BINUCLEAR METAL COMPLEXES FOR USE AS EMITTERS IN ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to binuclear metal complexes and electronic devices, in particular organic electroluminescent devices containing said metal complexes.

##STR00001##

Claims

1-16. (canceled)

17. A compound of formula (1): ##STR00844## wherein M is the same or different in each instance and is iridium or rhodium; D is the same or different in each instance and is C or N; X is the same or different in each instance and is CR or N; or two adjacent X together in the cycle containing E are CR or N and the third X is CR or N when either one D in the cycle coordinates as an anionic nitrogen atom to M or when E is N; E is C or N, wherein E can be N only when two adjacent X together in the cycle containing E are CR or N and the third X is CR or N; V is the same or different at each instance and is a group of the formula (2) or (3) ##STR00845## wherein the dotted bond bonded directly to the cycle is the bond to the corresponding 6-membered aryl or heteroaryl group of formula (1) and the two dotted bonds to A are each the bonds to the sub-ligands L; L is the same or different in each instance and is a bidentate monoanionic sub-ligand; X.sup.1 is the same or different in each instance and is CR or N; X.sup.2 is the same or different in each instance and is CR or N; or two adjacent X.sup.2 groups together are NR, O, or S, so as to define a five-membered ring, and the remaining X.sup.2 are the same or different in each instance and are CR or N; or two adjacent X.sup.2 groups together are CR or N when one of the X.sup.3 groups in the cycle is N, so as to define a five-membered ring; with the proviso that not more than two adjacent X.sup.2 groups are N; X.sup.3 is C in each instance or one X.sup.3 group is N and the other X.sup.3 groups in the same cycle are C; with the proviso that two adjacent X.sup.2 groups together are CR or N when one of the X.sup.3 groups in the cycle is N; A.sup.1 is the same or different in each instance and is C(R).sub.2 or O; A.sup.2 is the same or different in each instance and is CR, P(O), B, or SiR, with the proviso that, when A.sup.2 is P(O), B, or SiR, A.sup.1 is O and the A bonded to the A.sup.2 is not C(O)NR or C(O)O; A is the same or different in each instance and is CRCR, C(O)NR, C(O)O, CR.sub.2CR.sub.2, CR.sub.2O, or a group of formula (4): ##STR00846## wherein the dotted bond is the position of the bond of a bidentate sub-ligand L to the group of formula (4) and * is the position of the linkage of the group of formula (4) to the central cyclic group; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OR.sup.1, SR.sup.1, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, COO(cation), SO.sub.3(cation), OSO.sub.3(cation), OPO.sub.3(cation).sub.2, O(cation), N(R.sup.1).sub.3(anion), P(R.sup.1).sub.3(anion), a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group is in each case optionally substituted by one or more radicals R.sup.1 and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by Si(R.sup.1).sub.2, CO, NR.sup.1, O, S, or CONR.sup.1, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more radicals R.sup.1; and wherein two radicals R together optionally define a ring system; R is the same or different in each instance and is H, D, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group is in each case optionally substituted by one or more radicals R.sup.1 and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by Si(R.sup.1).sub.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more radicals R.sup.1; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, OR.sup.2, SR.sup.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, COO(cation), SO.sub.3(cation), OSO.sub.3(cation), OPO.sub.3(cation).sub.2, O(cation), N(R.sup.2).sub.3(anion), P(R.sup.2).sub.3(anion), a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group is in each case optionally substituted by one or more radicals R.sup.2, and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which are optionally substituted in each case by one or more radicals R.sup.2; and wherein two or more radicals R.sup.1 together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, or heteroaromatic organic radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms is also optionally replaced by F; cation is the same or different in each instance and is selected from the group consisting of proton, deuteron, alkali metal ions, alkaline earth metal ions, ammonium, tetraalkylammonium, and tetraalkylphosphonium; anion is the same or different in each instance and is selected from the group consisting of halides, carboxylates R.sup.2COO.sup., cyanide, cyanate, isocyanate, thiocyanate, thioisocyanate, hydroxide, BF.sub.4.sup., PF.sub.6.sup., B(C.sub.6F).sub.4.sup., carbonate, and sulfonates.

18. The compound of claim 17, wherein both metals M are Ir(III) and the compound is an uncharged compound.

19. The compound of claim 17, wherein the compound is selected from the group consisting of compounds of formulae (1), (1), and (1): ##STR00847## wherein the radicals R in the position ortho to the groups D and in the position ortho to the coordinating nitrogen atom in formula (1) are each the same or different in each instance and are selected from the group consisting of H, D, F, CH.sub.3, and CD.sub.3.

20. The compound of claim 17, wherein the compound is selected from the group consisting of compounds of formulae (1a) through (1h): ##STR00848## ##STR00849## wherein X in the five-membered ring of formulae (1d) through (1h) is the same or different in each instance and is CR or N.

21. The compound of claim 17, wherein the compound is selected from the group consisting of compounds of formulae (1a) through (1h): ##STR00850## ##STR00851## ##STR00852## wherein the radicals R in position ortho to the coordinating carbon or nitrogen atoms are each the same or different in each instance and are selected from the group consisting of H, D, F, CH.sub.3, and CD.sub.3.

22. The compound of claim 17, wherein the group of formula (2) is selected from the group consisting of structures of formulae (5) through (8) and the group of formula (3) is selected from the group consisting of structures of formulae (9) through (13): ##STR00853##

23. The compound of claim 17, wherein the group of formula (2) has a structure of the formula (5) and the group of the formula (3) has a structure of the formula (9) or (9) ##STR00854##

24. The compound of claim 17, wherein A is the same or different in each instance and is selected from the group consisting of C(O)O, C(O)NR, or a group of formula (4), wherein the group of formula (4) is selected from the group consisting of structures of formulae (14) through (38): ##STR00855## ##STR00856## ##STR00857## ##STR00858##

25. The compound of claim 17, wherein the group of formula (2) is selected from the group consisting of structures of formulae (2a) through (2i) and the group of formula (3) is selected from the group consisting of structures of formulae (3a) through (3i): ##STR00859## ##STR00860## ##STR00861##

26. The compound of claim 17, wherein V is selected from the group consisting of structures of formulae (5a) and (5a): ##STR00862##

27. The compound of claim 17, wherein the bidentate sub-ligands L are the same or different in each instance and are selected from the group consisting of structures of formulae (L-1), (L-2), and (L-3): ##STR00863## wherein the dotted bond is the bond of sub-ligand L to the group of formulae (2) or (3); CyC is the same or different in each instance and is a substituted or unsubstituted aryl or heteroaryl group having 5 to 14 aromatic ring atoms and coordinates to M via a carbon atom and is bonded to CyD via a covalent bond; CyD is the same or different in each instance and is a substituted or unsubstituted heteroaryl group having 5 to 14 aromatic ring atoms and coordinates to M via a nitrogen atom or via a carbene carbon atom and is bonded to CyC via a covalent bond; and wherein two or more of the optional substituents together optionally define a ring system.

28. A process for preparing the compound of claim 17 comprising reacting the ligand with metal alkoxides of formula (57), with metal ketoketonates of formula (58), with metal halides of formula (59), or with metal carboxylates of formula (60): ##STR00864## wherein Hal is F, Cl, Br, or I; the iridium or rhodium reactants are optionally in the form of the corresponding hydrates and/or iridium or rhodium compounds that bear both alkoxide and/or halide and/or hydroxyl; and wherein ketoketonate radicals are also optionally employed.

29. A formulation comprising at least one compound of claim 17 and at least one solvent.

31. An electronic device comprising at least one compound of claim 17.

32. The electronic device of claim 31, wherein the electronic device is an organic electroluminescent device and wherein the compound of formula (1) is present in the electroluminescent device as an emitting compound in one or more emitting layers.

Description

EXAMPLES

[0200] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature.

A: Synthesis of the Synthons

Example B1

[0201] ##STR00371##

[0202] A mixture of 23.0 g (100 mmol) of 2-(4-chlorophenyl)-2H-benzo-[d]-[1,2,3]-triazole [3933-77-5], 27.4 g (107 mmol) of bis(pinacolato)diborane [73183-34-3], 29.5 g (300 mmol) of potassium acetate, 1.1 g (4 mmol) of SPhos [657408-07-6], 650 mg (3 mmol) of palladium(II) acetate and 450 ml of 1,4-dioxane is heated under reflux for 16 h. The dioxane is removed on a rotary evaporator, the black residue is worked up by extraction with 1000 ml of ethyl acetate and 500 ml of water in a separating funnel, and the organic phase is washed once with 300 ml of water and once with 150 ml of saturated sodium chloride solution and filtered through a silica gel bed. The silica gel is washed with 2250 ml of ethyl acetate. The filtrate is dried over sodium sulfate and then concentrated. The residue is digested in 200 ml of n-heptane and the suspension is heated to reflux for 1 h. After cooling, the solids are filtered off with suction and washed with a little n-heptane. Yield: 26.0 g (81 mmol), 81%. Purity: about 96% by .sup.1H NMR.

Example B2

[0203] ##STR00372##

[0204] Procedure analogous to example B1, except using 5-chloro-2-(1H-pyrrol-1-yl)pyrimidine [860785-43-9] rather than 2-(4-chlorophenyl)-2H-benzo-[d]-[1,2,3]-triazole.

Example B3

[0205] ##STR00373##

[0206] A mixture of 10 g (50 mmol) of [4-(2-pyrimidinyl)phenyl]boronic acid [1615248-01-5], 18.1 g (50 mmol) of 1,3-dibromo-2-iodobenzene [19821-80-8], 15.9 g (150 mmol) of sodium carbonate, 390 mg (1.5 mmol) of triphenylphosphine, 110 mg (0.5 mmol) of palladium(II) acetate, 120 ml of toluene, 40 ml of ethanol and 120 ml of water is heated under reflux for 60 h. After cooling, the reaction mixture is worked up by extraction in a separating funnel. For this purpose, the organic phase is removed and the aqueous phase is extracted twice with 50 ml each time of ethyl acetate. Subsequently, the combined organic phases are washed twice with 100 ml each time of water and once with 50 ml of saturated sodium chloride solution, dried over sodium sulfate and concentrated to dryness. The residue is purified by column chromatography on silica gel with dichloromethane as eluent. Yield 8.1 g (21 mmol), 42%, 95% pure by .sup.1H NMR.

Example B160

[0207] ##STR00374##

[0208] A mixture of 10 g (50 mmol) of [4-(2-pyrimidinyl)phenyl]boronic acid [1615248-01-5], 11.3 g (50 mmol) of 1,3-dichloro-2-bromobenzene [19393-92-1], 15.9 g (150 mmol) of sodium carbonate, 1.2 g (1 mmol) of tetrakis(triphenylphosphine)palladium(0), 200 ml of 1,2-dimethoxyethane and 200 ml of water is heated under reflux for 20 h. After cooling, the reaction mixture is worked up by extraction in a separating funnel with 150 ml of toluene and 150 ml of water. The organic phase is removed and the aqueous phase is extracted twice with 50 ml each time of toluene. Subsequently, the combined organic phases are washed twice with 100 ml each time of water and once with 50 ml of saturated sodium chloride solution, dried over sodium sulfate and concentrated to dryness. The residue is purified by column chromatography on silica gel with ethyl acetate/heptane. A colorless oil is obtained. Yield: 10.5 g (35 mmol), 70%, 97% pure by .sup.1H NMR.

[0209] The following compounds can be prepared in an analogous manner:

TABLE-US-00003 Ex. Reactant Product Yield B4 [00375] [00376] 65% B5 [00377] [00378] 71% B6 B1 [00379] 69% B7 B2 [00380] 72%

Example B8

[0210] ##STR00381##

[0211] A mixture of 18.1 g (100 mmol) of 6-chlorotetralone [26673-31-4], 16.5 g (300 mmol) of propargylamine [2450-71-7], 796 mg [2 mmol] of sodium tetrachloroaurate(III) dihydrate and 200 ml of ethanol is stirred in an autoclave at 120 C. for 24 h. After cooling, the ethanol is removed under reduced pressure, the residue is taken up in 200 ml of ethyl acetate, the solution is washed three times with 200 ml of water and once with 100 ml of saturated sodium chloride solution and dried over magnesium sulfate, and then the latter is filtered off using a silica gel bed in the form of a slurry. After the ethyl acetate has been removed under reduced pressure, the residue is chromatographed on silica gel with n-heptane/ethyl acetate (1:2 v/v). Yield: 9.7 g (45 mmol), 45%. Purity: about 98% by .sup.1H NMR.

Example B9

[0212] ##STR00382##

[0213] A mixture of 25.1 g (100 mmol) of 2,5-dibromo-4-methylpyridine [3430-26-0], 15.6 g (100 mmol) of 4-chlorophenylboronic acid [1679-18-1], 27.6 g (200 mmol) of potassium carbonate, 1.57 g (6 mmol) of triphenylphosphine [603-35-0], 676 mg (3 mmol) of palladium(II) acetate [3375-31-3], 200 g of glass beads (diameter 3 mm), 200 ml of acetonitrile and 100 ml of ethanol is heated under reflux for 48 h. After cooling, the solvents are removed under reduced pressure, 500 ml of toluene are added, the mixture is washed twice with 300 ml each time of water and once with 200 ml of saturated sodium chloride solution, dried over magnesium sulfate and filtered through a silica gel bed in the form of a slurry, which is washed with 300 ml of toluene. After the toluene has been removed under reduced pressure, it is recrystallized once from methanol/ethanol (1:1 v/v) and once from n-heptane. Yield: 17.3 g (61 mmol), 61%. Purity: about 95%. .sup.1H NMR.

Example B10

[0214] ##STR00383##

[0215] B10 can be prepared analogously to the procedure in example B9. For this purpose, 4-bromo-6-tert-butylpyrimidine [19136-36-8] is used rather than 2,5-dibromo-4-methylpyridine. Yield: 70%.

Example B11

[0216] ##STR00384##

[0217] A mixture of 28.3 g (100 mmol) of B9, 12.8 g (105 mmol) of phenylboronic acid, 31.8 g (300 mmol) of sodium carbonate, 787 mg (3 mmol) of triphenylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 300 ml of toluene, 150 ml of ethanol and 300 ml of water is heated under reflux for 48 h. After cooling, the mixture is extended with 300 ml of toluene, and the organic phase is removed, washed once with 300 ml of water and once with 200 ml of saturated sodium chloride solution, and dried over magnesium sulfate. After the solvent has been removed, the residue is chromatographed on silica gel (toluene/ethyl acetate, 9:1 v/v). Yield: 17.1 g (61 mmol), 61%. Purity: about 97% by .sup.1H NMR.

[0218] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00004 Ex. Boronic ester Product Yield B12 [00385] [00386] 56% B13 [00387] [00388] 61% B14 [00389] [00390] 55%

Example B15

[0219] ##STR00391##

[0220] A mixture of 164.2 g (500 mmol) of 2-(1,1,2,2,3,3-hexamethylindan-5-yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane [152418-16-9] (boronic acids can be used analogously), 142.0 g (500 mmol) of 5-bromo-2-iodopyridine [223463-13-6], 159.0 g (1.5 mol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis(triphenylphosphino)palladium(0), 700 ml of toluene, 300 ml of ethanol and 700 ml of water is heated under reflux with good stirring for 16 h. After cooling, 1000 ml of toluene are added, the organic phase is removed and the aqueous phase is re-extracted with 300 ml of toluene. The combined organic phases are washed once with 500 ml of saturated sodium chloride solution. After the organic phase has been dried over sodium sulfate and the solvent has been removed under reduced pressure, the crude product is recrystallized twice from about 300 ml of EtOH. Yield: 130.8 g (365 mmol), 73%. Purity: about 95% by .sup.1H NMR.

[0221] It is analogously possible to prepare the compounds which follow, generally using 5-bromo-2-iodopyridine ([223463-13-6]) as pyridine derivative, which is not listed separately in the table which follows. Only different pyridine derivatives are listed explicitly in the table. Recrystallization can be accomplished using solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol. It is also possible to use these solvents for hot extraction, or to purify by chromatography on silica gel in an automated column system (Torrent from Axel Semrau).

TABLE-US-00005 Boronic acid/ester Ex. Pyridine Product Yield B16 [00392] [100124-06-9] [00393] 69% B17 [00394] [402936-15-6] [00395] 71% B18 [00396] [169126-63-0] [00397] 78% B19 [00398] [1801624-61-2] [00399] 78% B20 [00400] See WO 2016/124304 [00401] 81% B21 [00402] [98-80-6]/[1381937-40-1] [00403] 73% B22 [00404] [1609374-04-0] [00405] 68% B23 [00406] [1174312-53-8] [00407] 63%

Example B24

Variant A:

[0222] ##STR00408##

[0223] A mixture of 35.8 g (100 mmol) of B15, 25.4 g (100 mmol) of bis(pinacolato)diborane [73183-34-3], 49.1 g (500 mmol) of potassium acetate, 1.5 g (2 mmol) of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II) complex with DCM [95464-05-4], 200 g of glass beads (diameter 3 mm), 700 ml of 1,4-dioxane and 700 ml of toluene is heated under reflux for 16 h. After cooling, the suspension is filtered through a Celite bed and the solvent is removed under reduced pressure. The black residue is digested with 1000 ml of hot n-heptane, cyclohexane or toluene and filtered through a Celite bed while still hot, and then concentrated to about 200 ml, in the course of which the product begins to crystallize. Alternatively, hot extraction with ethyl acetate is possible. The crystallization is completed in a refrigerator overnight, and the crystals are filtered off and washed with a little n-heptane. A second product fraction can be obtained from the mother liquor. Yield: 31.6 g (78 mmol), 78%. Purity: about 95% by .sup.1H NMR.

Variant B: Conversion of Aryl Chlorides

[0224] As variant A, except that, rather than 1,1-bis(diphenylphosphino)-ferrocenedichloropalladium(II) complex with DCM, 2 mmol of SPhos [657408-07-6] and 1 mmol of palladium(II) acetate are used.

[0225] In an analogous manner, it is possible to prepare the following compounds, and it is also possible to use cyclohexane, toluene, acetonitrile or mixtures of said solvents for purification rather than n-heptane:

TABLE-US-00006 Bromide-Variant A Ex. Chloride-Variant B Product Yield B25 [00409] [27012-25-5] [00410] 85% B26 [00411] [1215073-34-9] [00412] 80% B27 [00413] [1035556-84-3] [00414] 83% B28 [00415] [1486482-87-4] [00416] 77% B29 [00417] B16 [00418] 67% B30 [00419] B17 [00420] 70% B31 [00421] B18 [00422] 80% B32 [00423] B19 [00424] 80% B33 [00425] B20 [00426] 78% B34 [00427] [31686-64-3] [00428] 74% B35 [00429] B21 [00430] 70% B36 [00431] [88345-95-3] [00432] 68% B37 [00433] [22960-25-4] [00434] 76% B38 [00435] [57669-37-1] [00436] 83% B39 [00437] [68473-51-8] [00438] 85% B40 [00439] [00440] 55% B14 B41 [00441] [463336-07-4] [00442] 72% B42 [00443] [1039080-00-6] [00444] 78% B43 [00445] [1492036-00-6] [00446] 82% B44 [00447] B21 [00448] 60% B45 [00449] B23 [00450] 75% B46 [00451] [1246851-70-6] [00452] 88% B47 [00453] [60781-85-3] [00454] 78% B48 [00455] [1338923-08-2] [00456] 82% B49 [00457] [1446208-20-3] [00458] 80% B50 [00459] [00460] 85% B10 B51 [00461] [00462] 88% B8 B52 [00463] [00464] 76% [102200-03-3] B53 [00465] [00466] 81% B11 B54 [00467] [00468] 78% B12 B55 [00469] [00470] 75% B13

Example B56

[0226] ##STR00471##

[0227] A mixture of 28.1 g (100 mmol) of B25, 28.2 g (100 mmol) of 1-bromo-2-iodobenzene [583-55-1], 31.8 g (300 mmol) of sodium carbonate, 787 mg (3 mmol) of triphenylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 300 ml of toluene, 150 ml of ethanol and 300 ml of water is heated under reflux for 24 h. After cooling, the mixture is extended with 500 ml of toluene, and the organic phase is removed, washed once with 500 ml of water and once with 500 ml of saturated sodium chloride solution and dried over magnesium sulfate. After the solvent has been removed, the residue is recrystallized from ethyl acetate/n-heptane or chromatographed on silica gel (toluene/ethyl acetate, 9:1 v/v). Yield: 22.7 g (73 mmol), 73%. Purity: about 97% by .sup.1H NMR.

[0228] The compounds which follow can be prepared in an analogous manner, and recrystallization can be accomplished using solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol, for example. It is also possible to use these solvents for hot extraction, or to purify by chromatography on silica gel in an automated column system (Torrent from Axel Semrau).

TABLE-US-00007 Ex. Boronic ester Product Yield B57 [00472] [00473] 56% B58 [00474] [00475] 72% B59 [00476] [00477] 71% B60 [00478] [00479] 70% B61 [00480] [00481] 69% B62 [00482] [00483] 67% B63 [00484] [00485] 63% B64 [00486] [00487] 70% B65 [00488] [00489] 73% B66 [00490] [00491] 72% B67 [00492] [00493] 48% B68 [00494] [00495] 65% B69 [00496] [00497] 65% B70 [00498] [00499] 68% B71 [00500] [00501] 77% B72 [00502] [00503] 70% B73 [00504] [00505] 66% B74 [00506] [00507] 71% B75 [00508] [00509] 64% B76 [00510] [00511] 58% B77 [00512] [00513] 62% B78 [00514] [00515] 75% B79 [00516] [00517] 78% B80 [00518] [00519] 82%

Example B81

[0229] ##STR00520##

[0230] A mixture of 36.4 g (100 mmol) of 2,2-(5-chloro-1,3-phenylene)bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane] [1417036-49-7], 65.2 g (210 mmol) of B56, 42.4 g (400 mmol) of sodium carbonate, 1.57 g (6 mmol) of triphenylphosphine, 500 mg (2 mmol) of palladium(II) acetate, 500 ml of toluene, 200 ml of ethanol and 500 ml of water is heated under reflux for 48 h. After cooling, the mixture is extended with 500 ml of toluene, and the organic phase is removed, washed once with 500 ml of water and once with 500 ml of saturated sodium chloride solution and dried over magnesium sulfate. After the solvent has been removed, the residue is chromatographed on silica gel (n-heptane/ethyl acetate, 2:1 v/v). Yield: 41.4 g (68 mmol), 68%. Purity: about 95% by .sup.1H NMR.

[0231] The compounds which follow can be prepared in an analogous manner, and recrystallization can be accomplished using solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol, for example. It is also possible to use these solvents for hot extraction, or to purify by chromatography on silica gel in an automated column system (Torrent from Axel Semrau).

TABLE-US-00008 Ex. Bromide Product Yield B82 [00521] [00522] 67% B83 [00523] [00524] 62% B84 [00525] [00526] 55% B85 [00527] [00528] 63% B86 [00529] [00530] 60% B87 [00531] [00532] 61% B88 [00533] [00534] 58% B89 [00535] [00536] 56% B90 [00537] [00538] 60% B91 [00539] [00540] 64% B92 [00541] [00542] 60% B200 [00543] [00544] 67%

Example B93

[0232] ##STR00545##

[0233] A mixture of 17.1 g (100 mmol) of 4-(2-pyridyl)phenol [51035-40-6] and 12.9 g (100 mmol) of diisopropylethylamine [7087-68-5] is stirred in 400 ml of dichloromethane at room temperature for 10 min. 6.2 ml (40 mmol) of 5-chloroisophthaloyl chloride [2855-02-9], dissolved in 30 ml of dichloromethane, are added dropwise, and the reaction mixture is stirred at room temperature for 14 h. Subsequently, 10 ml of water are added dropwise and the reaction mixture is transferred into a separating funnel. The organic phase is washed twice with 100 ml of water and once with 50 ml of saturated NaCl solution, dried over sodium sulfate and concentrated to dryness. Yield: 18.0 g (38 mmol), 95%. Purity: about 95% by .sup.1H NMR.

[0234] The following compounds can be prepared in an analogous manner: The molar amounts of the reactants used are specified if they differ from those as described in the procedure for B93.

TABLE-US-00009 Alcohol or amine Acid chloride Ex. Reaction time Product Yield B94 [00546] [00547] 90% B95 [00548] [00549] 96% B96 [00550] [00551] 88% B97 [00552] [00553] 76% B98 [00554] [00555] 80% B99 [00556] [00557] 73% B100 [00558] [00559] 78%

Example B101

[0235] ##STR00560##

[0236] 2.0 g (50 mmol) of sodium hydride (60% dispersion in paraffin oil) [7646-69-7] are suspended in 300 ml of THF, then 5.0 g (10 mmol) of B95 are added, and the suspension is stirred at room temperature for 30 minutes. Subsequently, 1.2 ml of iodomethane (50 mmol) [74-88-4] are added and the reaction mixture is stirred at room temperature for 50 h. 20 ml of conc. ammonia solution are added, the mixture is stirred for a further 30 minutes, and the solvent is largely drawn off under reduced pressure. The residue is taken up in 300 ml of dichloromethane, washed once with 200 ml of 5% by weight aqueous ammonia, twice with 100 ml each time of water and once with 100 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The dichloromethane is removed under reduced pressure and the crude product is recrystallized from ethyl acetate/methanol. Yield: 4.3 g (8 mmol), 80%. Purity: about 98% by .sup.1H NMR.

[0237] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00010 Ex. Reactant Product Yield B102 [00561] [00562] 70% B103 [00563] [00564] 69% B104 [00565] [00566] 72%

Example B105

[0238] ##STR00567##

[0239] A mixture of 36.4 g (100 mmol) of 2,2-(5-chloro-1,3-phenylene)bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane] [1417036-49-7], 70.6 g (210 mmol) of B69, 42.4 g (400 mmol) of sodium carbonate, 2.3 g (2 mmol) of tetrakis(triphenylphosphine)palladium(0), 1000 ml of 1,2-dimethoxyethane and 500 ml of water is heated under reflux for 48 h. After cooling, the precipitated solids are filtered off with suction and washed twice with 20 ml of ethanol. The solids are dissolved in 500 ml of dichloromethane and filtered through a Celite bed. The filtrate is concentrated down to 100 ml, then 400 ml of ethanol are added and the precipitated solids are filtered off with suction. The crude product is recrystallized once from ethyl acetate. Yield: 43.6 g (70 mmol), 70%. Purity: about 96% by .sup.1H NMR.

[0240] The compounds which follow can be prepared in an analogous manner, and recrystallization can be accomplished using solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol, for example. It is also possible to use these solvents for hot extraction, or to purify by chromatography on silica gel in an automated column system (Torrent from Axel Semrau).

TABLE-US-00011 B106 [00568] B68 [00569] 64% B107 [00570] B70 [00571] 54% B108 [00572] B72 [00573] 75% B109 [00574] B73 [00575] 71% B110 [00576] B74 [00577] 58% B111 [00578] B75 [00579] 60% B112 [00580] B76 [00581] 66% B113 [00582] B77 [00583] 70% B114 [00584] B78 [00585] 70% B115 [00586] B79 [00587] 63% B116 [00588] B71 [00589] 60% B117 [00590] B80 [00591] 61% B152 [00592] [1989597-40-1] [00593] 57% B153 [00594] [1989597-41-2] [00595] 60% B154 [00596] [1989597-56-9] [00597] 66% B155 [00598] [1989597-54-7] [00599] 62%

Example B119

[0241] ##STR00600##

[0242] A mixture of 57.1 g (100 mmol) of B81, 25.4 g (100 mmol) of bis(pinacolato)diborane [73183-34-3], 49.1 g (500 mmol) of potassium acetate, 2 mmol of SPhos [657408-07-6], 1 mmol of palladium(II) acetate, 200 g of glass beads (diameter 3 mm) and 700 ml of 1,4-dioxane is heated to reflux for 16 h while stirring. After cooling, the suspension is filtered through a Celite bed and the solvent is removed under reduced pressure. The black residue is digested with 1000 ml of hot ethyl acetate and filtered through a Celite bed while still hot, then concentrated to about 200 ml, in the course of which the product begins to crystallize. The crystallization is completed in a refrigerator overnight, and the crystals are filtered off and washed with a little ethyl acetate. A second product fraction can be obtained from the mother liquor. Yield: 31.6 g (78 mmol), 78%. Purity: about 95% by .sup.1H NMR.

[0243] The following compounds can be prepared in an analogous manner, and it is also possible to use toluene, n-heptane, cyclohexane or acetonitrile rather than ethyl acetate for recrystallization or for hot extraction in the case of sparingly soluble products:

TABLE-US-00012 Ex. Bromide Product Yield B120 [00601] [00602] 80% B121 [00603] [00604] 84% B122 [00605] [00606] 71% B123 [00607] [00608] 80% B124 [00609] [00610] 85% B125 [00611] [00612] 82% B126 [00613] [00614] 77% B127 [00615] [00616] 72% B128 [00617] [00618] 77% B129 [00619] [00620] 80% B130 [00621] [00622] 81% B131 [00623] [00624] 88% B132 [00625] [00626] 79% B133 [00627] [00628] 76% B134 [00629] [00630] 89% B135 [00631] [00632] 84% B136 [00633] [00634] 79% B137 [00635] [00636] 75% B138 [00637] [00638] 77% B139 [00639] [00640] 80% B140 [00641] [00642] 82% B141 [00643] [00644] 88% B142 [00645] [00646] 90% B143 [00647] [00648] 76% B144 [00649] [00650] 80% B145 [00651] [00652] 81% B146 [00653] [00654] 84% B147 [00655] [00656] 74% B148 [00657] [00658] 73% B149 [00659] [00660] 76% B150 [00661] [00662] 72% B151 [00663] [00664] 75% B156 [00665] [00666] 70% B157 [00667] [00668] 72% B158 [00669] [00670] 69% B159 [00671] [00672] 74% B120 [00673] [00674] 69%

B: Synthesis of the Ligands L and Ligand Precursors LV:

Example L1

Variant A:

[0244] ##STR00675##

[0245] A mixture of 5.9 g (15 mmol) of B3, 19.9 g (30.0 mmol) of B120, 9.2 g (87 mmol) of sodium carbonate, 340 mg (1.3 mmol) of triphenylphosphine, 98 mg (0.44 mmol) of palladium(II) acetate, 200 ml of toluene, 100 ml of ethanol and 200 ml of water is heated under reflux for 40 h. After cooling, the precipitated solids are filtered off with suction and washed twice with 30 ml each time of ethanol. The crude product is dissolved in 300 ml of dichloromethane and filtered through a silica gel bed. The silica gel bed is washed through three times with 200 ml each time of dichloromethane/ethyl acetate 1:1. The filtrate is washed twice with water and once with saturated sodium chloride solution and dried over sodium sulfate. The filtrate is concentrated to dryness. The residue is recrystallized from ethyl acetate at reflux. Yield: 8.8 g (10.7 mmol), 55%. Purity: about 99% by .sup.1H NMR.

Variant B:

[0246] A mixture of 4.5 g (15 mmol) of B160, 19.9 g (30.0 mmol) of B120, 13.8 g (87 mmol) of potassium phosphate monohydrate, 507 mg (0.6 mmol) of XPhos palladacycle Gen. 3 [1445085-55-1], 200 ml of THF and 100 ml of water is heated under reflux for 20 h. After cooling, the precipitated solids are filtered off with suction and washed with twice with 30 ml each time of water and twice with 30 ml each time of ethanol. The crude product is dissolved in 200 ml of dichloromethane and filtered through a silica gel bed. The silica gel bed is washed through three times with 200 ml each time of dichloromethane/ethyl acetate 1:1. The filtrate is washed twice with water and once with saturated sodium chloride solution, dried over sodium sulfate and concentrated to dryness. The residue is recrystallized from ethyl acetate at reflux. Yield: 12.0 g (9.2 mmol), 61%. Purity: about 99% by .sup.1H NMR.

[0247] The compounds which follow can be prepared analogously to the procedure described for L1 (variant B). In this case, it is also possible to use toluene, cyclohexane, ethyl acetate or dimethylformamide for purification by recrystallization or hot extraction. Alternatively, the ligands can be purified by chromatography.

TABLE-US-00013 Reac- Ex. tants Product Yield L2 B160 + B119 [00676] 64% L3 B160 + B123 [00677] 61% L4 B160 + B139 [00678] 68% L5 B160 + B149 [00679] 65% L6 B160 + B138 [00680] 66% L7 B160 + B127 [00681] 70% L8 B160 + B136 [00682] 57% L9 B160 + B140 [00683] 69% L10 B160 + B129 [00684] 64% L11 B160 + B125 [00685] 62% L12 B160 + B126 [00686] 63% L13 B160 + B128 [00687] 61% L14 B160 + B142 [00688] 67% L15 B4 + B119 [00689] 60% L16 B4 + B120 [00690] 58% L17 B4 + B127 [00691] 56% L18 B4 + B131 [00692] 53% L19 B4 + B146 [00693] 70% L20 B4 + B147 [00694] 58% L21 B4 + B122 [00695] 63% L22 B4 + B150 [00696] 57% L23 B4 + B131 [00697] 56% L24 B4 + B145 [00698] 65% L25 64 + B148 [00699] 60% L26 B5 + B119 [00700] 60% L27 B5 + B120 [00701] 58% L28 B5 + B143 [00702] 62% L29 B5 + B129 [00703] 57% L30 B5 + B144 [00704] 63% L31 B6 + B120 [00705] 65% L32 B6 + B143 [00706] 61% L33 B6 + B129 [00707] 55% L34 B6 + B119 [00708] 60% L35 B7 + B119 [00709] 62% L36 B7 + B128 [00710] 57% L37 B7 + B131 [00711] 50% L38 B7 + B150 [00712] 63% L39 B160 + B130 [00713] 58% L40 B160 + B156 [00714] 55% L41 B160 + B157 [00715] 58% L42 B160 + B158 [00716] 60% L43 B160 + B159 [00717] 59% L44 B160 + 15 mmol B123 + 15 mmol B139 [00718] 20% Chromatographic separation of the mixture on an automated column system (Torrent from A. Semrau) with isolation of the unsymmetric ligand L45 B160 + 15 mmol B120 + 15 mmol B156 [00719] 22% Chromatographic separation of the mixture on an automated column system (Torrent from A. Semrau) with isolation of the unsymmetric ligand LV100 B160 + B210 [00720] 68%

Example LV110

[0248] ##STR00721##

[0249] Analogous to F. Diness et al., Angew. Chem. Int. Ed., 2012, 51, 8012. A mixture of 21.3 g (20 mmol) of LV1, 11.8 g (100 mmol) of benzimidazole and 97.9 g (300 mmol) of cesium carbonate in 500 ml of N,N-dimethylacetamide is heated to 175 C. in a stirred autoclave for 18 h. After cooling, the solvent is largely drawn off and the residue is taken up in 500 ml of toluene, washed three times with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution, dried over magnesium sulfate and then filtered through a Celite bed in the form of a slurry. After the solvent has been removed under reduced pressure, the residue is recrystallized from ethyl acetate/methanol. Yield: 16.0 g (11 mmol), 55%. Purity: about 96% by .sup.1H NMR.

[0250] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00014 Ex. Reactants Product Yield LV111 [00722] [00723] 51% LV112 [00724] [00725] 57% LV113 [00726] [00727] 60%

Example LV120

[0251] ##STR00728##

[0252] To a solution of 14.6 g (10 mmol) of LV110 in 100 ml of DCM are added dropwise 2.8 ml (44 mmol) of methyl iodide [74-88-4] and the mixture is heated to 60 C. in a stirred autoclave for 24 h. After cooling, the solvent and excess methyl iodide are drawn off under reduced pressure. The ligand precursor thus obtained is converted without further purification. Yield: 20.3 g (10 mmol), quantitative. Purity: about 95% by .sup.1H NMR.

[0253] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00015 Product Ex. Reactant Yield LV121 [00729] quant. LV111 LV122 [00730] quant. LV112 LV123 [00731] quant. LV113

Example LV130

[0254] ##STR00732##

[0255] A mixture of 14.6 g (10 mmol) of LV110, 16.6 g (45 mmol) of diphenyliodonium tetrafluoroborate [313-39-3], 363 mg (2 mmol) of copper(II) acetate [142-71-2] in 200 ml of DMF is heated to 100 C. for 8 h. After cooling, the solvent is removed under reduced pressure, the residue is taken up in a mixture of 100 ml of dichloromethane, 100 ml of acetone and 20 ml of methanol and filtered through a silica gel bed, and the core fraction is extracted and concentrated to dryness. The ligand precursor thus obtained is converted without further purification. Yield: 14.8 g (7 mmol), 70%. Purity: about 90% by .sup.1H NMR.

[0256] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00016 Product Ex. Reactant Yield LV131 [00733] 65% LV111 LV132 [00734] 68% LV112 LV133 [00735] 63% LV113

C: Synthesis of the Metal Complexes:

Variant A:

Example Ir.SUB.2.(L1)

[0257] ##STR00736##

[0258] A mixture of 13.0 g (10 mmol) of ligand L1, 9.8 g (20 mmol) of trisacetylacetonatoiridium(III) [15635-87-7] and 100 g of hydroquinone [123-31-9] is initially charged in a 1000 ml two-neck round-bottom flask with a glass-sheathed magnetic bar. The flask is provided with a water separator (for media of lower density than water) and an air condenser with argon blanketing and placed into a metal heating bath. The apparatus is purged with argon from the top via the argon blanketing system for 15 min, allowing the argon to flow out of the side neck of the two-neck flask. Through the side neck of the two-neck flask, a glass-sheathed Pt-100 thermocouple is introduced into the flask and the end is positioned just above the magnetic stirrer bar. The apparatus is thermally insulated with several loose windings of domestic aluminum foil, the insulation being run up to the middle of the riser tube of the water separator. Then the apparatus is heated rapidly with a heated laboratory stirrer system to 250 C., measured with the Pt-100 thermal sensor which dips into the molten stirred reaction mixture. Over the next 2 h, the reaction mixture is kept at 250 C., in the course of which a small amount of condensate is distilled off and collects in the water separator. The reaction mixture is left to cool down to 190 C., then 100 ml of ethylene glycol are added dropwise. The mixture is left to cool down further to 80 C., then 500 ml of methanol are added dropwise and the mixture is heated at reflux for 1 h. The suspension thus obtained is filtered through a double-ended frit, and the solids are washed twice with 50 ml of methanol and dried under reduced pressure. The solids thus obtained are dissolved in 220 ml of dichloromethane and filtered through about 1 kg of silica gel in the form of a dichloromethane slurry (column diameter about 18 cm) with exclusion of air in the dark, leaving dark-colored components at the start. The core fraction is cut out and concentrated on a rotary evaporator, with simultaneous continuous dropwise addition of MeOH until crystallization. After removal with suction, washing with a little MeOH and drying under reduced pressure, further purification is effected by hot extraction five times with toluene (amount initially charged in each case about 150 ml, extraction thimble: standard Soxhlet thimbles made from cellulose from Whatman) with careful exclusion of air and light. Finally, the products are heat-treated at 280 C. under high vacuum. 10.8 g of red solid (6.4 mmol), 64%. Purity: >99.9% by HPLC.

[0259] The compounds which follow can be synthesized in an analogous manner. The metal complexes shown below can in principle be purified by chromatography, typically using an automated column system (Torrent from Axel Semrau), recrystallization or hot extraction (also abbreviated to HE in the table below). Residual solvents can be removed by heat treatment under high vacuum at typically 250-330 C.

[0260] In an analogous manner, it is possible to obtain mixed metallic RhIr complexes by first using just 10 mmol rather than 20 mmol of tris(acetylacetonato)iridium(III) [15635-87-7] and then, after half the reaction time specified, adding 4.0 g (10 mmol) of tris(acetylacetonato)rhodium(III) [14284-92-5].

Variant B: Carbene Complexes

[0261] A suspension of 10 mmol of the carbene ligand precursor LV and 40 mmol of Ag.sub.2O in 300 ml of dioxane is stirred at 30 C. for 12 h. Then 20 mmol of [Ir(COD)Cl].sub.2 [12112-67-3] are added and the mixture is heated under reflux for 8 h. The solids are filtered off while the mixture is still hot and they are washed three times with 50 ml each time of hot dioxane, and the filtrates are combined and concentrated to dryness under reduced pressure. The crude product thus obtained is chromatographed twice on basic alumina with ethyl acetate/cyclohexane or toluene. The product is purified further by continuous hot extraction five times with acetonitrile/dichloromethane and hot extraction twice with ethyl acetate/methanol (amount initially charged in each case about 200 ml, extraction thimble: standard Soxhlet thimbles made from cellulose from Whatman) with careful exclusion of air and light. Finally, the product is heat-treated under high vacuum. Purity: >99.8% by HPLC.

[0262] The compounds which follow can be prepared analogously to variants A and B

TABLE-US-00017 Ex. Reactant Product/reaction conditions/hot extractant (HE) Yield Variant A Rh.sub.2(L1) L1 Rh(acac).sub.3 [14284- 92-5] rather than Ir(acac).sub.3 [00737] 50% Rh.sub.2(L1) 250 C.; 2 h Hot extraction: toluene Ir.sub.2(L2) L2 [00738] 60% Ir.sub.2(L2) 250 C.; 4 h Hot extraction: ethyl acetate Rh.sub.2(L2) L2 Rh(acac).sub.3 [14284- 92-5] rather than Ir(acac) [00739] 48% Rh.sub.2(L2) 250 C.; 2 h Hot extraction: ethyl acetate Ir.sub.2(L3) L3 [00740] 56% Ir.sub.2(L3) 250 C.: 3 h HE: ethyl acetate/acetonitrile 4:1 Ir.sub.2(L4) L4 [00741] 62% Ir.sub.2(L4) 250 C.; 3 h HE: ethyl acetate/acetonitrile 2:1 Ir.sub.2(L5) L5 [00742] 52% Ir.sub.2(L5) 250 C.; 2 h Recrystallization: DMF Ir.sub.2(L6) L6 [00743] 65% Ir.sub.2(L6) 250 C.; 5 h Hot extraction: o-xylene Ir.sub.2(L7) L7 [00744] 60% Ir.sub.2(L7) 250 C./5 h Hot extraction: toluene Ir.sub.2(L8) L8 [00745] 43% Ir.sub.2(L8) 220 C.; 5 h Recrystallization: DMSO Ir.sub.2(L9) L9 [00746] 56% Ir.sub.2(L9) 250 C.; 3 h Hot extraction: toluene Ir.sub.2(L10) L10 [00747] 58% Ir.sub.2(L10) 250 C.; 1.5 h Hot extraction: ethyl acetate Ir.sub.2(L11) L11 [00748] 62% Ir.sub.2(L11) 250 C.; 2 h Hot extraction: n-butyl acetate Ir.sub.2(L12) L12 [00749] 58% Ir.sub.2(L12) 250 C.; 2 h Hot extraction: toluene Ir.sub.2(L13) L13 [00750] 61% Ir.sub.2(L13) 250 C.; 3 h Hot extraction: n-butyl acetate Ir.sub.2(L14) L14 [00751] 57% Ir.sub.2(L14) 260 C.; 3 h Hot extraction: o-xylene Ir.sub.2(L15) L15 [00752] 62% Ir.sub.2(L15) 250 C.; 2 h Hot extraction: toluene Ir.sub.2(L16) L16 [00753] 56% Ir.sub.2(L16) 250 C.; 2 h Hot extraction: ethyl acetate Ir.sub.2(L17) L17 [00754] 53% Ir.sub.2(L17) 265 C.; 3 h Hot extraction: toluene Ir.sub.2(L18) L18 [00755] 41% Ir.sub.2(L18) 255 C.; 2 h Recrystallization: DMF Ir.sub.2(L19) L19 [00756] 65% Ir.sub.2(L19) 250 C.; 3 h Hot extraction: o-xylene Ir.sub.2(L20) L20 [00757] 50% Ir.sub.2(L20) 250 C.; 3 h Hot extraction: cyclohexane Ir.sub.2(L21) L21 [00758] 55% Ir.sub.2(L21) 250 C.; 3 h Hot extraction: toluene Ir.sub.2(L22) L22 [00759] 58% Ir.sub.2(L22) 265 C.; 5 h Hot extraction: n-butyl acetate Ir.sub.2(L23) L23 [00760] 48% Ir.sub.2(L23) 250 C.; 3 h Hot extraction: n-butyl acetate Ir.sub.2(L24) L24 [00761] 63% Ir.sub.2(L24) 250 C.; 2 h Hot extraction: o-xylene Ir.sub.2(L25) L25 [00762] 54% Ir.sub.2(L25) 250 C.; 2 h Hot extraction: ethyl acetate Ir.sub.2(L26) L26 [00763] 63% Ir.sub.2(L26) 250 C.; 3.5 h Hot extraction: n-butyl acetate Ir.sub.2(L27) L27 [00764] 66% Ir.sub.2(L27) 260 C.; 3 h Hot extraction: ethyl acetate Ir.sub.2(L28) L28 [00765] 56% Ir.sub.2(L28) 250 C.; 3 h Hot extraction: n-butyl acetate Ir.sub.2(L29) L29 [00766] 60% Ir.sub.2(L29) 235 C.; 2 h Hot extraction: toluene Ir.sub.2(L30) L30 [00767] 52% Ir.sub.2(L30) 250 C.; 2 h Hot extraction: toluene Ir.sub.2(L31) L31 [00768] 48% Ir.sub.2(L31) 240 C.; 2 h Hot extraction: dichloromethane Ir.sub.2(L32) L32 [00769] 46% Ir.sub.2(L32) 230 C.; 2 h Hot extraction: toluene Ir.sub.2(L33) L33 [00770] 47% Ir.sub.2(L33) 250 C.; 2 h Recrystallization: dimethylformamide Ir.sub.2(L34) L34 [00771] 50% Ir.sub.2(L34) 250 C.; 3 h Hot extraction: n-butyl acetate Ir.sub.2(L35) L35 [00772] 43% Ir.sub.2(L35) 270 C.; 3 h Hot extraction: toluene Ir.sub.2(L36) L36 [00773] 52% Ir.sub.2(L36) 260 C.; 3 h Hot extraction: ethyl acetate Ir.sub.2(L37) L37 [00774] 41% Ir.sub.2(L37) 250 C.; 4 h Hot extraction; 2-propanol Ir.sub.2(L38) L38 [00775] 44% Ir.sub.2(L38) 250 C.; 3 h Hot extraction: ethyl acetate Ir.sub.2(L39) L39 [00776] 58% Ir.sub.2(L39) 260 C.; 3 h Hot extraction: ethyl acetate Ir.sub.2(L40) L40 [00777] 55% Ir.sub.2(L40) 260 C.; 3 h Hot extraction: ethyl acetate Ir.sub.2(L41) L41 [00778] 57% Ir.sub.2(L41) 260 C.; 3 h Hot extraction: toluene Ir.sub.2(L42) L42 [00779] 51% Ir.sub.2(L42) 260 C.; 3 h Hot extraction: toluene Ir.sub.2(L43) L43 [00780] 54% Ir.sub.2(L43) 260 C.; 3 h Hot extraction: butyl acetate Ir.sub.2(L44) L44 [00781] 50% Ir.sub.2(L44) 260 C.; 3 h Hot extraction: ethyl acetate Ir.sub.2(L45) L45 [00782] 57% Ir.sub.2(L45) 260 C.; 3 h Hot extraction: ethyl acetate Rh- Ir(L1) L1 Rh(acac).sub.3 Ir(acac).sub.3 [00783] 48% Rh-Ir(L1) 250 C.; 2 h Hot extraction: toluene Rh- Ir(L17) L17 Rh(acac).sub.3 Ir(acac).sub.3 [00784] 45% Rh-Ir(L17) 260 C.; 3 h Hot extraction: toluene Variant B - Carbene complexes Ir.sub.2(L120) LV120 [00785] 22% Ir.sub.2(L121) LV121 [00786] 25% Ir.sub.2(L122) LV122 [00787] 23% Ir.sub.2(L123) LV123 [00788] 27% Ir.sub.2(L130) LV130 [00789] 24% Ir.sub.2(L131) LV131 [00790] 20% Ir.sub.2(L132) LV132 [00791] 26% Ir.sub.2(L133) LV133 [00792] 28%

D: Functionalization of the Metal Complexes:

1) Halogenation of the Iridium Complexes:

[0263] To a solution or suspension of 10 mmol of a complex bearing AC-H groups (with A=1-4) in the para position to the iridium in the bidentate sub-ligand in 500 to 2000 ml of dichloromethane according to the solubility of the metal complexes is added, in the dark and with exclusion of air, at 30 to +30 C., A10.5 mmol of N-halosuccinimide (halogen: Cl, Br, I), and the mixture is stirred for 20 h. Complexes of sparing solubility in DCM may also be converted in other solvents (TCE, THF, DMF, chlorobenzene, etc.) and at elevated temperature. Subsequently, the solvent is substantially removed under reduced pressure. The residue is extracted by boiling with 100 ml of methanol, and the solids are filtered off with suction, washed three times with 30 ml of methanol and then dried under reduced pressure. This gives the iridium complexes brominated/halogenated in the para position to the iridium. Complexes having a HOMO (CV) of about 5.1 to 5.0 eV and of smaller magnitude have a tendency to oxidation (Ir(III).fwdarw.Ir(IV)), the oxidizing agent being bromine released from NBS. This oxidation reaction is apparent by a distinct green hue or brown hue in the otherwise yellow to red solutions/suspensions of the emitters. In such cases, 1-2 further equivalents of NBS are added. For workup, 300-500 ml of methanol and 4 ml of hydrazine hydrate as reducing agent are added, which causes the green or brown solutions/suspensions to turn yellow or red (reduction of Ir(IV).fwdarw.Ir(III)). Then the solvent is substantially drawn off under reduced pressure, 300 ml of methanol are added, and the solids are filtered off with suction, washed three times with 100 ml each time of methanol and dried under reduced pressure.

[0264] Substoichiometric brominations, for example mono- and dibrominations, of complexes having 4 CH groups in the para position to the iridium atoms usually proceed less selectively than the stoichiometric brominations. The crude products of these brominations can be separated by chromatography (CombiFlash Torrent from A. Semrau).

Synthesis of Ir.SUB.2.(L1-4Br):

[0265] ##STR00793##

[0266] To a suspension of 16.8 g (10 mmol) of Ir.sub.2(L1) in 2000 ml of DCM are added 5.0 g (45 mmol) of N-bromosuccinimide all at once and then the mixture is stirred for 20 h. 2 ml of hydrazine hydrate and then 300 ml of MeOH are added. After removing about 1900 ml of the DCM under reduced pressure, the red solids are filtered off with suction, washed three times with about 50 ml of methanol and dried under reduced pressure. Yield: 18.5 g (9.3 mmol), 93%; purity: >99.0% by NMR.

[0267] The following compounds can be synthesized in an analogous manner:

TABLE-US-00018 Ex. Reactant Product/amount of NBS Yield Rh.sub.2(L1-4Br) Rh.sub.2(L1) [00794] 90% Ir.sub.2(L2-4Br) Ir.sub.2(L2) [00795] 95% Rh.sub.2(L2-4Br) Rh.sub.2(L2) Rh.sub.2(L2-4Br) 88% 4.5 equiv. NBS Ir.sub.2(L3-4Br) Ir.sub.2(L3) Ir.sub.2(L3-4Br) 96% 4.5 equiv. NBS Ir.sub.2(L4-4Br) Ir.sub.2(L4) Ir.sub.2(L4-4Br) 92% 4.5 equiv. NBS Ir.sub.2(L5-4Br) Ir.sub.2(L5) Ir.sub.2(L5-4Br) 84% 5 equiv. NBS Ir.sub.2(L6-4Br) Ir.sub.2(L6) Ir.sub.2(L6-4Br) 95% 5 equiv NBS; 0.01 equiv HBr (aq) Ir.sub.2(L8-4Br) Ir.sub.2(L8) Ir.sub.2(L8-4Br) 83% 5 equiv. NBS Ir.sub.2(L9-4Br) Ir.sub.2(L9) Ir.sub.2(L9-4Br) 87% 4.5 equiv. NBS Ir.sub.2(L10-4Br) Ir.sub.2(L10) Ir.sub.2(L10-4Br) 88% 5 equiv. NBS Ir.sub.2(L11-4Br) Ir.sub.2(L11) I1-Ir.sub.2(L11-4Br) 91% 4.5 equiv. NBS Ir.sub.2(L12-4Br) Ir.sub.2(L12) Ir.sub.2(L12-4Br) 92% 4.5 equiv. NBS Ir.sub.2(L13-4Br) Ir.sub.2(L13) Ir.sub.2(L13-4Br) 94% 4.5 equiv. NBS Ir.sub.2(L14-4Br) Ir.sub.2(L14) Ir.sub.2(L14-4Br) 90% 5 equiv. NBS, 0.02 equiv. HBr (aq) Ir.sub.2(L15-4Br) Ir.sub.2(L15) [00796] 92% Ir.sub.2(L16-4Br) Ir.sub.2(L16) [00797] 86% Ir.sub.2(L18-4Br) Ir.sub.2(L18) Ir.sub.2(L18-4Br) 81% 5 equiv. NBS Ir.sub.2(L21-4Br) Ir.sub.2(L21) Ir.sub.2(L21-4Br) 95% 4.5 equiv. NBS Ir.sub.2(L23-4Br) Ir.sub.2(L23) Ir.sub.2(L23-4Br) 83% 5 equiv. NBS Ir.sub.2(L26-4Br) Ir.sub.2(L26) [00798] 90% Ir.sub.2(L27-4Br) Ir.sub.2(L27) [00799] 95% Ir.sub.2(L31-4Br) Ir.sub.2(L31) [00800] 86% L32(L32-4Br) Ir.sub.2(L32) Ir.sub.2(L32-4Br) 91% 4.5 equiv. NBS: Ir.sub.2(L33-4Br) Ir.sub.2(L33) [00801] 90% Ir.sub.2(L34-4Br) Ir.sub.2(L34) Ir.sub.2(L34-4Br) 85% 4.5 equiv. NBS Ir.sub.2(L35-4Br) Ir.sub.2(L35) [00802] 89% Ir.sub.2(L36-4-Br) Ir.sub.2(L36) [00803] 84% Ir.sub.2(L39-4Br) Ir.sub.2(L39) [00804] 88% Ir.sub.2(L120-4Br) Ir.sub.2(L120) [00805] 90% Ir.sub.2(L131-4Br) Ir.sub.2(L131) [00806] 87%
2) Suzuki Coupling with the Brominated Iridium Complexes:

Variant a, Biphasic Reaction Mixture:

[0268] To a suspension of 10 mmol of a brominated complex, 12-20 mmol of boronic acid or boronic ester per Br function and 60-100 mmol of tripotassium phosphate in a mixture of 300 ml of toluene, 100 ml of dioxane and 300 ml of water are added 0.6 mmol of tri-o-tolylphosphine and then 0.1 mmol of palladium(II) acetate, and the mixture is heated under reflux for 16 h. After cooling, 500 ml of water and 200 ml of toluene are added, the aqueous phase is removed, and the organic phase is washed three times with 200 ml of water and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a Celite bed and washed through with toluene, the toluene is removed almost completely under reduced pressure, 300 ml of methanol are added, and the precipitated crude product is filtered off with suction, washed three times with 50 ml each time of methanol and dried under reduced pressure. The crude product is chromatographed on silica gel in an automated column system (Torrent from Semrau). Subsequently, the complex is purified further by hot extraction in solvents such as ethyl acetate, toluene, dioxane, acetonitrile, cyclohexane, ortho- or para-xylene, n-butyl acetate etc. Alternatively, it is possible to recrystallize from these solvents and high boilers such as dimethylformamide, dimethyl sulfoxide or mesitylene. The metal complex is finally heat-treated. The heat treatment is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 200-350 C.

Variant B, Monophasic Reaction Mixture:

[0269] To a suspension of 10 mmol of a brominated complex, 12-20 mmol of boronic acid or boronic ester per Br function and 100-180 mmol of the base (potassium fluoride, tripotassium phosphate (anhydrous, monohydrate or trihydrate), potassium carbonate, cesium carbonate etc.) and 100 g of glass beads (diameter 3 mm) in 100 ml-500 ml of an aprotic solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.) is added 0.2 mmol of tetrakis(triphenylphosphine)palladium(0) [14221-01-3], and the mixture is heated under reflux for 24 h. Alternatively, it is possible to use other phosphines such as triphenylphosphine, tri-tert-butylphosphine, SPhos, XPhos, RuPhos, XanthPhos, etc. in combination with Pd(OAc).sub.2, the preferred phosphine:palladium ratio in the case of these phosphines being 3:1 to 1.2:1. The solvent is removed under reduced pressure, the product is taken up in a suitable solvent (toluene, dichloromethane, ethyl acetate, etc.) and purification is effected as described in Variant A.

Synthesis of Ir.SUB.2.100:

[0270] ##STR00807##

Variant B:

[0271] Use of 19.92 g (10.0 mmol) of Ir(L1-4Br) and 25.3 g (80.0 mmol) of 2-(3,5-di-tert-butylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1071924-13-4], 27.6 g (120 mmol) of tripotassium phosphate monohydrate, 116 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium(0), 500 ml of dry dimethyl sulfoxide, 100 C., 16 h. Chromatographic separation on silica gel with toluene/heptane (automated column system, Torrent from Axel Semrau), followed by hot extraction five times with ethyl acetate. Yield: 13.6 g (5.6 mmol), 56%; purity: about 99.9% by HPLC.

[0272] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00019 Reactant Variant/Reaction conditions Ex. Boronic acid Product/hot extractant (HE) Yield Rh.sub.2100 [00808] [00809] 28% Ir.sub.2101 [00810] [00811] 53% Ir.sub.2102 [00812] [00813] 56% Ir.sub.2103 [00814] [00815] 48% Ir.sub.2104 [00816] [00817] 47% Ir.sub.2105 [00818] [00819] 21% Ir.sub.2106 [00820] [00821] 51% Ir.sub.2107 [00822] [00823] 52% Ir.sub.2108 [00824] [00825] 50% Ir.sub.2109 [00826] [00827] 45% Ir.sub.2110 [00828] [00829] 48% Ir.sub.2111 [00830] [00831] 54% Ir.sub.2112 [00832] [00833] 47% Ir.sub.2113 [00834] [00835] 51%

3) Deuteration of Ir Complexes:

Example: Ir.SUB.2.(L12-D12)

[0273] ##STR00836##

[0274] A mixture of 2.12 g (1 mmol) of Ir.sub.2(L12), 68 mg (1 mmol) of sodium ethoxide, 5 ml of methanol-D4 and 80 ml of DMSO-D6 is heated to 120 C. for 2 h. After cooling to 50 C., 1 ml of DCI (10% aqueous solution) is added. The solvent is removed under reduced pressure and the residue is chromatographed with DCM on silica gel. Yield: 2.11 g (0.95 mmol), 95%, deuteration level >95%.

[0275] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00020 Ex. Reactant/product Yield Ir.sub.2(L17-D12) [00837] 90%

Example: Photophysical Properties of Ir.SUB.2.(L1)

[0276] The maximum in the photoluminescence spectrum in nm is determined in a degassed about 10.sup.5 molar solution of Ir.sub.2(L1) in toluene at room temperature at an excitation wavelength of 400 nm. The photoluminescence maximum is at 603 nm.

Device Examples

Example 1: Production of the OLEDs

[0277] The complexes of the invention can be processed from solution and lead, compared to vacuum-processed OLEDs, to much more easily producible OLEDs having properties that are nevertheless good. There are already many descriptions of the production of completely solution-based OLEDs in the literature, for example in WO 2004/037887. There have likewise been many descriptions of the production of vacuum-based OLEDs, including in WO 2004/058911. In the examples discussed hereinafter, layers applied in a solution-based and vacuum-based manner are combined within an OLED, and so the processing up to and including the emission layer is effected from solution and in the subsequent layers (hole blocker layer and electron transport layer) from vacuum. For this purpose, the previously described general methods are matched to the circumstances described here (layer thickness variation, materials) and combined as follows. The general structure is as follows: substrate/ITO (50 nm)/hole injection layer (HIL)/hole transport layer (HTL)/emission layer (EML)/hole blocker layer (HBL)/electron transport layer (ETL)/cathode (aluminum, 100 nm). Substrates used are glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm. For better processing, they are coated with PEDOT:PSS (poly(3,4-ethylenedioxy-2,5-thiophene) polystyrenesulfonate, purchased from Heraeus Precious Metals GmbH & Co. KG, Germany). PEDOT:PSS is spun on from water under air and subsequently baked under air at 180 C. for 10 minutes in order to remove residual water. The hole transport layer and the emission layer are applied to these coated glass plates. The hole transport layer used is crosslinkable. A polymer of the structure shown below is used, which can be synthesized according to WO 2010/097155 or WO 2013/156130:

##STR00838##

[0278] The hole transport polymer is dissolved in toluene. The typical solids content of such solutions is about 5 g/I when, as here, the layer thickness of 20 nm which is typical of a device is to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere, argon in the present case, and baked at 180 C. for 60 minutes.

[0279] The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). In addition, mixtures of a plurality of matrix materials and co-dopants may occur. Details given in such a form as TMM-A (92%):dopant (8%) mean here that the material TMM-A is present in the emission layer in a proportion by weight of 92% and dopant in a proportion by weight of 8%. The mixture for the emission layer is dissolved in toluene or optionally chlorobenzene. The typical solids content of such solutions is about 17 g/I when, as here, the layer thickness of 60 nm which is typical of a device is to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere, argon in the present case, and baked at 150 C. for 10 minutes. The materials used in the present case are shown in table 1.

TABLE-US-00021 TABLE 1 EML materials used [00839] [00840] [00841]

[0280] The materials for the hole blocker layer and electron transport layer are applied by thermal vapor deposition in a vacuum chamber. The electron transport layer, for example, may consist of more than one material, the materials being added to one another by co-evaporation in a particular proportion by volume. Details given in such a form as ETM1:ETM2 (50%:50%) mean here that the ETM1 and ETM2 materials are present in the layer in a proportion by volume of 50% each. The materials used in the present case are shown in table 2.

TABLE-US-00022 TABLE 2 HBL and ETL materials used [00842] [00843]

[0281] The cathode is formed by the thermal evaporation of a 100 nm aluminum layer. The OLEDs are characterized in a standard manner. The EML mixtures and structures of the OLED components examined are shown in table 3 and table 4. In all cases, intense yellow through orange-red to red emission is observed.

TABLE-US-00023 TABLE 3 EML mixtures of the OLED components examined Matrix A Co-matrix B Co-dopant C Dopant D Ex. material % material % material % material % E-1 A-1 30 B-1 34 C-1 30 Ir.sub.2(L1) 6 E-2 A-1 50 B-1 25 C-1 15 Ir.sub.2(L1) 10 E-3 A-1 40 B-1 45 Ir.sub.2(L1) 15 E-4 A-1 50 B-1 25 C-1 15 Rh.sub.2(L1) 10 E-5 A-1 50 B-1 25 C-1 15 Ir.sub.2(L2) 10 E-6 A-1 50 B-1 25 C-1 15 Rh.sub.2(L2) 10 E-7 A-1 50 B-1 25 C-1 15 Ir.sub.2(L3) 10 E-8 A-1 50 B-1 25 C-1 15 Ir.sub.2(L4) 10 E-9 A-1 50 B-1 25 C-1 15 Ir.sub.2(L5) 10 E-10 A-1 50 B-1 25 C-1 15 Ir.sub.2(L6) 10 E-11 A-1 50 B-1 25 C-1 15 Ir.sub.2(L7) 10 E-12 A-1 50 B-1 25 C-1 15 Ir.sub.2(L8) 10 E-13 A-1 50 B-1 25 C-1 15 Ir.sub.2(L9) 10 E-14 A-1 50 B-1 25 C-1 15 Ir.sub.2(L10) 10 E-15 A-1 50 B-1 25 C-1 15 Ir.sub.2(L11) 10 E-16 A-1 50 B-1 25 C-1 15 Ir.sub.2(L12) 10 E-17 A-1 50 B-1 25 C-1 15 Ir.sub.2(L13) 10 E-18 A-1 50 B-1 25 C-1 15 Ir.sub.2(L14) 10 E-19 A-1 50 B-1 25 C-1 15 Ir.sub.2(L15) 10 E-20 A-1 50 B-1 25 C-1 15 Ir.sub.2(L16) 10 E-21 A-1 50 B-1 25 C-1 15 Ir.sub.2(L17) 10 E-22 A-1 50 B-1 25 C-1 15 Ir.sub.2(L18) 10 E-23 A-1 50 B-1 25 C-1 15 Ir.sub.2(L19) 10 E-24 A-1 50 B-1 25 C-1 15 Ir.sub.2(L20) 10 E-25 A-1 50 B-1 25 C-1 15 Ir.sub.2(L21) 10 E-26 A-1 50 B-1 25 C-1 15 Ir.sub.2(L22) 10 E-27 A-1 50 B-1 25 C-1 15 Ir.sub.2(L23) 10 E-28 A-1 50 B-1 25 C-1 15 Ir.sub.2(L24) 10 E-29 A-1 50 B-1 25 C-1 15 Ir.sub.2(L25) 10 E-30 A-1 50 B-1 25 C-1 15 Ir.sub.2(L26) 10 E-31 A-1 50 B-1 25 C-1 15 Ir.sub.2(L27) 10 E-32 A-1 50 B-1 25 C-1 15 Ir.sub.2(L28) 10 E-33 A-1 50 B-1 25 C-1 15 Ir.sub.2(L29) 10 E-34 A-1 50 B-1 25 C-1 15 Ir.sub.2(L30) 10 E-35 A-1 50 B-1 25 C-1 15 Ir.sub.2(L31) 10 E-36 A-1 50 B-1 25 C-1 15 Ir.sub.2(L32) 10 E-37 A-1 50 B-1 25 C-1 15 Ir.sub.2(L33) 10 E-38 A-1 50 B-1 25 C-1 15 Ir.sub.2(L34) 10 E-39 A-1 50 B-1 25 C-1 15 Ir.sub.2(L35) 10 E-40 A-1 50 B-1 25 C-1 15 Ir.sub.2(L36) 10 E-41 A-1 50 B-1 25 C-1 15 Ir.sub.2(L37) 10 E-42 A-1 50 B-1 25 C-1 15 Ir.sub.2(L38) 10 E-43 A-1 50 B-1 25 C-1 15 Ir.sub.2(L39) 10 E-44 A-1 50 B-1 25 C-1 15 Ir.sub.2(L40) 10 E-45 A-1 50 B-1 25 C-1 15 Ir.sub.2(L41) 10 E-46 A-1 50 B-1 25 C-1 15 Ir.sub.2(L42) 10 E-47 A-1 50 B-1 25 C-1 15 Ir.sub.2(L43) 10 E-48 A-1 50 B-1 25 C-1 15 Ir.sub.2(L44) 10 E-49 A-1 50 B-1 25 C-1 15 Ir.sub.2(L45) 10 E-50 A-1 50 B-1 25 C-1 15 RhIr(L1) 10 E-51 A-1 50 B-1 25 C-1 15 RhIr(L17) 10 E-52 A-1 50 B-1 25 C-1 15 Ir.sub.2(L120) 10 E-53 A-1 50 B-1 25 C-1 15 Ir.sub.2(L121) 10 E-54 A-1 50 B-1 25 C-1 15 Ir.sub.2(L122) 10 E-55 A-1 50 B-1 25 C-1 15 Ir.sub.2(L123) 10 E-56 A-1 50 B-1 25 C-1 15 Ir.sub.2(L130) 10 E-57 A-1 50 B-1 25 C-1 15 Ir.sub.2(L131) 10 E-58 A-1 50 B-1 25 C-1 15 Ir.sub.2(L132) 10 E-59 A-1 50 B-1 25 C-1 15 Ir.sub.2(L133) 10 E-60 A-1 50 B-1 25 C-1 15 Ir.sub.2100 10 E-61 A-1 50 B-1 25 C-1 15 Rh.sub.2100 10 E-62 A-1 50 B-1 25 C-1 15 Ir.sub.2101 10 E-63 A-1 50 B-1 25 C-1 15 Ir.sub.2102 10 E-64 A-1 50 B-1 25 C-1 15 Ir.sub.2103 10 E-65 A-1 50 B-1 25 C-1 15 Ir.sub.2104 10 E-66 A-1 50 B-1 25 C-1 15 Ir.sub.2105 10 E-67 A-1 50 B-1 25 C-1 15 Ir.sub.2106 10 E-68 A-1 50 B-1 25 C-1 15 Ir.sub.2107 10 E-69 A-1 50 B-1 25 C-1 15 Ir.sub.2108 10 E-70 A-1 50 B-1 25 C-1 15 Ir.sub.2109 10 E-71 A-1 50 B-1 25 C-1 15 Ir.sub.2110 10 E-72 A-1 50 B-1 25 C-1 15 Ir.sub.2111 10 E-73 A-1 50 B-1 25 C-1 15 Ir.sub.2112 10 E-74 A-1 50 B-1 25 C-1 15 Ir.sub.2113 10 E-75 A-1 50 B-1 25 C-1 15 Ir.sub.2(L12-D12) 10 E-76 A-1 50 B-1 25 C-1 15 Ir.sub.2(L17-D12) 10

TABLE-US-00024 TABLE 4 Structure of the OLED components examined HTL EML HBL HIL (thick- (thick- (thick- ETL Ex. (thickness) ness) ness) ness) (thickness) E-1 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (60 nm) E-2 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-3 PEDOT HTL2 70 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-4 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-5 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-6 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-7 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-8 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-9 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-10 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-11 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-12 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-13 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-14 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-15 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-16 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-17 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-18 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-19 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-20 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-21 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-22 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-23 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-24 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-25 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-26 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-27 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-28 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-29 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-30 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-31 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-32 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-33 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-34 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-35 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-36 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-37 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-38 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-39 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-40 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-41 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-42 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-43 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-44 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-45 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-46 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-47 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-48 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-49 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-50 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-51 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-52 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-53 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-54 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-55 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-56 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-57 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-58 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-59 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-60 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-61 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-62 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-63 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-64 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-65 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-66 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-67 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-68 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-69 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-70 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-71 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-72 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-73 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-74 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-75 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm) E-76 PEDOT HTL2 60 nm ETM-1 ETM-1(50%):ETM-2 (60 nm) (20 nm) (10 nm) (50%) (40 nm)