Organic light emitting materials
09748500 · 2017-08-29
Assignee
Inventors
Cpc classification
C09K2211/185
CHEMISTRY; METALLURGY
C09K2211/1029
CHEMISTRY; METALLURGY
C09K2211/1088
CHEMISTRY; METALLURGY
International classification
Abstract
Phosphorescent iridium complexes comprising multi-alkyl-substituted aza-DBF and 2-phenylpyridine ligands is disclosed. These complexes are useful as emitters for phosphorescent OLEDs.
Claims
1. A compound having the formula Ir(L.sub.A).sub.n(L.sub.B).sub.3-n, having the structure: ##STR00348## wherein R.sub.a, R.sub.b, and R.sub.c each independently represent mono-, di-, tri-, tetra-substitution, or no substitution; wherein X is O, S, or Se; wherein n is an integer from 1 to 3; wherein R.sub.a, R.sub.b, and R.sub.c are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein (i) R.sup.1 and R.sup.4 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated, and R.sup.2 and R.sup.3 are hydrogen, or (ii) R.sup.1, R.sup.3, and R.sup.4 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated and R.sup.2 is hydrogen; and wherein any two substituents among R.sub.a to R.sub.c or R.sup.3 and R.sup.4 in option (ii) are optionally linked together to form a ring.
2. The compound of claim 1, wherein, when R.sup.1, R.sup.3, and R.sup.4 are alkyl or cycloalkyl, each is independently selected from the group consisting of 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, cyclopentyl, cyclohexyl, and combinations thereof, wherein each group is optionally partially or fully deuterated.
3. The compound of claim 1, wherein n is 1.
4. The compound of claim 1, wherein X is O.
5. The compound of claim 1, wherein R.sup.1 and R.sup.4 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated, and R.sup.2 and R.sup.3 are hydrogen.
6. The compound of claim 1, wherein R.sup.1, R.sup.3, and R.sup.4 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated and R.sup.2 is hydrogen.
7. The compound of claim 1, wherein the total carbon number of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are at least 3.
8. The compound of claim 1, wherein R.sub.a, R.sub.b, and R.sub.c are each independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
9. The compound of claim 1, wherein L.sub.A has a structure according to the following formula: ##STR00349## and is selected from the group consisting of L.sub.A1, L.sub.A1, L.sub.A9, L.sub.A15, L.sub.A21, L.sub.A27, L.sub.A33, L.sub.A39, L.sub.A45, L.sub.A51, L.sub.A57, L.sub.A63, L.sub.A69, L.sub.A75, L.sub.A81, L.sub.A87, L.sub.A93, L.sub.A100, L.sub.A106, L.sub.A109, L.sub.A110, L.sub.A113, L.sub.A122, L.sub.A123, L.sub.A124, L.sub.A133, L.sub.A139, L.sub.A145, L.sub.A151, L.sub.A157, L.sub.A163, L.sub.A169, L.sub.A175, L.sub.A181, L.sub.A187, L.sub.A1193, L.sub.A205, L.sub.A211, L.sub.A217, L.sub.A223, L.sub.A229, L.sub.A237, L.sub.A238, L.sub.A242, L.sub.A245, L.sub.A248, L.sub.A250, L.sub.A255, L.sub.A256, L.sub.A260, L.sub.A263, L.sub.A266, L.sub.A273, L.sub.A274, L.sub.A278, L.sub.A281, L.sub.A284, L.sub.A286, L.sub.A291, L.sub.A292, L.sub.A296, L.sub.A299, L.sub.A304, L.sub.A305, L.sub.A308, L.sub.A312, L.sub.A314, L.sub.A315, L.sub.A317, L.sub.A321-L.sub.A339, L.sub.A343-L.sub.A351, L.sub.A359, L.sub.A363, L.sub.A368, L.sub.A372, L.sub.A377, L.sub.A381, L.sub.A386, L.sub.A390, L.sub.A393, L.sub.A396, L.sub.A402, L.sub.A408, L.sub.A415, L.sub.A421, L.sub.A427, L.sub.A431 and L.sub.A434-L.sub.A438, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are as defined in Tables 1A and 1B shown below: TABLE-US-00006 TABLE 1A Ligand L.sub.A R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 L.sub.A3 CH.sub.3 H H CH.sub.3 H H H H L.sub.A9 CD.sub.3 H H CD.sub.3 H H H H L.sub.A15 CH.sub.3 H H CH.sub.3 CH.sub.3 H H H L.sub.A21 CD.sub.3 H H CD.sub.3 CD.sub.3 H H H L.sub.A27 CH.sub.3 H H CH.sub.3 H CH.sub.3 H H L.sub.A33 CD.sub.3 H H CD.sub.3 H CD.sub.3 H H L.sub.A39 CH.sub.3 H H CH.sub.3 H H CH.sub.3 H L.sub.A45 CD.sub.3 H H CD.sub.3 H H CD.sub.3 H L.sub.A51 CH.sub.3 H H CH.sub.3 H H H CH.sub.3 L.sub.A57 CD.sub.3 H H CD.sub.3 H H H CD.sub.3 L.sub.A63 CH.sub.3 H H CH.sub.3 CH(CH.sub.3).sub.2 H H H L.sub.A69 CD.sub.3 H H CD.sub.3 CD(CD.sub.3).sub.2 H H H L.sub.A75 CH.sub.3 H H CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A81 CD.sub.3 H H CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A87 CH.sub.3 H H CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A93 CD.sub.3 H H CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A100 CH.sub.2CH.sub.3 H H CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A106 CH.sub.3 H H CH.sub.2CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A109 CD.sub.2CD.sub.3 H H CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A110 CD.sub.2CD.sub.3 H H CD.sub.3 H CD(CH.sub.3).sub.2 H H L.sub.A113 CH.sub.2CH.sub.3 H H CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A119 CH.sub.3 H H CH.sub.2CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A122 CD.sub.2CD.sub.3 H H CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A123 CD.sub.3 H H CD.sub.2CH.sub.3 H H CD(CH.sub.3).sub.2 H L.sub.A124 CD.sub.3 H H CD.sub.2CH.sub.3 H H H CD.sub.3 L.sub.A127 CH.sub.3 H H CH.sub.3 H H H CH(CH.sub.3).sub.2 L.sub.A133 CD.sub.3 H H CD.sub.3 H H H CD(CD.sub.3).sub.2 L.sub.A139 CH.sub.3 H H CH.sub.3 H CH.sub.2CH(CH.sub.3).sub.2 H H L.sub.A145 CD.sub.3 H H CD.sub.3 H CD.sub.2CH(CH.sub.3).sub.2 H H L.sub.A151 CH.sub.3 H H CH.sub.3 H H CH.sub.2CH(CH.sub.3).sub.2 H L.sub.A157 CD.sub.3 H H CD.sub.3 H H CD.sub.2CH(CH.sub.3).sub.2 H L.sub.A163 CH.sub.3 H H CH.sub.3 CH.sub.3 CH.sub.3 H H L.sub.A169 CD.sub.3 H H CD.sub.3 CD.sub.3 CD.sub.3 H H L.sub.A175 CH.sub.3 H H CH.sub.3 H CH.sub.3 CH.sub.3 H L.sub.A181 CD.sub.3 H H CD.sub.3 H CD.sub.3 CD.sub.3 H L.sub.A187 CH.sub.3 H H CH.sub.3 H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A193 CD.sub.3 H H CD.sub.3 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A199 CH.sub.3 H H CH.sub.3 H CH.sub.3 CH(CH.sub.3).sub.2 H L.sub.A205 CD.sub.3 H H CD.sub.3 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A211 CH.sub.3 H H CH.sub.3 H CH.sub.2CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A217 CD.sub.3 H H CD.sub.3 H CD.sub.2CH(CH.sub.3).sub.2 CD.sub.3 H L.sub.A223 CH.sub.3 H H CH.sub.3 H CH.sub.3 CH.sub.2CH(CH.sub.3).sub.2 H L.sub.A229 CD.sub.3 H H CD.sub.3 H CD.sub.3 CD.sub.2CH(CH.sub.3).sub.2 H L.sub.A237 CH(CH.sub.3).sub.2 H H CH.sub.3 H H H H L.sub.A238 CH.sub.3 H H CH(CH.sub.3).sub.2 H H H H L.sub.A242 CH(CH.sub.3).sub.2 H H CH(CH.sub.3).sub.2 H H H H L.sub.A245 CD(CH.sub.3).sub.2 H H CD.sub.3 H H H H L.sub.A248 CD.sub.3 H H CD(CH.sub.3).sub.2 H H H H L.sub.A250 CD(CH.sub.3).sub.2 H H CD(CH.sub.3).sub.2 H H H H L.sub.A255 CH(CH.sub.3).sub.2 H H CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A256 CH.sub.3 H H CH(CH.sub.3).sub.2 H CH(CH.sub.3).sub.2 H H L.sub.A260 CH(CH.sub.3).sub.2 H H CH(CH.sub.3).sub.2 H CH(CH.sub.3).sub.2 H H L.sub.A263 CD(CH.sub.3).sub.2 H H CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A266 CD.sub.3 H H CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 H H L.sub.A268 CD(CH.sub.3).sub.2 H H CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 H H L.sub.A273 CH(CH.sub.3).sub.2 H H CH.sub.3 H CH.sub.3 CH(CH.sub.3).sub.2 H L.sub.A274 CH.sub.3 H H CH(CH.sub.3).sub.2 H CH.sub.3 CH(CH.sub.3).sub.2 H L.sub.A278 CH(CH.sub.3).sub.2 H H CH(CH.sub.3).sub.2 H CH.sub.3 CH(CH.sub.3).sub.2 H L.sub.A281 CD(CH.sub.3).sub.2 H H CD.sub.3 H CD.sub.3 CH(CH.sub.3).sub.2 H L.sub.A284 CD.sub.3 H H CD(CH.sub.3).sub.2 H CD.sub.3 CH(CH.sub.3).sub.2 H L.sub.A286 CD(CH.sub.3).sub.2 H H CD(CH.sub.3).sub.2 H CD.sub.3 CH(CH.sub.3).sub.2 H L.sub.A291 CH(CH.sub.3).sub.2 H H CH.sub.3 H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A292 CH.sub.3 H H CH(CH.sub.3).sub.2 H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A296 CH(CH.sub.3).sub.2 H H CH(CH.sub.3).sub.2 H CD(CH.sub.3).sub.2 CH.sub.3 H L.sub.A299 CD(CH.sub.3).sub.2 H H CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H L.sub.A302 CD.sub.3 H H CD(CH.sub.3).sub.2 H CD(CH.sub.3).sub.2 CD.sub.3 H L.sub.A304 CD(CH.sub.3).sub.2 H H CD(CH.sub.3).sub.2 H CD(CH.sub.3).sub.2 CD.sub.3 H L.sub.A305 CD(CH.sub.3).sub.2 H H CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A308 CD.sub.3 H H CD.sub.3 H CD(CH.sub.3).sub.2 H H L.sub.A312 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H H H L.sub.A314 CH.sub.3 H CH.sub.3 CH.sub.3 H H H H L.sub.A315 H CH.sub.3 CH.sub.3 CH.sub.3 H H H H L.sub.A317 CD.sub.3 H CD.sub.3 CD.sub.3 H H H H L.sub.A321 CD.sub.3 H CD.sub.3 CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A322 CD.sub.3 H CD.sub.3 CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A323 CD.sub.3 H CD.sub.3 CD.sub.3 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A324 CD.sub.3 H CD.sub.3 CD.sub.3 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A325 CD.sub.3 H CD.sub.3 CD(CH.sub.3).sub.2 H H H H L.sub.A326 CD.sub.3 H CD.sub.3 CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 H H L.sub.A327 CD.sub.3 H CD.sub.3 CD(CH.sub.3).sub.2 H H CD(CD.sub.3).sub.2 H L.sub.A328 CD.sub.3 H CD.sub.3 CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A329 CD.sub.3 H CD.sub.3 CD(CH.sub.3).sub.2 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A330 CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H H H H L.sub.A331 CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A332 CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A333 CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A334 CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A335 CD.sub.3 H CD(CH.sub.3).sub.2 CD(CH.sub.3).sub.2 H H H H L.sub.A336 CD.sub.3 H CD(CH.sub.3).sub.2 CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 H H L.sub.A337 CD.sub.3 H CD(CH.sub.3).sub.2 CD(CH.sub.3).sub.2 H H CD(CD.sub.3).sub.2 H L.sub.A338 CD.sub.3 H CD(CH.sub.3).sub.2 CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A339 CD.sub.3 H CD(CH.sub.3).sub.2 CD(CH.sub.3).sub.2 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A343 CD(CH.sub.3).sub.2 H CD.sub.3 CD.sub.3 H H H H L.sub.A344 CD(CH.sub.3).sub.2 H CD.sub.3 CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A345 CD(CH.sub.3).sub.2 H CD.sub.3 CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A346 CD(CH.sub.3).sub.2 H CD.sub.3 CD.sub.3 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A347 CD(CH.sub.3).sub.2 H CD.sub.3 CD.sub.3 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A348 CD.sub.3 H H CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 H H L.sub.A349 CD.sub.3 H H CD(CH.sub.3).sub.2 H H CD(CD.sub.3).sub.2 H L.sub.A350 CD.sub.3 H H CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A351 CD.sub.3 H H CD(CH.sub.3).sub.2 H CD.sub.3 CD(CD.sub.3).sub.2 H TABLE-US-00007 TABLE 1B Ligand L.sub.A R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 L.sub.A359
10. The compound of claim 1, wherein L.sub.B is selected from the group consisting of: ##STR00376## ##STR00377## ##STR00378## ##STR00379## ##STR00380## ##STR00381## ##STR00382## ##STR00383## ##STR00384## ##STR00385## ##STR00386## ##STR00387## ##STR00388## ##STR00389## ##STR00390## ##STR00391## ##STR00392## ##STR00393## ##STR00394## ##STR00395## ##STR00396## ##STR00397## ##STR00398## ##STR00399## ##STR00400## ##STR00401## ##STR00402## ##STR00403##
11. The compound of claim 1, wherein the compound is selected from the group consisting of: ##STR00404## ##STR00405## ##STR00406## ##STR00407## ##STR00408## ##STR00409## ##STR00410## ##STR00411## ##STR00412## ##STR00413## ##STR00414## ##STR00415## ##STR00416## ##STR00417## ##STR00418## ##STR00419## ##STR00420## ##STR00421## ##STR00422## ##STR00423## ##STR00424## ##STR00425##
12. A device comprising one or more organic light emitting devices, at least one of the one or more organic light emitting devices comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, the organic layer comprising a compound having a formula Ir(L.sub.A).sub.n(L.sub.B).sub.3-n, having the structure: ##STR00426## wherein R.sub.a, R.sub.b, and R.sub.c each independently represent mono-, di-, tri-, tetra-substitution, or no substitution; wherein X is O, S, or Se; wherein n is an integer from 1 to 3; wherein R.sub.a, R.sub.b, and R.sub.c are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein (i) R.sup.1 and R.sup.4 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated, and R.sup.2 and R.sup.3 are hydrogen, or (ii) R.sup.1, R.sup.3, and R.sup.4 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated and R.sup.2 is hydrogen; and wherein any two substituents among R.sup.1 to R.sup.4 and R.sub.a to R.sub.c are optionally linked together to form a ring.
13. The device of claim 12, wherein the device is selected from the group consisting of a consumer product, an electronic component module, an organic light-emitting device, and a lighting panel.
14. The device of claim 12, wherein the organic layer is an emissive layer and the compound is an emissive dopant or a non-emissive dopant.
15. The device of claim 12, wherein the organic layer further comprises 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.
16. The device of claim 12, wherein the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
17. The device of claim 12, wherein the organic layer further comprises a host and the host is selected from the group consisting of: ##STR00427## ##STR00428## ##STR00429## ##STR00430## and combinations thereof.
18. A formulation comprising a compound having a formula Ir(L.sub.A).sub.n(L.sub.B).sub.3-n, having the structure: ##STR00431## wherein R.sub.a, R.sub.b, and R.sub.c each independently represent mono-, di-, tri-, tetra-substitution, or no substitution; wherein X is O, S, or Se; wherein n is an integer from 1 to 3; wherein R.sub.a, R.sub.b, and R.sub.c are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfanyl, sulfonyl, phosphino, and combinations thereof; wherein (i) R.sup.1 and R.sup.4 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated, and R.sup.2 and R.sup.3 are hydrogen, or (ii) R.sup.1, R.sup.3, and R.sup.4 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated and R.sup.2 is hydrogen; and wherein any two substituents among R.sup.1 to R.sup.4 and R.sub.a to R.sub.c are optionally linked together to form a ring.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
DETAILED DESCRIPTION
(4) 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.
(5) 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.
(6) 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”), which 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.
(7)
(8) 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.
(9)
(10) The simple layered structure illustrated in
(11) 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
(12) 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), 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 OVJD. 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 is a preferred range. Materials with asymmetric structures may have better solution processibility 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.
(13) Devices fabricated in accordance with embodiments of the present invention 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.
(14) Devices fabricated in accordance with embodiments of the invention 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 invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. 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, 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, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, 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 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.
(15) 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.
(16) The term “halo,” “halogen,” or “halide” as used herein includes fluorine, chlorine, bromine, and iodine.
(17) The term “alkyl” as used herein contemplates both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, the alkyl group may be optionally substituted.
(18) The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.
(19) The term “alkenyl” as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted.
(20) The term “alkynyl” as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.
(21) The terms “aralkyl” or “arylalkyl” as used herein are used interchangeably and contemplate an alkyl group that has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted.
(22) The term “heterocyclic group” as used herein contemplates aromatic and non-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also means heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 or 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydropyran, tetrahydropyran, and the like. Additionally, the heterocyclic group may be optionally substituted.
(23) The term “aryl” or “aromatic group” as used herein contemplates single-ring groups and polycyclic 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 aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Additionally, the aryl group may be optionally substituted.
(24) The term “heteroaryl” as used herein contemplates single-ring hetero-aromatic groups that may include from one to three heteroatoms, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine and pyrimidine, and the like. The term heteroaryl also includes polycyclic hetero-aromatic systems having 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. Additionally, the heteroaryl group may be optionally substituted.
(25) The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl may be optionally substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfanyl, sulfonyl, phosphino, and combinations thereof.
(26) As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant position, such as carbon. Thus, for example, where R.sup.1 is mono-substituted, then one R.sup.1 must be other than H. Similarly, where R.sup.1 is di-substituted, then two of R.sup.1 must be other than H. Similarly, where R.sup.1 is unsubstituted, R.sup.1 is hydrogen for all available positions.
(27) 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 fragment 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.
(28) 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.
(29) The present disclosure provides a novel phosphorescent compound having the formula Ir(L.sub.A).sub.n(L.sub.B).sub.3-n, and having a structure of Formula I shown below:
(30) ##STR00003##
In Formula I, R.sub.a, R.sub.b, and R.sub.c each independently represent mono-, di-, tri-, tetra-substitution, or no substitution;
(31) wherein X is O, S, or Se; wherein n is an integer from 1 to 3;
(32) wherein R.sub.a, R.sub.b, and R.sub.c are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
(33) wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of hydrogen, deuterium, aryl, alkyl, cycloalkyl, and combinations thereof;
(34) wherein at least two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are alkyl, cycloalkyl, or combinations thereof; and
(35) wherein any adjacent substitutions in R.sup.1 to R.sup.4 and R.sub.a to R.sub.c are optionally linked together to form a ring.
(36) In some embodiments of the compound, at least two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, and combinations thereof, wherein each group is optionally partially or fully deuterated.
(37) In one embodiment of the compound having the structure of Formula I, n is 1.
(38) In one embodiment of the compound having the structure of Formula I, X is O.
(39) In one embodiment of the compound having the structure of Formula I, R.sup.1 and R.sup.4 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated, and R.sup.2 and R.sup.3 are hydrogen.
(40) In another embodiment of the compound having the structure of Formula I, R.sup.1 and R.sup.3 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated, and R.sup.2 and R.sup.4 are hydrogen.
(41) In one embodiment of the compound having the structure of Formula I, R.sup.3 and R.sup.4 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated, and R.sup.1 and R.sup.2 are hydrogen.
(42) In one preferred embodiment of the compound having the structure of Formula I, R.sup.1, R.sup.3, and R.sup.4 are each independently selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated and R.sup.2 is hydrogen.
(43) In one embodiment of the compound having the structure of Formula I, any two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are hydrogen.
(44) In another embodiment of the compound having the structure of Formula I, R.sup.1 is selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, wherein each group is optionally partially or fully deuterated.
(45) In one embodiment of the compound, the total number of carbon atoms in R.sup.1, R.sup.2, R.sup.3, and R.sup.4 combined is at least 3. In another embodiment of the compound, the total number of carbon atoms in R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is at least 4.
(46) In one embodiment of the compound, R.sub.a, R.sub.b, and R.sub.c are each independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
(47) In one embodiment of the compound, L.sub.A has a structure according to the following formula:
(48) ##STR00004##
and is selected from the group consisting of L.sub.A1 through L.sub.A438 wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are as defined in Tables 1A and 1B provided below:
(49) TABLE-US-00001 TABLE 1A Ligand L.sub.A R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 L.sub.A1 CH.sub.3 CH.sub.3 H H H H H H L.sub.A2 CH.sub.3 H CH.sub.3 H H H H H L.sub.A3 CH.sub.3 H H CH.sub.3 H H H H L.sub.A4 H CH.sub.3 CH.sub.3 H H H H H L.sub.A5 H CH.sub.3 H CH.sub.3 H H H H L.sub.A6 H H CH.sub.3 CH.sub.3 H H H H L.sub.A7 CD.sub.3 CD.sub.3 H H H H H H L.sub.A8 CD.sub.3 H CD.sub.3 H H H H H L.sub.A9 CD.sub.3 H H CD.sub.3 H H H H L.sub.A10 H CD.sub.3 CD.sub.3 H H H H H L.sub.A11 H CD.sub.3 H CD.sub.3 H H H H L.sub.A12 H H CD.sub.3 CD.sub.3 H H H H L.sub.A13 CH.sub.3 CH.sub.3 H H CH.sub.3 H H H L.sub.A14 CH.sub.3 H CH.sub.3 H CH.sub.3 H H H L.sub.A15 CH.sub.3 H H CH.sub.3 CH.sub.3 H H H L.sub.A16 H CH.sub.3 CH.sub.3 H CH.sub.3 H H H L.sub.A17 H CH.sub.3 H CH.sub.3 CH.sub.3 H H H L.sub.A18 H H CH.sub.3 CH.sub.3 CH.sub.3 H H H L.sub.A19 CD.sub.3 CD.sub.3 H H CD.sub.3 H H H L.sub.A20 CD.sub.3 H CD.sub.3 H CD.sub.3 H H H L.sub.A21 CD.sub.3 H H CD.sub.3 CD.sub.3 H H H L.sub.A22 H CD.sub.3 CD.sub.3 H CD.sub.3 H H H L.sub.A23 H CD.sub.3 H CD.sub.3 CD.sub.3 H H H L.sub.A24 H H CD.sub.3 CD.sub.3 CD.sub.3 H H H L.sub.A25 CH.sub.3 CH.sub.3 H H H CH.sub.3 H H L.sub.A26 CH.sub.3 H CH.sub.3 H H CH.sub.3 H H L.sub.A27 CH.sub.3 H H CH.sub.3 H CH.sub.3 H H L.sub.A28 H CH.sub.3 CH.sub.3 H H CH.sub.3 H H L.sub.A29 H CH.sub.3 H CH.sub.3 H CH.sub.3 H H L.sub.A30 H H CH.sub.3 CH.sub.3 H CH.sub.3 H H L.sub.A31 CD.sub.3 CD.sub.3 H H H CD.sub.3 H H L.sub.A32 CD.sub.3 H CD.sub.3 H H CD.sub.3 H H L.sub.A33 CD.sub.3 H H CD.sub.3 H CD.sub.3 H H L.sub.A34 H CD.sub.3 CD.sub.3 H H CD.sub.3 H H L.sub.A35 H CD.sub.3 H CD.sub.3 H CD.sub.3 H H L.sub.A36 H H CD.sub.3 CD.sub.3 H CD.sub.3 H H L.sub.A37 CH.sub.3 CH.sub.3 H H H H CH.sub.3 H L.sub.A38 CH.sub.3 H CH.sub.3 H H H CH.sub.3 H L.sub.A39 CH.sub.3 H H CH.sub.3 H H CH.sub.3 H L.sub.A40 H CH.sub.3 CH.sub.3 H H H CH.sub.3 H L.sub.A41 H CH.sub.3 H CH.sub.3 H H CH.sub.3 H L.sub.A42 H H CH.sub.3 CH.sub.3 H H CH.sub.3 H L.sub.A43 CD.sub.3 CD.sub.3 H H H H CD.sub.3 H L.sub.A44 CD.sub.3 H CD.sub.3 H H H CD.sub.3 H L.sub.A45 CD.sub.3 H H CD.sub.3 H H CD.sub.3 H L.sub.A46 H CD.sub.3 CD.sub.3 H H H CD.sub.3 H L.sub.A47 H CD.sub.3 H CD.sub.3 H H CD.sub.3 H L.sub.A48 H H CD.sub.3 CD.sub.3 H H CD.sub.3 H L.sub.A49 CH.sub.3 CH.sub.3 H H H H H CH.sub.3 L.sub.A50 CH.sub.3 H CH.sub.3 H H H H CH.sub.3 L.sub.A51 CH.sub.3 H H CH.sub.3 H H H CH.sub.3 L.sub.A52 H CH.sub.3 CH.sub.3 H H H H CH.sub.3 L.sub.A53 H CH.sub.3 H CH.sub.3 H H H CH.sub.3 L.sub.A54 H H CH.sub.3 CH.sub.3 H H H CH.sub.3 L.sub.A55 CD.sub.3 CD.sub.3 H H H H H CD.sub.3 L.sub.A56 CD.sub.3 H CD.sub.3 H H H H CD.sub.3 L.sub.A57 CD.sub.3 H H CD.sub.3 H H H CD.sub.3 L.sub.A58 H CD.sub.3 CD.sub.3 H H H H CD.sub.3 L.sub.A59 H CD.sub.3 H CD.sub.3 H H H CD.sub.3 L.sub.A60 H H CD.sub.3 CD.sub.3 H H H CD.sub.3 L.sub.A61 CH.sub.3 CH.sub.3 H H CH(CH.sub.3).sub.2 H H H L.sub.A62 CH.sub.3 H CH.sub.3 H CH(CH.sub.3).sub.2 H H H L.sub.A63 CH.sub.3 H H CH.sub.3 CH(CH.sub.3).sub.2 H H H L.sub.A64 H CH.sub.3 CH.sub.3 H CH(CH.sub.3).sub.2 H H H L.sub.A65 H CH.sub.3 H CH.sub.3 CH(CH.sub.3).sub.2 H H H L.sub.A66 H H CH.sub.3 CH.sub.3 CH(CH.sub.3).sub.2 H H H L.sub.A67 CD.sub.3 CD.sub.3 H H CD(CD.sub.3).sub.2 H H H L.sub.A68 CD.sub.3 H CD.sub.3 H CD(CD.sub.3).sub.2 H H H L.sub.A69 CD.sub.3 H H CD.sub.3 CD(CD.sub.3).sub.2 H H H L.sub.A70 H CD.sub.3 CD.sub.3 H CD(CD.sub.3).sub.2 H H H L.sub.A71 H CD.sub.3 H CD.sub.3 CD(CD.sub.3).sub.2 H H H L.sub.A72 H H CD.sub.3 CD.sub.3 CD(CD.sub.3).sub.2 H H H L.sub.A73 CH.sub.3 CH.sub.3 H H H CH(CH.sub.3).sub.2 H H L.sub.A74 CH.sub.3 H CH.sub.3 H H CH(CH.sub.3).sub.2 H H L.sub.A75 CH.sub.3 H H CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A76 H CH.sub.3 CH.sub.3 H H CH(CH.sub.3).sub.2 H H L.sub.A77 H CH.sub.3 H CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A78 H H CH.sub.3 CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A79 CD.sub.3 CD.sub.3 H H H CD(CD.sub.3).sub.2 H H L.sub.A80 CD.sub.3 H CD.sub.3 H H CD(CD.sub.3).sub.2 H H L.sub.A81 CD.sub.3 H H CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A82 H CD.sub.3 CD.sub.3 H H CD(CD.sub.3).sub.2 H H L.sub.A83 H CD.sub.3 H CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A84 H H CD.sub.3 CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A85 CH.sub.3 CH.sub.3 H H H H CH(CH.sub.3).sub.2 H L.sub.A86 CH.sub.3 H CH.sub.3 H H H CH(CH.sub.3).sub.2 H L.sub.A87 CH.sub.3 H H CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A88 H CH.sub.3 CH.sub.3 H H H CH(CH.sub.3).sub.2 H L.sub.A89 H CH.sub.3 H CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A90 H H CH.sub.3 CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A91 CD.sub.3 CD.sub.3 H H H H CD(CD.sub.3).sub.2 H L.sub.A92 CD.sub.3 H CD.sub.3 H H H CD(CD.sub.3).sub.2 H L.sub.A93 CD.sub.3 H H CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A94 H CD.sub.3 CD.sub.3 H H H CD(CD.sub.3).sub.2 H L.sub.A95 H CD.sub.3 H CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A96 H H CD.sub.3 CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A97 CD.sub.3 H CD.sub.3 H H H CD(CH.sub.3).sub.2 H L.sub.A98 CH.sub.2CH.sub.3 CH.sub.3 H H H CH(CH.sub.3).sub.2 H H L.sub.A99 CH.sub.2CH.sub.3 H CH.sub.3 H H CH(CH.sub.3).sub.2 H H L.sub.A100 CH.sub.2CH.sub.3 H H CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A101 H CH.sub.2CH.sub.3 CH.sub.3 H H CH(CH.sub.3).sub.2 H H L.sub.A102 H CH.sub.2CH.sub.3 H CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A103 H H CH.sub.2CH.sub.3 CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A104 H H CH.sub.3 CH.sub.2CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A105 H CH.sub.3 H CH.sub.2CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A106 CH.sub.3 H H CH.sub.2CH.sub.3 H CH(CH.sub.3).sub.2 H H L.sub.A107 CD.sub.2CD.sub.3 CD.sub.3 H H H CD(CD.sub.3).sub.2 H H L.sub.A108 CD.sub.2CD.sub.3 H CD.sub.3 H H CD(CD.sub.3).sub.2 H H L.sub.A109 CD.sub.2CD.sub.3 H H CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A110 CD.sub.2CD.sub.3 H H CD.sub.3 H CD(CH.sub.3).sub.2 H H L.sub.A111 CH.sub.2CH.sub.3 CH.sub.3 H H H H CH(CH.sub.3).sub.2 H L.sub.A112 CH.sub.2CH.sub.3 H CH.sub.3 H H H CH(CH.sub.3).sub.2 H L.sub.A113 CH.sub.2CH.sub.3 H H CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A114 H CH.sub.2CH.sub.3 CH.sub.3 H H H CH(CH.sub.3).sub.2 H L.sub.A115 H CH.sub.2CH.sub.3 H CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A116 H H CH.sub.2CH.sub.3 CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A117 H H CH.sub.3 CH.sub.2CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A118 H CH.sub.3 H CH.sub.2CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A119 CH.sub.3 H H CH.sub.2CH.sub.3 H H CH(CH.sub.3).sub.2 H L.sub.A120 CD.sub.2CD.sub.3 CD.sub.3 H H H H CD(CD.sub.3).sub.2 H L.sub.A121 CD.sub.2CD.sub.3 H CD.sub.3 H H H CD(CD.sub.3).sub.2 H L.sub.A122 CD.sub.2CD.sub.3 H H CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A123 CD.sub.3 H H CD.sub.2CH.sub.3 H H CD(CH.sub.3).sub.2 H L.sub.A124 CD.sub.3 H H CD.sub.2CH.sub.3 H H H CD.sub.3 L.sub.A125 CH.sub.3 CH.sub.3 H H H H H CH(CH.sub.3).sub.2 L.sub.A126 CH.sub.3 H CH.sub.3 H H H H CH(CH.sub.3).sub.2 L.sub.A127 CH.sub.3 H H CH.sub.3 H H H CH(CH.sub.3).sub.2 L.sub.A128 H CH.sub.3 CH.sub.3 H H H H CH(CH.sub.3).sub.2 L.sub.A129 H CH.sub.3 H 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CD.sub.3 H CD.sub.3 CH(CH.sub.3).sub.2 H L.sub.A284 CD.sub.3 H H CD(CH.sub.3).sub.2 H CD.sub.3 CH(CH.sub.3).sub.2 H L.sub.A285 CD(CH.sub.3).sub.2 H CD(CH.sub.3).sub.2 H H CD.sub.3 CH(CH.sub.3).sub.2 H L.sub.A286 CD(CH.sub.3).sub.2 H H CD(CH.sub.3).sub.2 H CD.sub.3 CH(CH.sub.3).sub.2 H L.sub.A287 CH(CH.sub.3).sub.2 CH.sub.3 H H H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A288 CH.sub.3 CH(CH.sub.3).sub.2 H H H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A289 CH(CH.sub.3).sub.2 H CH.sub.3 H H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A290 CH.sub.3 H CH(CH.sub.3).sub.2 H H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A291 CH(CH.sub.3).sub.2 H H CH.sub.3 H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A292 CH.sub.3 H H CH(CH.sub.3).sub.2 H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A293 H CH(CH.sub.3).sub.2 CH.sub.3 H H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A294 H CH(CH.sub.3).sub.2 H CH.sub.3 H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A295 H H CH(CH.sub.3).sub.2 CH.sub.3 H CH(CH.sub.3).sub.2 CH.sub.3 H L.sub.A296 CH(CH.sub.3).sub.2 H H CH(CH.sub.3).sub.2 H CD(CH.sub.3).sub.2 CH.sub.3 H L.sub.A297 CD(CH.sub.3).sub.2 CD.sub.3 H H H CD(CH.sub.3).sub.2 CD.sub.3 H L.sub.A298 CD(CH.sub.3).sub.2 H CD.sub.3 H H CD(CH.sub.3).sub.2 CD.sub.3 H L.sub.A299 CD(CH.sub.3).sub.2 H H CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H L.sub.A300 H CD(CH.sub.3).sub.2 CD.sub.3 H H CD(CH.sub.3).sub.2 CD.sub.3 H L.sub.A301 H CD(CH.sub.3).sub.2 H CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H L.sub.A302 CD.sub.3 H H CD(CH.sub.3).sub.2 H CD(CH.sub.3).sub.2 CD.sub.3 H L.sub.A303 CD(CH.sub.3).sub.2 H CD(CH.sub.3).sub.2 H H CD(CH.sub.3).sub.2 CD.sub.3 H L.sub.A304 CD(CH.sub.3).sub.2 H H CD(CH.sub.3).sub.2 H CD(CH.sub.3).sub.2 CD.sub.3 H L.sub.A305 CD(CH.sub.3).sub.2 H H CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A306 CD.sub.3 CD.sub.3 H H H CD(CH.sub.3).sub.2 H H L.sub.A307 CD.sub.3 H CD.sub.3 H H CD(CH.sub.3).sub.2 H H L.sub.A308 CD.sub.3 H H CD.sub.3 H CD(CH.sub.3).sub.2 H H L.sub.A309 H CD.sub.3 CD.sub.3 H H CD(CH.sub.3).sub.2 H H L.sub.A310 H CD.sub.3 H CD.sub.3 H CD(CH.sub.3).sub.2 H H L.sub.A311 H H CD.sub.3 CD.sub.3 H CD(CH.sub.3).sub.2 H H L.sub.A312 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H H H L.sub.A313 CH.sub.3 CH.sub.3 CH.sub.3 H H H H H L.sub.A314 CH.sub.3 H CH.sub.3 CH.sub.3 H H H H L.sub.A315 H CH.sub.3 CH.sub.3 CH.sub.3 H H H H L.sub.A316 CD.sub.3 CD.sub.3 CD.sub.3 H H H H H L.sub.A317 CD.sub.3 H CD.sub.3 CD.sub.3 H H H H L.sub.A318 CD.sub.3 CD.sub.3 H CD.sub.3 H H H H L.sub.A319 H CD.sub.3 CD.sub.3 CD.sub.3 H H H H L.sub.A320 CD.sub.3 CD.sub.3 CD.sub.3 CD.sub.3 H H H H L.sub.A321 CD.sub.3 H CD.sub.3 CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A322 CD.sub.3 H CD.sub.3 CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A323 CD.sub.3 H CD.sub.3 CD.sub.3 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A324 CD.sub.3 H CD.sub.3 CD.sub.3 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A325 CD.sub.3 H CD.sub.3 CD(CH.sub.3).sub.2 H H H H L.sub.A326 CD.sub.3 H CD.sub.3 CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 H H L.sub.A327 CD.sub.3 H CD.sub.3 CD(CH.sub.3).sub.2 H H CD(CD.sub.3).sub.2 H L.sub.A328 CD.sub.3 H CD.sub.3 CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A329 CD.sub.3 H CD.sub.3 CD(CH.sub.3).sub.2 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A330 CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H H H H L.sub.A331 CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A332 CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A333 CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A334 CD.sub.3 H CD(CH.sub.3).sub.2 CD.sub.3 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A335 CD.sub.3 H CD(CH.sub.3).sub.2 CD(CH.sub.3).sub.2 H H H H L.sub.A336 CD.sub.3 H CD(CH.sub.3).sub.2 CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 H H L.sub.A337 CD.sub.3 H CD(CH.sub.3).sub.2 CD(CH.sub.3).sub.2 H H CD(CD.sub.3).sub.2 H L.sub.A338 CD.sub.3 H CD(CH.sub.3).sub.2 CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A339 CD.sub.3 H CD(CH.sub.3).sub.2 CD(CH.sub.3).sub.2 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A340 CD(CH.sub.3).sub.2 H CD.sub.3 H H H CD(CD.sub.3).sub.2 H L.sub.A341 CD(CH.sub.3).sub.2 H CD.sub.3 H H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A342 CD(CH.sub.3).sub.2 H CD.sub.3 H H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A343 CD(CH.sub.3).sub.2 H CD.sub.3 CD.sub.3 H H H H L.sub.A344 CD(CH.sub.3).sub.2 H CD.sub.3 CD.sub.3 H CD(CD.sub.3).sub.2 H H L.sub.A345 CD(CH.sub.3).sub.2 H CD.sub.3 CD.sub.3 H H CD(CD.sub.3).sub.2 H L.sub.A346 CD(CH.sub.3).sub.2 H CD.sub.3 CD.sub.3 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A347 CD(CH.sub.3).sub.2 H CD.sub.3 CD.sub.3 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A348 CD.sub.3 H H CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 H H L.sub.A349 CD.sub.3 H H CD(CH.sub.3).sub.2 H H CD(CD.sub.3).sub.2 H L.sub.A350 CD.sub.3 H H CD(CH.sub.3).sub.2 H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A351 CD.sub.3 H H CD(CH.sub.3).sub.2 H CD.sub.3 CD(CD.sub.3).sub.2 H L.sub.A352 CD.sub.3 H CD(CH.sub.3).sub.2 H H H H H L.sub.A353 CD.sub.3 H CD(CH.sub.3).sub.2 H H CD(CD.sub.3).sub.2 H H L.sub.A354 CD.sub.3 H CD(CH.sub.3).sub.2 H H H CD(CD.sub.3).sub.2 H L.sub.A355 CD.sub.3 H CD(CH.sub.3).sub.2 H H CD(CD.sub.3).sub.2 CD.sub.3 H L.sub.A356 CD.sub.3 H CD(CH.sub.3).sub.2 H H CD.sub.3 CD(CD.sub.3).sub.2 H
(50) TABLE-US-00002 TABLE 1B Ligand L.sub.A R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 L.sub.A357
(51) In another embodiment of the compound, L.sub.B is selected from the group consisting of:
(52) ##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##
(53) In one embodiment of the compound, the compound is selected from the group consisting of:
(54) ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146##
(55) According to another aspect of the present disclosure, a device comprising one or more organic light emitting devices is disclosed. At least one of the one or more organic light emitting devices comprise: an anode; a cathode; and an organic layer disposed between the anode and the cathode. The organic layer comprises a compound having the formula Ir(L.sub.A).sub.n(L.sub.B).sub.3-n, and having the structure according to Formula I shown below:
(56) ##STR00147##
In Formula I, R.sub.a, R.sub.b, and R.sub.c each independently represent mono-, di-, tri-, tetra-substitution, or no substitution;
(57) wherein X is O, S, or Se;
(58) wherein n is an integer from 1 to 3;
(59) wherein R.sub.a, R.sub.b, and R.sub.c are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
(60) wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of hydrogen, deuterium, aryl, alkyl, cycloalkyl, and combinations thereof;
(61) wherein at least two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are alkyl, cycloalkyl, or combinations thereof; and
(62) wherein any adjacent substitutions in R.sup.1 to R.sup.4 and R.sub.a to R.sub.c are optionally linked together to form a ring.
(63) In one embodiment of the device, the device is selected from the group consisting of a consumer product, an electronic component module, an organic light-emitting device, and a lighting panel.
(64) In some embodiments of the device, the organic layer is an emissive layer and the compound is an emissive dopant or a non-emissive dopant.
(65) The organic layer can 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.
(66) In one embodiment of the device, the organic layer further comprises a host material, wherein the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
(67) In another embodiment of the device, the host material can be a specific compound selected from the group consisting of:
(68) ##STR00148## ##STR00149## ##STR00150## ##STR00151##
and combinations thereof.
(69) In another embodiment of the device, the host material can include a metal complex.
(70) According to another aspect of the present disclosure, a formulation comprising a compound having a formula Ir(L.sub.A).sub.n(L.sub.B).sub.3-n, having the structure:
(71) ##STR00152##
is disclosed.
(72) In Formula I, R.sub.a, R.sub.b, and R.sub.c each independently represent mono-, di-, tri-, tetra-substitution, or no substitution;
(73) wherein X is O, S, or Se;
(74) wherein n is an integer from 1 to 3;
(75) wherein R.sub.a, R.sub.b, and R.sub.c are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfanyl, sulfonyl, phosphino, and combinations thereof;
(76) wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of hydrogen, deuterium, aryl, alkyl, cycloalkyl, and combinations thereof;
(77) wherein at least two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are alkyl, cycloalkyl, or combinations thereof; and
(78) wherein any adjacent substitutions in R.sup.1 to R.sup.4 and R.sub.a to R.sub.c are optionally linked together to form a ring.
(79) In some embodiments, the compound can be an emissive dopant in an OLED. 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), triplet-triplet annihilation, or combinations of these processes.
(80) Combination with Other Materials
(81) 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.
(82) HIL/HTL:
(83) A hole injecting/transporting material to be used in the present invention 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 compound.
(84) Examples of aromatic amine derivatives used in HIL or HTL include, but are not limited to the following general structures:
(85) ##STR00153##
(86) 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. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
(87) In one aspect, Ar.sup.1 to Ar.sup.9 is independently selected from the group consisting of:
(88) ##STR00154##
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.
(89) Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:
(90) ##STR00155##
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.
(91) 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.
(92) Host:
(93) The light emitting layer of the organic EL device of the present invention 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. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.
(94) Examples of metal complexes used as host are preferred to have the following general formula:
(95) ##STR00156##
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.
(96) In one aspect, the metal complexes are:
(97) ##STR00157##
wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
(98) In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y.sup.103-Y.sup.104) is a carbene ligand.
(99) Examples of organic compounds used as host are 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. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
(100) In one aspect, the host compound contains at least one of the following groups in the molecule:
(101) ##STR00158## ##STR00159##
wherein R.sup.101 to R.sup.107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, 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. k is an integer from 0 to 20 or 1 to 20; k′″ is an integer from 0 to 20. X.sup.101 to X.sup.108 is selected from C (including CH) or N. Z.sup.101 and Z.sup.102 is selected from NR.sup.101, O, or S.
HBL:
(102) 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 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.
(103) In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
(104) In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
(105) ##STR00160##
wherein k is an integer from 1 to 20; L.sup.101 is an another ligand, k′ is an integer from 1 to 3.
ETL:
(106) 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.
(107) In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
(108) ##STR00161##
wherein R.sup.101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, 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.
(109) In another aspect, the metal complexes used in ETL include, but are not limited to the following general formula:
(110) ##STR00162##
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.
(111) In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.
(112) In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exciton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table A below. Table A lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.
(113) TABLE-US-00003 TABLE A MATERIAL EXAMPLES OF MATERIAL PUBLICATIONS Hole injection materials Phthalocyanine and porphyrin compounds CH.sub.xF.sub.y
.sub.n Appl. Phys. Lett. 78, polymer 673 (2001) Conducting polymers (e.g., PEDOT:PSS, polyaniline, polythiophene)
(114) The present disclosure describes novel iridium complexes comprising dialkyl-substituted aza-DBF and 2-phenylpyridine ligands. The dialkyl substitution appears to improve OLED device performance such as CIE color and extending the lifetime.
(115) Molecular modification of iridium complexes can effectively change material device performance. In this disclosure, the inventors discovered that aza-DBF ligand with multi-alkyl-substitution on DBF ring on heteroleptic iridium complex can improve the device lifetime and color CIE. The improved color CIE was unexpected. It was found that in many cases when methyl group is in R.sub.1 position the color CIE of the particular compound is always slightly red shifted compared to the non-substituted compounds (e.g. R.sub.1 is hydrogen).
DEVICE EXAMPLES
(116) All example devices were fabricated by high vacuum (<10.sup.−7 Torr) thermal evaporation. The anode electrode is 1200 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF 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, and a moisture getter was incorporated inside the package. The organic stack of the device examples consisted of sequentially, from the ITO surface, 100 Å of LG-101 (available from LG Chem. Inc.) as the hole injection layer (HIL), 450 Å of Compound D as the hole transporting layer (HTL), 400 Å of the invention compound doped in Compound B as host with 10 or 15 weight percent of the iridium phosphorescent compound as the emissive layer (EML), 50 {acute over (Å)} of Compound C as a blocking layer (BL), 450 Å of Alq (tris-8-hydroxyquinoline aluminum) as the ETL. The comparative Example with Compound A was fabricated similarly to the Device Examples. The device results and data are summarized in Tables 1 and 2. As used herein, Alq, Compounds A, B, C and D have the following structures:
(117) ##STR00339## ##STR00340##
(118) TABLE-US-00004 TABLE 1 Device Structures of Inventive Compound and Comparative Compound Device HIL HTL EML (300 Å, doping %) BL ETL Comparative LG-101 Compound D Compound Compound A Compound C Alq Example 1 100 Å 300 Å B as host 10% 50 Å 450 Å Comparative LG-101 Compound D Compound Compound A Compound C Alq Example 2 100 Å 300 Å B as host 15% 50 Å 450 Å Inventive LG-101 Compound D Compound Compound 1 Compound C Alq Example 1 100 Å 300 Å B as host 10% 50 Å 450 Å Inventive LG-101 Compound D Compound Compound 1 Compound C Alq Example 2 100 Å 300 Å B as host 15% 50 Å 450 Å Inventive LG-101 Compound D Compound Compound 2 Compound C Alq Example 3 100 Å 300 Å B as host 10% 50 Å 450 Å Inventive LG-101 Compound D Compound Compound 2 Compound C Alq Example 4 100 Å 300 Å B as host 15% 50 Å 450 Å
(119) TABLE-US-00005 TABLE 2 VTE Device Results λmax FWHM Dopant Device x y (nm) (nm) (%) Comparative Example 1 0.337 0.630 528 59 10 (Dopant Compound A) Comparative Example 2 0.344 0.627 530 60 15 (Dopant Compound A) Inventive Example 1 0.310 0.640 520 61 10 (Dopant Compound 1) Inventive Example 2 0.315 0.638 520 63 15 (Dopant Compound 1) Inventive Example 3 0.332 0.632 526 60 10 (Dopant Compound 2) Inventive Example 4 0.339 0.628 528 61 15 (Dopant Compound 2)
(120) Table 2 is the summary of EL of comparative and inventive devices at 1000 nits. The emission wavelengths of invention Compound 1 and Compound 2 emission peak max with doping concentration at 10% were 520 nm and 526 nm. Compared to the comparative Compound A, which exhibited emission peak max of 528 nm at 10% doping concentration, the inventive compounds blue shifted about 8 and 2 nm, respectively. Similarly, the emission wavelengths of invention Compound 1 and Compound 2 at doping concentration of 15% were 520 nm and 528 nm, respectively, whereas the comparative Compound A exhibited emission peak max of 530 nm. Thus, the emission wavelengths of the inventive compounds blue shifted at 15% doping concentration also. The device results demonstrate that multi-alkylation can result in blue shift of emission spectrum which is a desired property for OLED device.
Synthesis Example 1 for an Example of the Novel Compound, Compound IrLA8(LB1)2
(121) ##STR00341##
(122) An iridium precursor (1.69 g, 2.368 mmol) and 2,4-bis(methyl-d.sub.3)-8-(pyridin-2-yl)benzofuro[2,3-b]pyridine (0.996 g, 3.55 mmol) were added to a 100 mL round-bottom flask equipped with a magnetic stir bar. Anhydrous DMF (25 mL) and 2-ethoxyethanol (25 mL) were added to the reaction mixture. The reaction flask was then placed into an oil bath and gradually heated to 130° C. for 16 hours. Then, the reaction mixture was concentrated in a vacuum. The residue was then dissolved in CH.sub.2Cl.sub.2, filtered through a pad of Celite, eluting with CH.sub.2Cl.sub.2 and EtOAc, and concentrated in a vacuum. The crude product was purified via flash chromatography on a (2×120) g column (CH.sub.2Cl.sub.2) to provide Compound IrL.sub.A8(L.sub.B1).sub.2 as an orange powder (0.77 g, 41%).
Synthesis Example 2 for an Example of the Novel Compound, Compound IrLA7(LB1)2
(123) ##STR00342##
(124) An iridium precursor (1.85 g, 2.59 mmol) and 2,3-bis(methyl-d.sub.3)-8-(pyridin-2-yl)benzofuro[2,3-b]pyridine (1.09 g, 3.89 mmol) were added to a 100 mL round-bottom flask equipped with a magnetic stir bar. Anhydrous DMF (26 mL) and 2-ethoxyethanol (26 mL) were added to the reaction mixture. The reaction flask was then placed into an oil bath, gradually heated to 130° C. for 16 hours. Then, the reaction mixture was concentrated in a vacuum. The residue was then dissolved in CH.sub.2Cl.sub.2, filtered through a pad of celite, eluting with CH.sub.2Cl.sub.2 and EtOAc, and concentrated in a vacuum. The crude product was purified via flash chromatography on a (2×220) g column (CH.sub.2Cl.sub.2) to provide Compound IrL.sub.A7(L.sub.B1).sub.2 as an orange solid (1.0 g, 49%).
Synthesis Example 3 for an Example of the Novel Compound, Compound IrLA9(LB1)2
(125) ##STR00343##
(126) A mixture of iridium precursor (2.1 g, 2.94 mmol), aza dibenzofuran pyridine ligand (1.485 g, 5.3 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) was heated at 130° C. for 18 hours. The reaction mixture was concentrated to remove solvents and filtered through a small plug of silica gel and further chromatographed to give 1.2 g of Compound IrL.sub.A9(L.sub.B1).sub.2 (52.3% yield).
Synthesis Example 4 for an Example of the Novel Compound, Compound IrLA9(LB12)2
(127) ##STR00344##
(128) A mixture of iridium precursor (2.3 g, 2.94 mmol), aza dibenzofuran pyridine ligand (1.485 g, 5.29 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) was heated at 130° C. for 18 hours. The reaction mixture was concentrated to remove solvents and filtered through a small plug of silica gel and further chromatographed to give 0.47 g of Compound IrL.sub.A9(L.sub.B12).sub.2 (18.8% yield).
Synthesis Example 5 for an Example of the Novel Compound, Compound IrLA81(LB1)2
(129) ##STR00345##
(130) A mixture of iridium precursor (1.35 g, 1.89 mmol), aza dibenzofuran pyridine ligand (0.935 g, 2.84 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) was heated at 130° C. for 18 hours. The reaction mixture was concentrated to remove solvents and filtered through a small plug of silica gel and further chromatographed to give 0.77 g of Compound IrL.sub.A81(L.sub.B1).sub.2 (49.1% yield).
Synthesis Example 6 for an Example of the Novel Compound, Compound IrLA81(LB9)2
(131) ##STR00346##
(132) A mixture of iridium precursor (2.1 g, 2.001 mmol), aza dibenzofuran pyridine ligand (0.991 g, 3.01 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) was heated at 130° C. for 18 hours. The reaction mixture was concentrated to remove solvents and filtered through a small plug of silica gel and further chromatographed to give 0.86 g of Compound IrL.sub.A81(L.sub.B9).sub.2 (49.7% yield).
Synthesis Example 7 for an Example of the Novel Compound, Compound IrLA80(LB9)2
(133) ##STR00347##
(134) A mixture of iridium precursor (0.93 g, 1.23 mmol), aza dibenzofuran pyridine ligand (0.608 g, 1.845 mmol), 2-ethoxyethanol (13 mL) and DMF (13 mL) was heated at 130° C. for 19 hours. The reaction mixture was concentrated to remove solvents and filtered through a small plug of silica gel and further chromatographed to give 0.43 g of Compound IrL.sub.A80(L.sub.B9).sub.2 (40.5% yield).
(135) 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.