.D168 R.sup.D246 L.sub.C1201 R.sup.D10 R.sup.D193 L.sub.C1255 R.sup.D55 R.sup.D193 L.sub.C1309 R.sup.D37 R.sup.D193 L.sub.C1363 R.sup.D143 R.sup.D193 L.sub.C1202 R.sup.D10 R.sup.D194 L.sub.C1256 R.sup.D55 R.sup.D194 L.sub.C1310 R.sup.D37 R.sup.D194 L.sub.C1364 R.sup.D143 R.sup.D194 L.sub.C1203 R.sup.D10 R.sup.D195 L.sub.C1257 R.sup.D55 R.sup.D195 L.sub.C1311 R.sup.D37 R.sup.D195 L.sub.C1365 R.sup.D143 R.sup.D195 L.sub.C1204 R.sup.D10 R.sup.D196 L.sub.C1258 R.sup.D55 R.sup.D196 L.sub.C1312 R.sup.D37 R.sup.D196 L.sub.C1366 R.sup.D143 R.sup.D196 L.sub.C1205 R.sup.D10 R.sup.D197 L.sub.C1259 R.sup.D55 R.sup.D197 L.sub.C1313 R.sup.D37 R.sup.D197 L.sub.C1367 R.sup.D143 R.sup.D197 L.sub.C1206 R.sup.D10 R.sup.D198 L.sub.C1260 R.sup.D55 R.sup.D198 L.sub.C1314 R.sup.D37 R.sup.D198 L.sub.C1368 R.sup.D143 R.sup.D198 L.sub.C1207 R.sup.D10 R.sup.D199 L.sub.C1261 R.sup.D55 R.sup.D199 L.sub.C1315 R.sup.D37 R.sup.D199 L.sub.C1369 R.sup.D143 R.sup.D199 L.sub.C1208 R.sup.D10 R.sup.D200 L.sub.C1262 R.sup.D55 R.sup.D200 L.sub.C1316 R.sup.D37 R.sup.D200 L.sub.C1370 R.sup.D143 R.sup.D200 L.sub.C1209 R.sup.D10 R.sup.D201 L.sub.C1263 R.sup.D55 R.sup.D201 L.sub.C1317 R.sup.D37 R.sup.D201 L.sub.C1371 R.sup.D143 R.sup.D201 L.sub.C1210 R.sup.D10 R.sup.D202 L.sub.C1264 R.sup.D55 R.sup.D202 L.sub.C1318 R.sup.D37 R.sup.D202 L.sub.C1372 R.sup.D143 R.sup.D202 L.sub.C1211 R.sup.D10 R.sup.D203 L.sub.C1265 R.sup.D55 R.sup.D203 L.sub.C1319 R.sup.D37 R.sup.D203 L.sub.C1373 R.sup.D143 R.sup.D203 L.sub.C1212 R.sup.D10 R.sup.D204 L.sub.C1266 R.sup.D55 R.sup.D204 L.sub.C1320 R.sup.D37 R.sup.D204 L.sub.C1374 R.sup.D143 R.sup.D204 L.sub.C1213 R.sup.D10 R.sup.D205 L.sub.C1267 R.sup.D55 R.sup.D205 L.sub.C1321 R.sup.D37 R.sup.D205 L.sub.C1375 R.sup.D143 R.sup.D205 L.sub.C1214 R.sup.D10 R.sup.D206 L.sub.C1268 R.sup.D55 R.sup.D206 L.sub.C1322 R.sup.D37 R.sup.D206 L.sub.C1376 R.sup.D143 R.sup.D206 L.sub.C1215 R.sup.D10 R.sup.D207 L.sub.C1269 R.sup.D55 R.sup.D207 L.sub.C1323 R.sup.D37 R.sup.D207 L.sub.C1377 R.sup.D143 R.sup.D207 L.sub.C1216 R.sup.D10 R.sup.D208 L.sub.C1270 R.sup.D55 R.sup.D208 L.sub.C1324 R.sup.D37 R.sup.D208 L.sub.C1378 R.sup.D143 R.sup.D208 L.sub.C1217 R.sup.D10 R.sup.D209 L.sub.C1271 R.sup.D55 R.sup.D209 L.sub.C1325 R.sup.D37 R.sup.D209 L.sub.C1379 R.sup.D143 R.sup.D209 L.sub.C1218 R.sup.D10 R.sup.D210 L.sub.C1272 R.sup.D55 R.sup.D210 L.sub.C1326 R.sup.D37 R.sup.D210 L.sub.C1380 R.sup.D143 R.sup.D210 L.sub.C1219 R.sup.D10 R.sup.D211 L.sub.C1273 R.sup.D55 R.sup.D211 L.sub.C1327 R.sup.D37 R.sup.D211 L.sub.C1381 R.sup.D143 R.sup.D211 L.sub.C1220 R.sup.D10 R.sup.D212 L.sub.C1274 R.sup.D55 R.sup.D212 L.sub.C1328 R.sup.D37 R.sup.D212 L.sub.C1382 R.sup.D143 R.sup.D212 L.sub.C1221 R.sup.D10 R.sup.D213 L.sub.C1275 R.sup.D55 R.sup.D213 L.sub.C1329 R.sup.D37 R.sup.D213 L.sub.C1383 R.sup.D143 R.sup.D213 L.sub.C1222 R.sup.D10 R.sup.D214 L.sub.C1276 R.sup.D55 R.sup.D214 L.sub.C1330 R.sup.D37 R.sup.D214 L.sub.C1384 R.sup.D143 R.sup.D214 L.sub.C1223 R.sup.D10 R.sup.D215 L.sub.C1277 R.sup.D55 R.sup.D215 L.sub.C1331 R.sup.D37 R.sup.D215 L.sub.C1385 R.sup.D143 R.sup.D215 L.sub.C1224 R.sup.D10 R.sup.D216 L.sub.C1278 R.sup.D55 R.sup.D216 L.sub.C1332 R.sup.D37 R.sup.D216 L.sub.C1386 R.sup.D143 R.sup.D216 L.sub.C1225 R.sup.D10 R.sup.D217 L.sub.C1279 R.sup.D55 R.sup.D217 L.sub.C1333 R.sup.D37 R.sup.D217 L.sub.C1387 R.sup.D143 R.sup.D217 L.sub.C1226 R.sup.D10 R.sup.D218 L.sub.C1280 R.sup.D55 R.sup.D218 L.sub.C1334 R.sup.D37 R.sup.D218 L.sub.C1388 R.sup.D143 R.sup.D218 L.sub.C1227 R.sup.D10 R.sup.D219 L.sub.C1281 R.sup.D55 R.sup.D219 L.sub.C1335 R.sup.D37 R.sup.D219 L.sub.C1389 R.sup.D143 R.sup.D219 L.sub.C1228 R.sup.D10 R.sup.D220 L.sub.C1282 R.sup.D55 R.sup.D220 L.sub.C1336 R.sup.D37 R.sup.D220 L.sub.C1390 R.sup.D143 R.sup.D220 L.sub.C1229 R.sup.D10 R.sup.D221 L.sub.C1283 R.sup.D55 R.sup.D221 L.sub.C1337 R.sup.D37 R.sup.D221 L.sub.C1391 R.sup.D143 R.sup.D221 L.sub.C1230 R.sup.D10 R.sup.D222 L.sub.C1284 R.sup.D55 R.sup.D222 L.sub.C1338 R.sup.D37 R.sup.D222 L.sub.C1392 R.sup.D143 R.sup.D222 L.sub.C1231 R.sup.D10 R.sup.D223 L.sub.C1285 R.sup.D55 R.sup.D223 L.sub.C1339 R.sup.D37 R.sup.D223 L.sub.C1393 R.sup.D143 R.sup.D223 L.sub.C1232 R.sup.D10 R.sup.D224 L.sub.C1286 R.sup.D55 R.sup.D224 L.sub.C1340 R.sup.D37 R.sup.D224 L.sub.C1394 R.sup.D143 R.sup.D224 L.sub.C1233 R.sup.D10 R.sup.D225 L.sub.C1287 R.sup.D55 R.sup.D225 L.sub.C1341 R.sup.D37 R.sup.D225 L.sub.C1395 R.sup.D143 R.sup.D225 L.sub.C1234 R.sup.D10 R.sup.D226 L.sub.C1288 R.sup.D55 R.sup.D226 L.sub.C1342 R.sup.D37 R.sup.D226 L.sub.C1396 R.sup.D143 R.sup.D226 L.sub.C1235 R.sup.D10 R.sup.D227 L.sub.C1289 R.sup.D55 R.sup.D227 L.sub.C1343 R.sup.D37 R.sup.D227 L.sub.C1397 R.sup.D143 R.sup.D227 L.sub.C1236 R.sup.D10 R.sup.D228 L.sub.C1290 R.sup.D55 R.sup.D228 L.sub.C1344 R.sup.D37 R.sup.D228 L.sub.C1398 R.sup.D143 R.sup.D228 L.sub.C1237 R.sup.D10 R.sup.D229 L.sub.C1291 R.sup.D55 R.sup.D229 L.sub.C1345 R.sup.D37 R.sup.D229 L.sub.C1399 R.sup.D143 R.sup.D229 L.sub.C1238 R.sup.D10 R.sup.D230 L.sub.C1292 R.sup.D55 R.sup.D230 L.sub.C1346 R.sup.D37 R.sup.D230 L.sub.C1400 R.sup.D143 R.sup.D230 L.sub.C1239 R.sup.D10 R.sup.D231 L.sub.C1293 R.sup.D55 R.sup.D231 L.sub.C1347 R.sup.D37 R.sup.D231 L.sub.C1401 R.sup.D143 R.sup.D231 L.sub.C1240 R.sup.D10 R.sup.D232 L.sub.C1294 R.sup.D55 R.sup.D232 L.sub.C1348 R.sup.D37 R.sup.D232 L.sub.C1402 R.sup.D143 R.sup.D232 L.sub.C1241 R.sup.D10 R.sup.D233 L.sub.C1295 R.sup.D55 R.sup.D233 L.sub.C1349 R.sup.D37 R.sup.D233 L.sub.C1403 R.sup.D143 R.sup.D233 L.sub.C1242 R.sup.D10 R.sup.D234 L.sub.C1296 R.sup.D55 R.sup.D234 L.sub.C1350 R.sup.D37 R.sup.D234 L.sub.C1404 R.sup.D143 R.sup.D234 L.sub.C1243 R.sup.D10 R.sup.D235 L.sub.C1297 R.sup.D55 R.sup.D235 L.sub.C1351 R.sup.D37 R.sup.D235 L.sub.C1405 R.sup.D143 R.sup.D235 L.sub.C1244 R.sup.D10 R.sup.D236 L.sub.C1298 R.sup.D55 R.sup.D236 L.sub.C1352 R.sup.D37 R.sup.D236 L.sub.C1406 R.sup.D143 R.sup.D236 L.sub.C1245 R.sup.D10 R.sup.D237 L.sub.C1299 R.sup.D55 R.sup.D237 L.sub.C1353 R.sup.D37 R.sup.D237 L.sub.C1407 R.sup.D143 R.sup.D237 L.sub.C1246 R.sup.D10 R.sup.D238 L.sub.C1300 R.sup.D55 R.sup.D238 L.sub.C1354 R.sup.D37 R.sup.D238 L.sub.C1408 R.sup.D143 R.sup.D238 L.sub.C1247 R.sup.D10 R.sup.D239 L.sub.C1301 R.sup.D55 R.sup.D239 L.sub.C1355 R.sup.D37 R.sup.D239 L.sub.C1409 R.sup.D143 R.sup.D239 L.sub.C1248 R.sup.D10 R.sup.D240 L.sub.C1302 R.sup.D55 R.sup.D240 L.sub.C1356 R.sup.D37 R.sup.D240 L.sub.C1410 R.sup.D143 R.sup.D240 L.sub.C1249 R.sup.D10 R.sup.D241 L.sub.C1303 R.sup.D55 R.sup.D241 L.sub.C1357 R.sup.D37 R.sup.D241 L.sub.C1411 R.sup.D143 R.sup.D241 L.sub.C1250 R.sup.D10 R.sup.D242 L.sub.C1304 R.sup.D55 R.sup.D242 L.sub.C1358 R.sup.D37 R.sup.D242 L.sub.C1412 R.sup.D143 R.sup.D242 L.sub.C1251 R.sup.D10 R.sup.D243 L.sub.C1305 R.sup.D55 R.sup.D243 L.sub.C1359 R.sup.D37 R.sup.D243 L.sub.C1413 R.sup.D143 R.sup.D243 L.sub.C1252 R.sup.D10 R.sup.D244 L.sub.C1306 R.sup.D55 R.sup.D244 L.sub.C1360 R.sup.D37 R.sup.D244 L.sub.C1414 R.sup.D143 R.sup.D244 L.sub.C1253 R.sup.D10 R.sup.D245 L.sub.C1307 R.sup.D55 R.sup.D245 L.sub.C1361 R.sup.D37 R.sup.D245 L.sub.C1415 R.sup.D143 R.sup.D245 L.sub.C1254 R.sup.D10 R.sup.D246 L.sub.C1308 R.sup.D55 R.sup.D246 L.sub.C1362 R.sup.D37 R.sup.D246 L.sub.C1416 R.sup.D143 R.sup.D246
wherein R.sup.D1 to R.sup.D246 have the structures of the following LIST 9:
##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144##
[0136] In some embodiments, the compound has the formula Ir(L.sub.A)(L.sub.Bk).sub.2 or Ir(L.sub.A).sub.2(L.sub.Bk), wherein the compound is selected from the group consisting of only those compounds having one of the following structures for the L.sub.Bk ligand: L.sub.B1, L.sub.B2, L.sub.B18, L.sub.B28, L.sub.B38, L.sub.B108, L.sub.B118, L.sub.B122, L.sub.B124, L.sub.B126, L.sub.B128, L.sub.B130, L.sub.B32, L.sub.B134, L.sub.B136, L.sub.B138, L.sub.B140, L.sub.B142, L.sub.B144, L.sub.B156, L.sub.B58, L.sub.B160, L.sub.B162, L.sub.B164, L.sub.B168, L.sub.B172, L.sub.B175, L.sub.B204, L.sub.B206, L.sub.B214, L.sub.B216, L.sub.B218, L.sub.B220, L.sub.B222, L.sub.B231, L.sub.B233, L.sub.B235, L.sub.B237, L.sub.B240, L.sub.B242, L.sub.B244, L.sub.B246, L.sub.B248, L.sub.B250, L.sub.B252, L.sub.B254, L.sub.B256, L.sub.B258, L.sub.B260, L.sub.B262, L.sub.B263, L.sub.B264, L.sub.B265, L.sub.B266, L.sub.B267, L.sub.B268, L.sub.B269, and L.sub.B270.
[0137] In some embodiments, the compound has the formula Ir(L.sub.A)(L.sub.Bk).sub.2 or Ir(L.sub.A).sub.2(L.sub.Bk), wherein the compound is selected from the group consisting of only those compounds having one of the following structures for the L.sub.Bk ligand: L.sub.B1, L.sub.B2, L.sub.B18, L.sub.B28, L.sub.B38, L.sub.B108, L.sub.B118, L.sub.B122, L.sub.B124, L.sub.B126, L.sub.B128, L.sub.B132, L.sub.B136, L.sub.B138, L.sub.B142, L.sub.B156, L.sub.B162, L.sub.B204, L.sub.B206, L.sub.B214, L.sub.B216, L.sub.B218, L.sub.B220, L.sub.B231, L.sub.B233, L.sub.B237, L.sub.B265, L.sub.B266, L.sub.B267, L.sub.B268, L.sub.B269, and L.sub.B270.
[0138] In some embodiments, the compound has the formula Ir(L.sub.A).sub.2(L.sub.Cj-I) or Ir(L.sub.A).sub.2(L.sub.Cj-II), wherein the compound is selected from the group consisting of only those compounds having L.sub.Cj-I or L.sub.Cj-II ligand whose corresponding R.sup.201 and R.sup.202 are defined to be one the following structures:
##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150##
[0139] In some embodiments, the compound has the formula Ir(L.sub.A).sub.2(L.sub.Cj-I) or Ir(L.sub.A).sub.2(L.sub.Cj-II), wherein the compound is selected from the group consisting of only those compounds having L.sub.Cj-I or L.sub.Cj-II ligand whose corresponding R.sup.201 and R.sup.202 are defined to be one of the following structures:
##STR00151## ##STR00152## ##STR00153##
[0140] In some embodiments, the compound has the formula Ir(L.sub.A).sub.2(L.sub.Cj-I), and the compound is selected from the group consisting of only those compounds having one of the following structures for the L.sub.Cj-I ligand:
##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158##
[0141] In some embodiments, the compound is selected from the group consisting of the following LIST 10:
##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178##
[0142] In some embodiments, the compound has the Formula II:
##STR00179##
wherein:
[0143] M.sup.1 is Pd or Pt;
[0144] moieties E and F are each independently a 5-membered or 6-membered carbocyclic or heterocyclic ring;
[0145] Z.sup.3 and Z.sup.4 are each independently C or N;
[0146] K.sup.1, K.sup.2, K.sup.3, and K.sup.4 are each independently selected from the group consisting of a direct bond, O, and S, wherein at least two of K.sup.1, K.sup.2, K.sup.3, and K.sup.4 are direct bonds;
[0147] L.sup.1, L.sup.2, and L.sup.3 are each independently selected from the group consisting of a single bond, absent a bond, O, Se, S, SO, SO.sub.2, C═CR′R″, C═NR′, C═O, CR′R″, SiR′R″, BR′, P(O)R′, and NR′, wherein at least one of L.sup.1 and L.sup.2 is present;
[0148] X.sup.3′ and X.sup.4′ are each independently C or N;
[0149] R.sup.E and R.sup.F each independently represent mono, up to a maximum allowed substitution, or no substitution;
[0150] each of R′, R″, R.sup.E, and R.sup.F is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof; and
[0151] two substituents can be joined or fused together to form a ring where chemically feasible.
[0152] In some embodiments, moiety E and moiety F are both 6-membered aromatic rings.
[0153] In some embodiments, moiety F is a 5-membered or 6-membered heteroaromatic ring.
[0154] In some embodiments, L.sup.1 is O or CR′R″.
[0155] In some embodiments, Z.sup.3 is N and Z.sup.4 is C. In some embodiments, Z.sup.3 is C and Z.sup.4 is N.
[0156] In some embodiments, L.sup.2 is a direct bond. In some embodiments, L.sup.2 is NR′.
[0157] In some embodiments, each of K.sup.1, K.sup.2, K.sup.3, and K.sup.4 is a direct bond.
[0158] In some embodiments, one of K.sup.1, K.sup.2, K.sup.3, and K.sup.4 is O. In some embodiments, one of K.sup.1, and K.sup.2 is O. In some embodiments, one of K.sup.3, and K.sup.4 is O.
[0159] In some embodiments, X.sup.3′ and X.sup.4′ are both C.
[0160] In some embodiments, the compound is selected from the group consisting of:
##STR00180## ##STR00181##
wherein:
[0161] R.sup.X and R.sup.Y are each selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;
[0162] R.sup.G represents mono, up to a maximum allowed substitution, or no substitution; and
[0163] R.sup.G for each occurrence is independently a hydrogen or a substituent selected from the group consisting of the Preferred general substituents defined herein.
[0164] In some embodiments, the compound is selected from the group consisting of the structures of the following LIST 11:
##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191## ##STR00192## ##STR00193## ##STR00194##
[0165] In yet another aspect, the present disclosure also provides a compound having formula of Ir(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z, wherein:
[0166] L.sup.1, L.sup.2 and L.sup.3 can be the same or different;
[0167] x is 1, 2, or 3;
[0168] y is 0, 1, or 2;
[0169] z is 0, 1, or 2;
[0170] x+y+z is 3;
[0171] L.sup.1 each independently have a structure of
##STR00195##
[0172] L.sup.2, and L.sup.3 each independently have a structure of
##STR00196##
[0173] Z1 and Z2 are each independently C or N;
[0174] moieties AA and BB are each independently monocyclic or polycyclic ring comprising 5-membered or 6-membered carbocyclic and/or heterocyclic aromatic rings;
[0175] each of R.sub.a and R.sub.b independently represents mono, up to maximum allowed substitutions, or no substitution;
[0176] each R.sub.a, R.sub.b, R.sub.a1, R.sub.b1, and R.sub.c1 is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
[0177] any two of R.sub.a and R.sub.b are optionally joined or fused to form a ring;
[0178] the compound has a highest occupied molecular orbital (HOMO) energy and a lowest unoccupied molecular orbital (LUMO) energy; ΔE is the energy gap between the HOMO energy and the LUMO energy;
[0179] the compound has a triplet energy T.sub.1 of E.sub.T;
[0180] a≤ΔE−E.sub.T≤b, and
[0181] a is 0.00 up to 0.15 eV, and b is 0.05 up to 0.40 eV.
[0182] In some embodiments, moieties AA and BB may be each independently benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, or fluorene.
[0183] In some embodiments, each of R.sub.a and R.sub.b may be independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
[0184] In some of the above embodiments, each of L.sup.1, L.sup.2, and L.sup.3 may be independently selected from the group consisting of:
##STR00197##
[0185] each of Y.sup.1 and Y.sup.10 is independently C or N;
[0186] Y′ is selected from the group consisting of BR.sub.e, BR.sub.eR.sub.f, NR.sub.e, PR.sub.e, P(O)R.sub.e, O, S, Se, C═O, C═S, C═Se, C═NR.sub.e, C═CR.sub.eR.sub.f, S═O, SO.sub.2, CR.sub.eR.sub.f, SiR.sub.eR.sub.f, and GeR.sub.eR.sub.f;
[0187] R.sub.c represents mono, up to maximum allowed substitutions, or no substitution;
[0188] each R.sub.e, R.sub.f, and R.sub.c is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
[0189] any two of R, R′, R.sub.a, R.sub.b, and R.sub.c are optionally joined or fused to form a ring.
[0190] In some of the above embodiments, each of L.sup.2 and L.sup.3 may be independently
##STR00198##
[0191] In some of the above embodiments, each of L.sup.1, L.sup.2, and L.sup.3 may be different.
[0192] In some of the above embodiments, y may be 1 or 2.
[0193] In some of the above embodiments, z may be 1 or 2.
[0194] In some of the above embodiments, the compound has a first group and a second group with the first group not overlapping with the second group;
wherein at least 80% of the singlet excited state population of the lowest singlet excitation state are localized in the first group; and at least 80% of the triplet excited state population of the lowest triplet excitation state are localized in the second group.
[0195] In some of the above embodiments, the compound has a first group and a second group with the first group not overlapping with the second group;
wherein at least 85% of the singlet excited state population of the lowest singlet excitation state are localized in the first group; and at least 85% of the triplet excited state population of the lowest triplet excitation state are localized in the second group.
[0196] In some of the above embodiments, the compound has a first group and a second group with the first group not overlapping with the second group;
wherein at least 90% of the singlet excited state population of the lowest singlet excitation state are localized in the first group; and at least 90% of the triplet excited state population of the lowest triplet excitation state are localized in the second group.
[0197] In some of the above embodiments, the compound has a first group and a second group with the first group not overlapping with the second group;
wherein at least 95% of the singlet excited state population of the lowest singlet excitation state are localized in the first group; and at least 95% of the triplet excited state population of the lowest triplet excitation state are localized in the second group.
[0198] In some of the above embodiments, at least one of R.sub.a, R.sub.b, or R.sub.c comprises a chemical group containing at least three 6-membered aromatic rings that are not fused next to each other.
[0199] In some of the above embodiments, the emitter has the formula selected from the group consisting of Ir(L.sup.1)(L.sup.2)(L.sup.3), Ir(L.sup.1).sub.2(L.sup.2), and Ir(L.sup.1).sub.3.
[0200] In some of the above embodiments, a is about 0.05 eV. In some of the above embodiments, a is about 0.10 eV. In some of the above embodiments, a is about 0.15 eV.
[0201] In some of the above embodiments, b is about 0.35 eV. In some of the above embodiments, b is about 0.25 eV. In some of the above embodiments, b is about 0.15 eV. In some of the above embodiments, b is about 0.05 eV.
[0202] In some of the above embodiments, E.sub.T is no more than 2.60 eV. In some of the above embodiments, E.sub.T is no more than 2.55 eV. In some of the above embodiments, E.sub.T is no more than 2.50 eV.
[0203] It should be understood that ΔE can be experimentally measured through cyclic voltammetry (CV) or be obtained through DFT calculations. E.sub.T can be experimentally measured through photoluminescence spectroscopy or be obtained through DFT calculations. It should be understood that these calculations obtained with the DFT functional set and basis set as identified herein are theoretical. Computational composite protocols, such as Gaussian with the CEP-31G basis set used herein, rely on the assumption that electronic effects are additive and, therefore, larger basis sets can be used to extrapolate to the complete basis set (CBS) limit. However, when the goal of a study is to understand variations in HOMO, LUMO, S.sub.1, T.sub.1, bond dissociation energies, etc. over a series of structurally-related compounds, the additive effects are expected to be similar. Accordingly, while absolute errors from using the B3LYP may be significant compared to other computational methods, the relative differences between the HOMO, LUMO, S.sub.1, T.sub.1, and bond dissociation energy values calculated with B3LYP protocol are expected to reproduce experiment quite well. See, e.g., Hong et al., Chem. Mater. 2016, 28, 5791-98, 5792-93 and Supplemental Information (discussing the reliability of DFT calculations in the context of OLED materials). Moreover, with respect to iridium or platinum complexes that are useful in the OLED art, the data obtained from DFT calculations correlates very well to actual experimental data. See Tavasli et al., J. Mater. Chem. 2012, 22, 6419-29, 6422 (Table 3) (showing DFT calculations closely correlating with actual data for a variety of emissive complexes); Morello, G. R., J. Mol. Model. 2017, 23:174 (studying of a variety of DFT functional sets and basis sets and concluding the combination of B3LYP and CEP-31G is particularly accurate for emissive complexes).
[0204] In some embodiments, the compound having a first ligand L.sub.A of Formula I described herein can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, percent deuteration has its ordinary meaning and includes the percent of possible hydrogen atoms (e.g., positions that are hydrogen, deuterium, or halogen) that are replaced by deuterium atoms.
C. The OLEDs and the Devices of the Present Disclosure
[0205] In another aspect, the present disclosure also provides an OLED device comprising a first organic layer that contains a compound as disclosed in the above compounds section of the present disclosure.
[0206] In some embodiments, the OLED comprises an anode, a cathode, and a first organic layer disposed between the anode and the cathode. The first organic layer can comprise a compound comprising a first ligand L.sub.A of Formula I as described herein.
[0207] In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.
[0208] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host is an unfused substituent independently selected from the group consisting of C.sub.nH.sub.2n+1, OC.sub.nH.sub.2n+1, OAr.sub.1, N(C.sub.nH.sub.2n+1).sub.2, N(Ar.sub.1)(Ar.sub.2), CH═CH—C.sub.nH.sub.2n+1, C≡CC.sub.nH.sub.2n+1, Ar.sub.1, Ar.sub.1—Ar.sub.2, C.sub.nH.sub.2n—Ar.sub.1, or no substitution, wherein n is from 1 to 10; and wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
[0209] In some embodiments, the organic layer may further comprise a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, triazine, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).
[0210] In some embodiments, the host may be selected from the HOST Group consisting of:
##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206##
and combinations thereof.
[0211] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.
[0212] In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further comprise an acceptor; and wherein the acceptor may be selected from the group consisting of fluorescent emitter, delayed fluorescence emitter, and combination thereof.
[0213] In yet another aspect, the OLED of the present disclosure may also comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure.
[0214] In some embodiments, the emissive region can comprise a compound comprising a first ligand L.sub.A of Formula I as described herein.
[0215] In some embodiments, at least one of the anode, the cathode, or a new layer disposed over the organic emissive layer functions as an enhancement layer. The enhancement layer comprises a plasmonic material exhibiting surface plasmon resonance that non-radiatively couples to the emitter material and transfers excited state energy from the emitter material to non-radiative mode of surface plasmon polariton. The enhancement layer is provided no more than a threshold distance away from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer and the threshold distance is where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed over the enhancement layer on the opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on opposite side of the emissive layer from the enhancement layer but still outcouples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters the energy from the surface plasmon polaritons. In some embodiments this energy is scattered as photons to free space. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device such as but not limited to the organic waveguide mode, the substrate mode, or another waveguiding mode. If energy is scattered to the non-free space mode of the OLED other outcoupling schemes could be incorporated to extract that energy to free space. In some embodiments, one or more intervening layer can be disposed between the enhancement layer and the outcoupling layer. The examples for interventing layer(s) can be dielectric materials, including organic, inorganic, perovskites, oxides, and may include stacks and/or mixtures of these materials.
[0216] The enhancement layer modifies the effective properties of the medium in which the emitter material resides resulting in any or all of the following: a decreased rate of emission, a modification of emission line-shape, a change in emission intensity with angle, a change in the stability of the emitter material, a change in the efficiency of the OLED, and reduced efficiency roll-off of the OLED device. Placement of the enhancement layer on the cathode side, anode side, or on both sides results in OLED devices which take advantage of any of the above-mentioned effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLEDs according to the present disclosure may include any of the other functional layers often found in OLEDs.
[0217] The enhancement layer can be comprised of plasmonic materials, optically active metamaterials, or hyperbolic metamaterials. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material includes at least one metal. In such embodiments the metal may include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials where the medium as a whole acts differently than the sum of its material parts. In particular, we define optically active metamaterials as materials which have both negative permittivity and negative permeability. Hyperbolic metamaterials, on the other hand, are anisotropic media in which the permittivity or permeability are of different sign for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinguished from many other photonic structures such as Distributed Bragg Reflectors (“DBRs”) in that the medium should appear uniform in the direction of propagation on the length scale of the wavelength of light. Using terminology that one skilled in the art can understand: the dielectric constant of the metamaterials in the direction of propagation can be described with the effective medium approximation. Plasmonic materials and metamaterials provide methods for controlling the propagation of light that can enhance OLED performance in a number of ways.
[0218] In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and the sub-wavelength-sized features have sharp edges.
[0219] In some embodiments, the outcoupling layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles and in other embodiments the outcoupling layer is composed of a plurality of nanoparticles disposed over a material. In these embodiments the outcoupling may be tunable by at least one of varying a size of the plurality of nanoparticles, varying a shape of the plurality of nanoparticles, changing a material of the plurality of nanoparticles, adjusting a thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, varying a thickness of the enhancement layer, and/or varying the material of the enhancement layer. The plurality of nanoparticles of the device may be formed from at least one of metal, dielectric material, semiconductor materials, an alloy of metal, a mixture of dielectric materials, a stack or layering of one or more materials, and/or a core of one type of material and that is coated with a shell of a different type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles wherein the metal is selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles may have additional layer disposed over them. In some embodiments, the polarization of the emission can be tuned using the outcoupling layer. Varying the dimensionality and periodicity of the outcoupling layer can select a type of polarization that is preferentially outcoupled to air. In some embodiments the outcoupling layer also acts as an electrode of the device.
[0220] In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compounds section of the present disclosure.
[0221] In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer can comprise a compound comprising a first ligand L.sub.A of Formula I as described herein.
[0222] In some embodiments, the consumer product can be one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.
[0223] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
[0224] Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
[0225] The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
[0226] More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
[0227]
[0228] More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F.sub.4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
[0229]
[0230] The simple layered structure illustrated in
[0231] Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in
[0232] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP, also referred to as organic vapor jet deposition (OVJD)), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons are a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
[0233] Devices fabricated in accordance with embodiments of the present disclosure may
further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
[0234] Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25° C.), but could be used outside this temperature range, for example, from −40 degree C. to +80° C.
[0235] More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
[0236] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
[0237] In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
[0238] In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
[0239] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. application Ser. No. 15/700,352, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others). When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments.
[0240] In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter.
[0241] According to another aspect, a formulation comprising the compound described herein is also disclosed.
[0242] The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
[0243] In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, electron blocking material, hole blocking material, and an electron transport material, disclosed herein.
[0244] The present disclosure encompasses any chemical structure comprising the novel compound of the present disclosure, or a monovalent or polyvalent variant thereof. In other words, the inventive compound, or a monovalent or polyvalent variant thereof, can be a part of a larger chemical structure. Such chemical structure can be selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule (also known as supermolecule). As used herein, a “monovalent variant of a compound” refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a “polyvalent variant of a compound” refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond or bonds to the rest of the chemical structure. In the instance of a supramolecule, the inventive compound can also be incorporated into the supramolecule complex without covalent bonds.
D. Combination of the Compounds of the Present Disclosure with Other Materials
[0245] The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
a) Conductivity Dopants:
[0246] A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
[0247] Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.
##STR00207## ##STR00208## ##STR00209##
b) HIL/HTL:
[0248] A hole injecting/transporting material to be used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO.sub.x; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
[0249] Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
##STR00210##
[0250] Each of Ar.sup.1 to Ar.sup.9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
[0251] In one aspect, Ar.sup.1 to Ar.sup.9 is independently selected from the group consisting of:
##STR00211##
wherein k is an integer from 1 to 20; X.sup.101 to X.sup.108 is C (including CH) or N; Z.sup.101 is NAr.sup.1, O, or S; Ar.sup.1 has the same group defined above.
[0252] Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:
##STR00212##
wherein Met is a metal, which can have an atomic weight greater than 40; (Y.sup.101-Y.sup.102) is a bidentate ligand, Y.sup.101 and Y.sup.102 are independently selected from C, N, O, P, and S; L.sup.101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
[0253] In one aspect, (Y.sup.101-Y.sup.102) is a 2-phenylpyridine derivative. In another aspect, (Y.sup.101-Y.sup.102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc.sup.+/Fc couple less than about 0.6 V.
[0254] Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.
##STR00213## ##STR00214## ##STR00215## ##STR00216## ##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230##
c) EBL:
[0255] An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
d) Hosts:
[0256] The light emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
[0257] Examples of metal complexes used as host are preferred to have the following general formula:
##STR00231##
wherein Met is a metal; (Y.sup.103-Y.sup.104) is a bidentate ligand, Y.sup.103 and Y.sup.104 are independently selected from C, N, O, P, and S; L.sup.101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
[0258] In one aspect, the metal complexes are:
##STR00232##
wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
[0259] In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y.sup.103-Y.sup.104) is a carbene ligand.
[0260] In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
[0261] In one aspect, the host compound contains at least one of the following groups in the molecule:
##STR00233## ##STR00234##
wherein R.sup.101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20. X.sup.101 to X.sup.108 are independently selected from C (including CH) or N. Z.sup.101 and Z.sup.102 are independently selected from NR.sup.101, O, or S.
[0262] Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, U.S. Pat. No. 9,466,803,
##STR00235## ##STR00236## ##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247## ##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## ##STR00259## ##STR00260## ##STR00261## ##STR00262##
e) Additional Emitters:
[0263] One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
[0264] Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.
##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267## ##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## ##STR00274## ##STR00275## ##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280## ##STR00281## ##STR00282## ##STR00283## ##STR00284## ##STR00285## ##STR00286##
f) HBL:
[0265] A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
[0266] In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
[0267] In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
##STR00287##
wherein k is an integer from 1 to 20; L.sup.101 is another ligand, k′ is an integer from 1 to 3.
g) ETL:
[0268] Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
[0269] In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
##STR00288##
wherein R.sup.101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar.sup.1 to Ar.sup.3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X.sup.101 to X.sup.108 is selected from C (including CH) or N.
[0270] In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
##STR00289##
wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L.sup.101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
[0271] Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,
##STR00290## ##STR00291## ##STR00292## ##STR00293## ##STR00294## ##STR00295## ##STR00296## ##STR00297## ##STR00298##
h) Charge Generation Layer (CGL)
[0272] In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
[0273] In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. The minimum amount of hydrogen of the compound being deuterated is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
[0274] It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.
E. Experimental Data
[0275] Synthesis of a Comparative Compound
##STR00299## ##STR00300##
[0276] Step 1
Synthesis of 4-bromo-3′,5′-di-tert-butyl-3,5-dimethyl-1,1′-biphenyl
[0277] Potassium carbonate (17.1 g, 124 mmol) in water (10 ml) was added to (3,5-di-tert-butylphenyl) boronic acid (7.72 g, 33.0 mmol) and 2-bromo-5-iodo-1,3-dimethylbenzene (10.0 g, 32.2 mmol) in 1,4-dioxane (70.0 ml). The resulting mixture was degassed for 20 min. by nitrogen. Pd(Ph.sub.3P).sub.4 (1.96 g, 1.696 mmol) was then added, and the reaction mixture was further degassed for 10 min. The reaction mixture was then heated at 105° C. for 18 h. The reaction mixture was cooled to room temperature. The solvent was removed in vacuo, then the resultant brown residue was purified by column chromatography to give 4-bromo-3′,5′-di-tert-butyl-3,5-dimethyl-1,1′-biphenyl (9.68 g, 24.73 mmol, 77% yield) as a colorless solid
[0278] Step 2
Synthesis of (3′,5′-di-tert-butyl-3,5-dimethyl-[1,1′-biphenyl]-4-yl) boronic acid
[0279] In a 2-necked round bottomed flask under nitrogen, 4-bromo-3′,5′-di-tert-butyl-3,5-dimethyl-1,1′-biphenyl (9.65 g, 24.66 mmol) was dissolved in anhydrous Tetrahydrofuran (80 ml) and the reaction mixture was cooled to −78° C. BuLi (11.5 ml, 28.8 mmol) was added dropwise so that the mixture did not heat above −60° C. The mixture was stirred for 20 min then triisopropyl borate (8.4 ml, 36.2 mmol) was added dropwise. The mixture was stirred at −78° C. for 1 h then allowed to warm to room temperature and stirred for 3 h. The mixture was cooled to 0° C. then 1 M HCl (40 mL) was added, and the mixture was stirred for 5 min before warming to room temperature.
Brine (50 mL) was added and the THF phase was separated. The aqueous phase was extracted with THF (2×100 mL). The combined organic phases were washed with brine (2×40 mL), dried over Na.sub.2SO.sub.4, filtered, and evaporated to give (3′,5′-di-tert-butyl-3,5-dimethyl-[1,1′-biphenyl]-4-yl) boronic acid as a brown oil which was used crude in the next step.
[0280] Step 3
Synthesis of 8-(4-(3′,5′-di-tert-butyl-3,5-dimethyl-[1,1′-biphenyl]-4-yl)-5-methylpyridin-2-yl)-2-methylbenzofuro[2,3-b] pyridine
[0281] Potassium phosphate tribasic hydrate (5.28 g, 24.87 mmol), (3′,5′-di-tert-butyl-3,5-dimethyl-[1,1′-biphenyl]-4-yl) boronic acid (8.34 g, 24.65 mmol) and 8-(4-chloro-5-methylpyridin-2-yl)-2-methylbenzofuro[2,3-b] pyridine (2.61 g, 8.45 mmol) were dissolved in toluene (45.0 ml) and water (1.5 ml). The resulting mixture was degassed for 20 min, SPhos Pd G2 (0.189 g, 0.262 mmol) was then added, and the reaction mixture was further degassed for 10 min. The reaction mixture was then heated at 110° C. for 18 h. The solvent was removed in vacuo to leave a brown residue. The crude product was purified by column chromatography to give the product as a colorless solid. Crystallization from methanol provided of 8-(4-(3′,5′-di-tert-butyl-3,5-dimethyl-[1,1′-biphenyl]-4-yl)-5-methylpyridin-2-yl)-2-methylbenzofuro[2,3-b] pyridine (2.38 g, 4.18 mmol, 49.5% yield) as a colorless solid.
[0282] Step 4
Di-μ-chloro-tetrakis [κ2(C2, N)-(5-(2,2-dimethylpropyl-1,1-d.SUB.2.)-2-(4-(methyl-d.SUB.3.)-phenyl-2′-yl) pyridin-1-yl] diiridium (III)
[0283] A 5 L 4-neck flask was charged with 2-ethoxyethanol (2250 mL) and DIUF water (750 mL) and the mixture sparged with nitrogen for 15 minutes. Iridium (III) chloride hydrate (205.7 g, 650 mmol, 1.0 equiv) and 5-(2,2-dimethylpropyl-1,1-d.sub.2)-2-(4-(methyl-d.sub.3)-phenyl) pyridine (350 g, 1430 mmol, 2.2 equiv) were added then the reaction mixture heated at reflux for 65 hours. The reaction mixture was cooled to room temperature, the solid filtered and washed thoroughly with methanol (400 mL). The solid was air-dried to give di-μ-chloro-tetrakis [κ2(C2, N)-(5-(2,2-dimethyl-propyl-1,1-d.sub.2)-2-(4-(methyl-d.sub.3)-phenyl-2′-yl) pyridin-1-yl] diiridium (III) (338.7 g, 73% yield) as a dark yellow solid.
[0284] Step 5
[Ir(5-(2,2-dimethylpropyl-1,1-d.SUB.2.)-2-(4-(methyl-d.SUB.3.)-phenyl-2′-yl)pyridin(-1H)).SUB.2.-MeOH).SUB.2.] trifluoromethanesulfonate
[0285] A 22 L 4-neck flask was charged with di-μ-chloro-tetrakis[κ2(C2,N)-(5-(2,2-dimethylpropyl-1,1-d.sub.2)-2-(4-(methyl-d.sub.3)-phenyl-2′-yl)pyridin-1-yl]diiridium(III) (338.7 g, 237 mmol, 1.0 equiv) in dichloromethane (8300 mL). The flask was wrapped with a black plastic bag to exclude light and a solution of silver trifluoromethanesulfonate (146 g, 568 mmol, 2.37 equiv) in methanol (1500 mL) added. The reaction mixture was stirred at room temperature under nitrogen for 20 hours. The reaction mixture was filtered through a pad of silica gel (430 g) topped with Celite (100 g), rinsing thoroughly with dichloromethane (2000 mL). The filtrate was concentrated under reduced pressure and the residue dried in a vacuum oven to give [Ir(5-(2,2-dimethyl-propyl-1,1-d.sub.2)-2-(4-(methyl-d.sub.3)-phenyl-2′-yl) pyridine(-1H)).sub.2(MeOH).sub.2] trifluoro-methane sulfonate (391.1 g, 92% yield) as a yellow solid.
[0286] Step 6
Mer-Bis[5-(2,2-dimethylpropyl-1,1-d.SUB.2.)-2-(4-(methyl-d.SUB.3.)-phenyl-2′-yl)pyridin-1-yl]-[8-((4-(3′,5′-di-tert-butyl)-3,5-dimethyl-[1,1′-biphenyl]-4-yl)-(5-methyl-pyridin-2-yl)-1-yl)-2-methylbenzofuro[2,3-b]pyridin-7′-yl]iridium(III) (mer-2021-ADS-UDC-Ir1030)
[0287] A 250 mL 4-neck round bottom flask, equipped with a stir bar, condenser and thermowell, was charged with [Ir(5-(2,2-dimethylpropyl-1,1-d.sub.2)-2-(4-(methyl-d.sub.3)-phenyl)-2′-yl)pyridin(-1H)).sub.2(MeOH).sub.2] trifluoromethane-sulfonate (1.5 g, 1.7 mmol, 1.0 equiv), 8-(4-(3′,5′-di-tert-butyl)-3,5-dimethyl-[1,1′-biphenyl]-4-yl)-5-methylpyridin-2-yl)-2-methylbenzofuro[2,3-b]-pyridine (0.942 g, 1.7 mmol, 1.0 equiv) and acetone (56 mL). Triethylamine (0.69 mL, 5.0 mmol, 3.0 equiv) was added then the reaction mixture heated at 50° C. overnight with good stirring. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The solid was dissolved in dichloromethane (20 mL) and filtered through a short pad (1-2 inches) of Celite®. The recovered material was triturated with a minimum volume of methanol and filtered. The solid was dried overnight in a vacuum oven at 60° C. to give mer-11 (˜1.3 g) as an orange solid.
[0288] Step 7
Bis[(5-(2,2-dimethylpropyl-1,1-d.SUB.2.)-2-(4-(methyl-d.SUB.3.)-phenyl)-2′-yl) pyridin-1-yl] [8-((4-(3′,5′-di-tert-butyl)-3,5-dimethyl-[1,1′-biphenyl]-4-yl)-(5-methyl-pyridin-2-yl)-1-yl)-2-methylbenzofuro[2,3-b] pyridin-7′-yl] iridium (III)(12)
[0289] Mer-11 was subjected to photolysis to yield the Comparison Compound (12).
[0290] Synthesis of an Inventive Compound
##STR00301## ##STR00302## ##STR00303##
[0291] Step 1′
8-Methoxy-2-methylbenzofuro[2,3-b] pyridine (27.5 g, 129 mmol) and pyridine hydrochloride (95 g, 822 mmol) were charged into the reaction flask and it the mixture was heated in an oil bath set at 190-200° C. for 18 hours. The reaction mixture was cooled to approximately 120° C., then 400 mL of water was carefully added to the reaction mixture. The reaction mixture was then cooled to room temperature. This aqueous mixture was basified using saturated aqueous sodium bicarbonate. 2-Methylbenzofuro[2,3-b]pyridin-8-ol (tan solid, 25 g, 95% yield) was isolated via filtration then was dried under vacuum.
[0292] Step 2′
2-Methylbenzofuro[2,3-b] pyridin-8-ol (14 g, 70.3 mmol) and pyridine (14.21 ml, 176 mmol) were cold in the ice bath and trifluoromethanesulfonic anhydride (17.70 ml, 105 mmol) was added. The reaction mixture was stirred at ambient temperature for 3 h, diluted with ethyl acetate and washed with sat. NaHCO3. The organic layer was dried over sodium sulfate, filtered, and evaporated. The residue was subjected to column chromatography on silica gel, eluted with DCM, providing 20 g (88% yield) of 2-methylbenzofuro[2,3-b] pyridin-8-yl trifluoromethanesulfonate.
[0293] Step 3′
2-Methylbenzofuro[2,3-b]pyridin-8-yl trifluoromethanesulfonate (6.0 g, 18.1 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (6.9 g, 1.5 eq.), potassium acetate (5.3 g, 3 eq.), tricyclohexylphosphane tetrafluoroborate salt (0.5 g, 8 mol. %) and Pd.sub.2(dba).sub.3 (2 mol %) were suspended in 50 mL of dioxane and 5 mL of water. The reaction mixture was degassed and heated at 100° C. for 18 h. The reaction mixture was cooled down, diluted with water (500 mL), and extracted with EtOAc. The organic fractions were combined and evaporated. The residue was subjected to column chromatography on silica gel, eluted with heptanes/ethyl acetate mixture, providing 2-methyl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzofuran[2,3-b] pyridine as white solid (4.3 g, 77% yield).
[0294] Step 4′
2-Methyl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzofuran[2,3-b] pyridine (7.5 g, 24.26 mmol), 2,4-dibromo-5-methylpyridine (6.09 g, 24.26 mmol) and potassium carbonate (10.06 g, 72.8 mmol) were suspended in the mixture of MeCN (150 mL) and MeOH (75 mL), added Pd (PPh.sub.3).sub.4 (0.561 g, 0.485 mmol). The reaction mixture was degassed and heated at 70° C. for 18 h. The reaction mixture was cooled down, diluted with water (500 mL), and extracted with EtOAc. The organic fractions were combined and evaporated. The residue was subjected to column chromatography on silica gel, eluted with DCM/EtOAc 9/1 (v/v), providing 8-(4-bromo-5-methylpyridin-2-yl)-2-methylbenzofuro[2,3-b] pyridine (7.1 g, 20.10 mmol, 83% yield) as a white solid.
[0295] Step 5′
2-Bromo-5-chloro-1,3-dimethylbenzene (5 g, 22.78 mmol) was dissolved in 50 mL of dry THF and cooled in IPA/dry ice bath. Added nbutyllithium in hexanes 1.4 mol. solution (25.6 ml, 41.0 mmol) via canula, stirred 1 h at −78°, then added 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.42 ml, 45.6 mmol) via syringe, stirred overnight at room temperature. The reaction mixture was diluted with water and extracted with ethyl acetate. Organic fractions were combined, filtered, and evaporated. Purification by column chromatography on silica gel column eluted with heptanes/ethyl acetate 9/1 (v/v), provided 2-(4-chloro-2,6-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane as white solid (4.0 g, 66% yield).
[0296] Step 6′
2-(4-Chloro-2,6-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.1 g, 30 mmol) and 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (12 g, 1.6 eq.), potassium acetate (8.9 g, 3 eq.) was suspended in dioxane with 400 mg of Pd.sub.2dba.sub.3 and 750 mg of Xphos. The reaction mixture was degassed and heated to 95° for 12 h. The reaction mixture was cooled down, diluted with water, and extracted with ethyl acetate. Organic fractions were combined, filtered, and evaporated. Purification by column chromatography on silica gel column provided 2,2′-(2,6-dimethyl-1,4-phenylene) bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) as white crystalline material (6.5 g, 60% yield).
[0297] Step 7′
2,2′-(2,6-Dimethyl-1,4-phenylene) bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (3.14 g, 8.8 mmol), 2,4-di-tert-butyl-6-chloro-1,3,5-triazine (2.0 g, 8.8 mmol), potassium carbonate (3.64 g, 3 eq.) and Pd (PPh.sub.3).sub.4 (2 mol %) were suspended in 100 ml of DME with 2% of water. The reaction mixture was degassed and heated to 95° for 12 h. The reaction mixture was cooled down to room temperature, diluted with water and extracted with ethyl acetate. Organic fractions were combined, dried over sodium sulfate, filtered, and evaporated. The residue was subjected to column chromatography on silica gel, providing 2.8 g of 2,4-di-tert-butyl-6-(3,5-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)-1,3,5-triazine (75% yield).
[0298] Step 8′
Iridium triflate complex (7.0 g 7.85 mmol) and 8-(4-bromo-5-methylpyridin-2-yl)-2-methylbenzofuro[2,3-b] pyridine (5.0 g, 14 mmol) was suspended in 180 mL of methanol; the reaction mixture was degassed and heated to reflux for 6 days. The reaction mixture was evaporated, the crude product was subjected to column chromatography on silica gel, eluted with mixture toluene/DCM/heptanes, providing iridium complex bromide (4.0 g, 50% yield).
[0299] Step 9′
Iridium complex (3.0 g, 2.9 mmol), boronic ester (2.5 g, 2 eq.), potassium phosphate tribasic monohydrate (2.0 g, 3 eq.) and Sphos Gen 2 catalyst (2 mol %) were suspended in toluene 100 mL/water 3 mL. The reaction mixture was degassed and heated to reflux for 12 h. The organic layer was separated, washed with water, and evaporated. Purification by column chromatography on silica gel column, eluted with toluene/heptanes/DCM 4/3/3 (v/v/v) followed by crystallization from EtOH provided target compound as bright yellow crystalline material (600 mg, 15% yield).
Device Examples
[0300] All example devices were fabricated by high vacuum (<10.sup.−7 Torr) thermal evaporation. The anode electrode was 800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of Liq (8-hydroxyquinoline lithium) followed by 1,000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H.sub.2O and O.sub.2) immediately after fabrication with a moisture getter incorporated inside the package. The organic stack of the device examples consisted of sequentially, from the ITO Surface: 100 Å of HAT-CN as the hole injection layer (HIL); 400 Å of HTM as a hole transporting layer (HTL); emissive layer (EML) with thickness 400 Å. Emissive layer containing H-host (H1): E-host (H2) in 6:4 ratio and 12 weight % of green emitter. 350 Å of Liq (8-hydroxyquinoline lithium) doped with 35% of ETM as the ETL. Table 1 shows the schematic device structure. The chemical structures of the device materials are shown below.
##STR00304## ##STR00305## ##STR00306##
[0301] Upon fabrication the devices were measured for EL, JVL and lifetested at DC 80 mA/cm.sup.2. LT97 at 9,000 nits was calculated from 80 mA/cm.sup.2 LT data assuming acceleration factor 1.8. Voltage, LE, EQE, and PE were tested at DC 10 mA/cm.sup.2. Device performance is shown in the Table 2.
TABLE-US-00002 TABLE 1 Schematic Device Structure Layer Material Thickness [Å] Anode ITO 800 HIL HAT-CN 100 HTL HTM 400 EBL EBM 50 Green EML H1:H2:example dopant 400 ETL Liq:ETM 35% 350 EIL Liq 10 Cathode Al 1,000
TABLE-US-00003 TABLE 2 Device performance 1931 CIE At 10 mA/cm.sup.2 At 9K nits λ max FWHM Valtage LE EQE PE calculated 97% Emitter 12% x y [nm] [nm] [V] [cd/A] [%] [lm/W] [h] Inventive Example 0.372 0.609 533 61 4.6 97.8 25.5 66.5 1.8* Comparative Example 0.355 0.622 530 58 4.6 97.7 25.3 66.5 1 *Normalized to comparative example.
[0302] The above data shows that the device lifetime of Inventive Example is almost double the Comparative Example, which is beyond any value that could be attributed to experimental error and the observed improvement is significant and unexpected. Without being bound by any theory, it is presumed that the triazine moiety in the inventive example may promote the electron stability of the dopant in the OLED device.