BINUCLEAR AND TRINUCLEAR METAL COMPLEXES COMPOSED OF TWO INTER-LINKED TRIPODAL HEXADENTATE LIGANDS FOR USE IN ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to bi- and trinuclear metal complexes and to electronic devices, in particular organic electroluminescent devices, containing these complexes.

Claims

1-16. (canceled)

17. A compound of formula (1) or formula (2): ##STR01583## wherein M is on each occurrence, identically or differently, iridium or rhodium; Q is an aryl or heteroaryl group having 6 to 10 aromatic ring atoms and which is coordinated to each of the two or three M identically or differently in each case via a carbon or nitrogen atom and which is optionally substituted by one or more radicals R; and wherein the coordinating atoms in Q are not bonded in the ortho position to one another; D is on each occurrence, identically or differently, C or N; X is on each occurrence, identically or differently, CR or N; p is 0 or 1; V is on each occurrence, identically or differently, a group of formulae (3) or (4): ##STR01584## wherein one of the dashed bonds is the bond to the corresponding 6-membered aryl or heteroaryl ring group of formula (1) or (2) and the two other dashed bonds are each the bonds to part-ligands L; L is on each occurrence, identically or differently, a bidentate, monoanionic part-ligand; X.sup.1 is on each occurrence, identically or differently, CR or N; A.sup.1 is on each occurrence, identically or differently, C(R).sub.2 or O; A.sup.2 is on each occurrence, identically or differently, 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 this A.sup.2 is not C(O)NR or C(O)O; A is on each occurrence, identically or differently, CRCR, C(O)NR, C(O)O, CR.sub.2CR.sub.2, CR.sub.2O, or a group of formula (5): ##STR01585## wherein the dashed bond is the position of the bond from a bidentate part-ligand L or from the corresponding 6-membered aryl or heteroaryl ring group of formula (1) or (2) to this structure and * is the position of the linking of the unit of formula (5) to the central cyclic group of formulae (3) or (4); X.sup.2 is on each occurrence, identically or differently, CR or N or two adjacent groups X.sup.2 together are NR, O, or S, so as to define a five-membered ring, and the remaining X.sup.2 are, identically or differently on each occurrence, CR or N; or two adjacent groups X.sup.2 together are CR or N if one of the groups X.sup.3 in the ring are N, so as to define a five-membered ring; with the proviso that a maximum of two adjacent groups X.sup.2 are N; X.sup.3 is on each occurrence C, or one group X.sup.3 is N and the other group X.sup.3 in the same ring is C; with the proviso that two adjacent groups X.sup.2 together are CR or N if one of the groups X.sup.3 in the ring is N; R is on each occurrence, identically or differently, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl, or alkynyl group is in each case optionally substituted by one or more radicals R.sup.1, wherein one or more non-adjacent 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, which in each case is optionally substituted by one or more radicals R.sup.1; and wherein two radicals R also optionally define a ring system with one another; R is on each occurrence, identically or differently, H, D, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl group is in each case optionally substituted by one or more radicals R.sup.1 and wherein one or more non-adjacent 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, which is in each case optionally substituted by one or more radicals R.sup.1; R.sup.1 is on each occurrence, identically or differently, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl, or alkynyl group is in each case optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent 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, which is in each case optionally substituted by one or more radicals R.sup.2; and wherein two or more radicals R.sup.1 also optionally define a ring system with one another; R.sup.2 is on each occurrence, identically or differently, H, D, F, or an aliphatic, aromatic, or heteroaromatic organic radical having 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by F; cation is selected on each occurrence, identically or differently, from the group consisting of proton, deuteron, alkali metal ions, alkaline-earth metal ions, ammonium, tetraalkylammonium, and tetraalkylphosphonium; and anion is selected on each occurrence, identically or differently, 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.5).sub.4.sup., carbonate, and sulfonates.

18. The compound of claim 17, wherein the compound is selected from the group consisting of compounds of formulae (1a) and (2a): ##STR01586## wherein the radical R in the ortho position to D is in each case selected, identically or differently on each occurrence, from the group consisting of H, D, F, CH.sub.3, and CD.sub.3.

19. The compound of claim 1, wherein Q in formula (1) is a group of formulae (Q-1) through (Q3) and Q in formula (2) is a group of one of formulae (Q-4) through (Q-15) when p is 0 or a group of formulae (Q-16) through (Q-19) when p is 1: ##STR01587## ##STR01588## ##STR01589## wherein the dashed bond in each case indicates the linking within the formula (1) or (2); and * indicates the position at which the group is coordinated to M.

20. The compound of claim 17, wherein the group of formula (3) is selected from the group consisting of structures of formulae (6) through (9) and wherein the group of formula (4) is selected from group consisting of structures of formulae (10) to (14): ##STR01590## ##STR01591##

21. The compound of claim 17, wherein the group of formula (3) has a structure of formula (6) and wherein the group of formula (4) has a structure of formula (10) or (10): ##STR01592##

22. The compound of claim 17, wherein A is selected, identically or differently on each occurrence, from the group consisting of C(O)O, C(O)NR or a group of formula (5), wherein the group of formula (5) is selected from the group consisting of structures of formulae (15) through (39): ##STR01593## ##STR01594## ##STR01595##

23. The compound of claim 17, wherein the group of formula (3) is selected from the group consisting of formulae (3a) through (3m) and the group of formula (4) is selected from the group consisting of formulae (4a) through (4m): ##STR01596## ##STR01597## ##STR01598## ##STR01599## ##STR01600##

24. The compound of claim 17, wherein the group of formula (3) is a group of formula (6a): ##STR01601##

25. The compound of claim 17, wherein all four part-ligands L when p is 0 or all six part-ligands L when p is 1 are identical and are identically substituted.

26. The compound of claim 17, wherein the bidentate part-ligands L are selected, identically or differently on each occurrence, from the structures of formulae (L-1), (L-2), and (L-3): ##STR01602## wherein the dashed bond is the bond from the part-ligand L to the group of formula (3) or (4); CyC is, identically or differently on each occurrence, a substituted or unsubstituted aryl or heteroaryl group having 5 to 14 aromatic ring atoms, which is coordinated to M via a carbon atom and which is bonded to CyD via a covalent bond; CyD is, identically or differently on each occurrence, a substituted or unsubstituted heteroaryl group having 5 to 14 aromatic ring atoms, which is coordinated to M via a nitrogen atom or via a carbene carbon atom and which is bonded to CyC via a covalent bond; and a plurality of the optional substituents optionally define a ring system with one another.

27. A process for preparing the compound of claim 17, comprising reacting the free ligand with metal alkoxides of formula (58), metal ketoketonates of formula (59), metal halides of formula (60), or metal carboxylates of formula (61), or with iridium or rhodium compounds which carry both alkoxide and/or halide and/or hydroxyl and ketoketonate radicals, ##STR01603## wherein Hal is F, C.sub.1, Br, or I; and the iridium and rhodium starting materials are optionally in the form of the corresponding hydrates.

28. A mixture comprising at least one compound of claim 17 and at least one further compound, in particular a host material.

29. The mixture of claim 28, wherein the at least one further compound is a host material.

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

31. A formulation comprising at least one mixture of 28 and at least one solvent.

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

33. The electronic device of claim 32, wherein the electronic device is an organic electroluminescent device, wherein the at least one compound is employed as an emitting compound in one or more emitting layers of the organic electroluminescent device.

34. The compound of claim 17, wherein R.sup.2 is a hydrocarbon radical.

Description

EXAMPLES

[0204] The following syntheses are carried out, unless indicated otherwise, 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 numbers in square brackets or the numbers indicated for individual compounds refer to the CAS numbers of the compounds known from the literature.

A: Synthesis of Building Blocks B

Example B1

[0205] ##STR00373##

[0206] A mixture of 23.8 g (100 mmol) of 4,6-dibromopyrimidine [36847-10-6], 41.3 g (200 mmol) of (4-chloronaphthalen-1-yl)boronic acid [147102-97-4], 63.6 g (600 mmol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis-(triphenylphosphine)palladium(0) [14221-01-3], 800 ml of toluene, 300 ml of ethanol and 700 ml of water is heated under reflux for 24 h. After cooling, the organic phase is separated off, washed 2 with 300 ml of water and once with 200 ml of saturated NaCl solution, filtered through a Celite bed, and the filtrate is evaporated to dryness. The residue is purified twice by recrystallisation from acetonitrile. Yield 20.5 g (51 mmol), 51%; purity: 95% according to .sup.1H-NMR.

Example B204

[0207] ##STR00374##

[0208] Building block B204 can be prepared analogously to the procedure for B1, replacing 4,6-dibromopyrimidine by 4,6-dibromo-5-methylpyrimidine [83941-93-9] and replacing (4-chloronaphthalen-1-yl)boronic acid by 4-chlorophenylboronic acid [1679-18-1]. Yield 55%.

Example B2

[0209] ##STR00375##

[0210] 134 g of 4-chlorophenylboronic acid (860 mmol) [1679-18-1], 250.0 g of 5-bromo-2-iodopyridine (880 mmol) [223463-13-6] and 232.7 g of potassium carbonate (1.68 mol) are weighed out into a 4 I four-necked flask with reflux condenser, argon blanketing, precision glass stirrer and internal thermometer, the flask is inertised with argon, and 1500 ml of acetonitrile and 1000 ml of absolute ethanol are added. 100 g of glass beads (diameter 3 mm) are added, and the suspension is homogenised for 5 minutes. 5.8 g of bis(triphenylphosphine)palladium(II) chloride (8.3 mmol) [13965-03-2] are then added. The reaction mixture is warmed under reflux overnight with vigorous stirring. After cooling, the solvent is removed in a rotary evaporator, and the residue is worked up by extraction with toluene and water in a separating funnel. The organic phase is washed 2 with 500 ml of water and 1 with 300 ml of saturated sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent is subsequently removed in vacuo. The residue is taken up in dichloromethane and filtered through a silica gel frit. The silica gel bed is rinsed twice with 500 ml of dichloromethane each time. 800 ml of ethanol are added to the filtrate, the dichloromethane is stripped off in a rotary evaporator to 500 mbar. After removal of the dichloromethane in the rotary evaporator, a solid precipitates out of the ethanol which remains and is filtered off with suction and washed with ethanol. The yellow solid obtained is recrystallised from 800 ml of acetonitrile under reflux, giving a beige solid. Yield: 152.2 g (567.0 mmol), 66%; purity: about 95% according to .sup.1H-NMR.

Example B3

[0211] ##STR00376##

[0212] Building block B3 can be prepared analogously to the procedure for B2, replacing 5-bromo-2-iodopyridine by 2,4-dibromopyridine [58530-53-3]. Yield 54%.

Example B4

[0213] ##STR00377##

[0214] 162.0 g (600 mmol) of B2, 158.0 g (622 mmol) of bis(pinacolato)diborane [73183-34-3], 180.1 g (1.83 mol) of potassium acetate [127-08-2] and 8.9 g (12.1 mmol) of trans-dichlorobis(tricyclohexylphosphine)palladium(II) [29934-17-6] are weighed out into a 4 l four-necked flask with reflux condenser, precision glass stirrer, heating bath and argon connection, and 2200 ml of 1,4-dioxane are added. 100 g of glass beads (diameter 3 mm) are added, the reaction mixture is inertised with argon and stirred under reflux for 24 h. After cooling, the solvent is removed in vacuo, the residue obtained is worked up by extraction with 1000 ml of ethyl acetate and 1500 ml of water in a separating funnel. The organic phase is washed 1 with 500 ml of water and 1 with 300 ml of saturated sodium chloride solution, dried over anhydrous sodium sulfate and filtered through a frit packed with silica gel. The silica gel bed is rinsed 2 with 500 ml of ethyl acetate, and the filtrate obtained is evaporated in vacuo. The brown solid obtained is recrystallised from 1000 ml of n-heptane under reflux, giving a beige solid. Yield: 150.9 g (478 mmol), 80%; purity: 97% according to .sup.1H-NMR.

Example B5

[0215] ##STR00378##

[0216] Building block B5 can be prepared analogously to the procedure for B4 starting from compound B3. 12.1 mmol of trans-dichlorobis(tricyclohexyl-phosphine)palladium(II) are replaced by 12 mmol of [1,1-bis(diphenyl-phosphino)ferrocene]palladium(II) dichloride complex with dichloromethane [95464-05-4]. Yield: 75%.

Example B6

[0217] ##STR00379##

[0218] 31.5 g (100 mmol) of B4, 28.4 g of 5-bromo-2-iodopyridine (100 mmol) [223463-13-6] and 34.6 g of potassium carbonate (250 mmol) are weighed out into a 2 l four-necked flask with reflux condenser, argon blanketing, precision glass stirrer and internal thermometer, the flask is inertised with argon, and 500 ml of acetonitrile and 350 ml of absolute ethanol are added. 30 g of glass beads (diameter 3 mm) are added, and the suspension is homogenised for 5 minutes. 702 mg of bis(triphenylphosphine)-palladium(II) chloride (1 mmol) [13965-03-2] are then added. The reaction mixture is warmed under reflux overnight with vigorous stirring. After cooling, the solvent is removed in a rotary evaporator, and the residue is worked up by extraction with toluene and water in a separating funnel. The organic phase is washed 2 with 500 ml of water and 1 with 300 ml of saturated sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent is subsequently removed in vacuo. The residue is taken up in dichloromethane and filtered through a silica gel frit, the silica gel is rinsed twice with 200 ml of dichloromethane/ethyl acetate 1:1 each time, the dichloromethane is stripped off in a rotary evaporator to 500 mbar. During removal of the dichloromethane in the rotary evaporator, a solid precipitates out of the ethyl acetate which remains and is filtered off with suction and washed with ethyl acetate. The crude product is recrystallised again from ethyl acetate. Yield: 24.2 g (72 mmol), 72%; purity: about 95% according to .sup.1H-NMR.

Example B7

[0219] Procedure analogous to the description for B6. Recrystallisation from acetonitrile instead of from ethyl acetate. Yield 68%.

##STR00380##

Example B8

[0220] ##STR00381##

[0221] A mixture of 30.1 g (100 mmol) of 4,6-bis(4-chlorophenyl)pyrimidine [141034-82-4], 54.6 g (215 mmol) of bis(pinacolato)diborane [73183-34-3], 58.9 g (600 mmol) of potassium acetate, 2.3 g (8 mmol) of S-Phos [657408-07-6], 1.3 g (6 mmol) of palladium(II) acetate, 900 ml of 1,4-dioxane is heated under reflux for 16 h. The dioxane is removed in a rotary evaporator, and the black residue is worked up by extraction with 1000 ml of ethyl acetate and 500 ml of water in a separating funnel, the organic phase is washed 1 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 rinsed 2 with 250 ml of ethyl acetate. The filtrate is dried over sodium sulfate and evaporated to 150 ml. 400 ml of n-heptane are then added, and the remaining ethyl acetate is stripped off in the rotary evaporator to 200 mbar at a bath temperature of 55 C. During removal of the ethyl acetate in the rotary evaporator, a solid precipitates out of the n-heptane which remains. The precipitated solid is heated under reflux for 30 min and, after cooling, filtered off and washed 2 with 30 ml of n-heptane each time. Yield: 37.8 g (78 mmol), 78%. Purity: about 98% according to .sup.1H NMR.

[0222] The following compounds can be prepared analogously:

TABLE-US-00004 Product/ reaction conditions if Ex. Strarting material different Yield B9 [00382] [00383] 91% B10 [00384] [00385] 87% B11 [00386] [00387] 90% B12 [00388] [00389] 82% B13 [00390] [00391] 66% B14 [00392] [00393] 63% B15 [00394] [00395] 85% B16 [00396] [00397] 87% B17 [00398] [00399] 85% B205 [00400] [00401] 82%

Example B18

[0223] ##STR00402##

[0224] 34.6 g (100 mmol) of B6, 25.4 g (100 mmol) of bis(pinacolato)diborane [73183-34-3], 29.4 g (300 mol) of potassium acetate [127-08-2] and 1.63 g (2 mmol) of ([1,1-bis(diphenylphosphino)ferrocene]palladium(II) dichloride complex with dichloromethane [95464-05-4] are weighed out into a 1000 ml four-necked flask with reflux condenser, precision glass stirrer, heating bath and argon connection, and 500 ml of 1,4-dioxane are added. 30 g of glass beads (diameter 3 mm) are added, and the reaction mixture is inertised with argon and stirred under reflux for 24 h. After cooling, the solvent is removed in vacuo, the residue obtained is worked up by extraction with 600 ml of ethyl acetate and 600 ml of water in a separating funnel. The organic phase is washed 1 with 500 ml of water and 1 with 300 ml of saturated sodium chloride solution, dried over anhydrous sodium sulfate and filtered through a frit packed with silica gel. The silica-gel bed is rinsed 2 with 500 ml of ethyl acetate, and the filtrate obtained is evaporated in vacuo. 500 ml of n-heptane are added to the brown solid obtained, and the suspension formed is boiled under reflux for 1 h. The solid is filtered off with suction and washed with 50 ml of n-heptane, giving a beige solid. Yield: 34.6 g (89 mmol), 89%; purity: 98% according to .sup.1H-NMR.

Example B19

[0225] ##STR00403##

[0226] Procedure analogous to that of Example B18. B6 is replaced by B7 as starting material. Yield: 82%.

Example B20

[0227] ##STR00404##

[0228] A mixture of 48.4 g (100 mmol) of B8, 56.6 g (200 mmol) of 1-bromo-2-iodobenzene [583-55-1], 63.6 g (600 mmol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis(triphenylphosphine)palladium(0) [14221-01-3], 1000 ml of 1,2-dimethoxyethane and 500 ml of water is heated under reflux for 60 h. After cooling, the solid which has precipitated out is filtered off with suction and washed 3 with 100 ml of ethanol. The crude product is dissolved in 1000 ml of dichloromethane and filtered through a silica-gel bed which has been pre-slurried with dichloromethane. The silica gel is rinsed 3 with 100 ml of ethyl acetate each time. The dichloromethane is removed in a rotary evaporator to 500 mbar at a bath temperature of 50 C. During the removal of the dichloromethane in the rotary evaporator, a solid precipitates out of the ethyl acetate which remains. The solid which has precipitated out is filtered off and washed 2 with 20 ml of ethyl acetate. The solid obtained is recrystallised again from 2000 ml of boiling ethyl acetate. Yield 29.3 g (54 mmol), 54%; purity: 97% according to .sup.1H-NMR.

[0229] The following compounds can be prepared analogously, where solvents such as, for example, ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol can be used for the recrystallisation. It is also possible to carry out a hot extraction with these solvents, or the purification can be carried out by chromatography on silica gel on an automated column (Torrent from Axel Semrau).

TABLE-US-00005 Product/reaction conditions if Ex. Starting material different Yield B21 B9 [00405] 42% B22 B10 [00406] 53% B23 B11 [00407] 47% B24 B12 [00408] 40% B25 B13 [00409] 32% B26 B14 [00410] 35% B27 B15 [00411] 47% B28 B16 [00412] 41% B29 B17 [00413] 44% B30 B18, 1 equiv. of 1-bromo-2- iodobenzene [00414] 67% B31 B19, 1 equiv. of 1-bromo-2- iodobenzene [00415] 52% B206 B205 [00416] 46%

Example B32

[0230] ##STR00417##

[0231] 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 at 120 C. in an autoclave for 24 h. After cooling, the ethanol is removed in vacuo, the residue is taken up in 200 ml of ethyl acetate, the solution is washed three times with 200 ml of water, once with 100 ml of saturated sodium chloride solution, dried over magnesium sulfate and then filtered off from the latter through a pre-slurried silica-gel bed. After removal of the ethyl acetate in vacuo, the residue is chromatographed on silica gel with n-heptane/ethyl acetate (1:2 vv). Yield: 9.7 g (45 mmol), 45%. Purity: about 98% according to .sup.1H-NMR.

Example B33

[0232] ##STR00418##

[0233] 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 in vacuo, 500 ml of toluene are added, the mixture is washed twice with 300 ml of water each time, once with 200 ml of saturated sodium chloride solution, dried over magnesium sulfate, filtered off through a pre-slurried silica-gel bed, and the latter is rinsed with 300 ml of toluene. After removal of the toluene in vacuo, the product is recrystallised once from methanol/ethanol (1:1 vv) and once from n-heptane. Yield: 17.3 g (61 mmol), 61%. Purity: about 95% according to .sup.1H-NMR.

Example B34

[0234] ##STR00419##

[0235] B34 can be prepared analogously to the procedure described for Example B33. To this end, 2,5-dibromo-4-methylpyridine is replaced by 4-bromo-6-tert-butylpyrimidine [19136-36-8]. Yield: 70%.

Example B35

[0236] ##STR00420##

[0237] A mixture of 28.3 g (100 mmol) of B33, 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, the organic phase is separated off, washed once with 300 ml of water, once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. After removal of the solvent, the residue is chromatographed on silica gel (toluene/ethyl acetate, 9:1 vv). Yield: 17.1 g (61 mmol), 61%. Purity: about 97% according to .sup.1H-NMR.

[0238] The following compounds can be synthesised analogously:

TABLE-US-00006 Ex. Boronic ester Product Yield B36 [00421] [00422] 56% B37 [00423] [00424] 61% B38 [00425] [00426] 55% B199 [00427] [00428] 65%

Example B39

[0239] ##STR00429##

[0240] 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 employed 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 for 16 h with vigorous stirring. After cooling, 1000 ml of toluene are added, the organic phase is separated off, and the aqueous phase is then 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 in vacuo, the crude product is recrystallised twice from about 300 ml of EtOH. Yield: 130.8 g (365 mmol), 73%. Purity: about 95% according to .sup.1H-NMR.

[0241] The following compounds can be prepared analogously, where the pyridine derivative employed is generally 5-bromo-2-iodopyridine ([223463-13-6]), which is not shown separately in the following table: only different pyridine derivatives are explicitly shown in the table. Solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol can be used for the recrystallisation. It is also possible to carry out a hot extraction with these solvents, or the purification can be carried out by chromatography on silica gel on an automated column (Torrent from Axel Semrau).

TABLE-US-00007 Boronic acid/ester Ex. Pyridine Product Yield B40 [00430] [00431] 69% B41 [00432] [00433] 71% B42 [00434] [00435] 78% B43 [00436] [00437] 78% B44 [00438] [00439] 81% B45 [00440] [00441] 73% B46 [00442] [00443] 68% B47 [00444] [00445] 63%

Example B48

Variant A:

[0242] ##STR00446##

[0243] A mixture of 35.8 g (100 mmol) of B39, 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)ferrocenepalladium(II) dichloride complex with dichloromethane [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 in vacuo. The black residue is digested with 1000 ml of hot n-heptane, cyclohexane or toluene, filtered off while still hot through a Celite bed, then evaporated to about 200 ml, during which the product begins to crystallise. Alternatively, a hot extraction can be carried out with ethyl acetate. The crystallisation is completed overnight in the refrigerator, 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% according to .sup.1H-NMR.

Variant B: Reaction of Aryl Chlorides

[0244] As for variant A, but the 1,1-bis(diphenylphosphino)ferrocenepalladium(II) dichloride complex with dichloromethane is replaced by 2 mmol of S-Phos [657408-07-6] and 1 mmol of palladium(II) acetate.

[0245] The following compounds can be prepared analogously, where cyclohexane, toluene, acetonitrile or mixtures of the said solvents can also be used instead of n-heptane for the purification:

TABLE-US-00008 Bromidevariant A Ex. Chloridevariant B Product Yield B49 [00447] [00448] 85% B50 [00449] [00450] 80% B51 [00451] [00452] 83% B52 [00453] [00454] 77% B53 [00455] [00456] 67% B54 [00457] [00458] 70% B55 [00459] [00460] 80% B56 [00461] [00462] 80% B57 [00463] [00464] 78% B58 [00465] [00466] 74% B59 [00467] [00468] 70% B60 [00469] [00470] 68% B61 [00471] [00472] 76% B62 [00473] [00474] 83% B63 [00475] [00476] 85% B64 [00477] [00478] 55% B65 [00479] [00480] 72% B66 [00481] [00482] 78% B67 [00483] [00484] 82% B68 [00485] [00486] 60% B69 [00487] [00488] 75% B70 [00489] [00490] 88% B71 [00491] [00492] 78% B72 [00493] [00494] 82% B73 [00495] [00496] 80% B74 [00497] [00498] 85% B75 [00499] [00500] 88% B76 [00501] [00502] 76% B77 [00503] [00504] 81% B78 [00505] [00506] 78% B79 [00507] [00508] 75% B200 [00509] [00510] 78%

Example B80

[0246] ##STR00511##

[0247] A mixture of 28.1 g (100 mmol) of B49, 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, the organic phase is separated off, washed once with 500 ml of water, once with 500 ml of saturated sodium chloride solution and dried over magnesium sulfate. After removal of the solvent, the residue is recrystallised from ethyl acetate/n-heptane or chromatographed on silica gel (toluene/ethyl acetate, 9:1 vv). Yield: 22.7 g (73 mmol), 73%. Purity: about 97% according to .sup.1H-NMR.

[0248] The following compounds can be prepared analogously, where solvents such as, for example, ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol can be used for the recrystallisation. It is also possible to carry out a hot extraction with these solvents, or the purification can be carried out by chromatography on silica gel on an automated column (Torrent from Axel Semrau).

TABLE-US-00009 Ex. Boronic ester Product Yield B81 [00512] [00513] 56% B82 [00514] [00515] 72% B83 [00516] [00517] 71% B84 [00518] [00519] 70% B85 [00520] [00521] 69% B86 [00522] [00523] 67% B87 [00524] [00525] 63% B88 [00526] [00527] 70% B89 [00528] [00529] 73% B90 [00530] [00531] 72% B91 [00532] [00533] 48% B92 [00534] [00535] 65% B93 [00536] [00537] 65% B94 [00538] [00539] 68% B95 [00540] [00541] 77% B96 [00542] [00543] 70% B97 [00544] [00545] 66% B98 [00546] [00547] 71% B99 [00548] [00549] 64% B100 [00550] [00551] 58% B101 [00552] [00553] 62% B102 [00554] [00555] 75% B103 [00556] [00557] 78% B104 [00558] [00559] 82% B201 [00560] [00561] 74%

Example B106

[0249] ##STR00562##

a)

##STR00563##

[0250] Preparation in accordance with G. Markopoulos et al., Angew. Chem., Int. Ed., 2012, 51, 12884.

b)

##STR00564##

[0251] Procedure in accordance with JP 2000-169400. 5.7 g (105 mmol) of sodium methoxide are added in portions to a solution of 36.6 g (100 mmol) of 1,3-bis(2-bromophenyl)-2-propen-1-one [126824-93-9], step a), in 300 ml of dry acetone, and the mixture is then stirred at 40 C. for 12 h. The solvent is removed in vacuo, the residue is taken up in ethyl acetate, washed three times with 200 ml of water each time, twice with 200 ml of saturated sodium chloride solution each time and dried over magnesium sulfate. The oil obtained after removal of the solvent in vacuo is subjected to flash chromatography (Torrent CombiFlash, Axel Semrau). Yield: 17.9 g (44 mmol), 44%. Purity: about 97% according to .sup.1H-NMR.

c)

##STR00565##

[0252] 2.4 g (2.4 mmol) of anhydrous copper(I) chloride [7758-89-6] are added at 0 C. to a solution of 2-chlorophenylmagnesium bromide (200 mmol) [36692-27-0] in 200 ml of di-n-butyl ether, and the mixture is stirred for a further 30 min. A solution of 40.6 g (100 mmol) of step b) in 200 ml of toluene is then added dropwise over the course of 30 min., and the mixture is stirred at 0 C. for a further 5 h. The reaction mixture is quenched by careful addition of 100 ml of water and then with 220 ml of 1N hydrochloric acid. The organic phase is separated off, washed twice with 200 ml of water each time, once with 200 ml of saturated sodium hydrogencarbonate solution, once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The oil obtained after removal of the solvent in vacuo is filtered through silica gel with toluene. The crude product obtained in this way is reacted further without further purification. Yield: 49.8 g (96 mmol), 96%. Purity: about 90-95% according to .sup.1H-NMR.

d)

##STR00566##

[0253] 1.0 ml of trifluoromethanesulfonic acid and then, in portions, 50 g of phosphorus pentoxide are added to a solution, cooled to 0 C., of 51.9 g (100 mmol) of step c) in 500 ml of dichloromethane (DCM). The mixture is allowed to warm to room temperature and is stirred for a further 2 h. The supernatant is decanted off from the phosphorus pentoxide, the latter is suspended in 200 ml of DCM, and the supernatant is again decanted off. The combined DCM phases are washed twice with water and once with saturated sodium chloride solution and dried over magnesium sulfate. The wax obtained after removal of the solvent in vacuo is subjected to flash chromatography (Torrent CombiFlash, Axel Semrau). Yield: 31.5 g (63 mmol), 63%, isomer mixture. Purity: about 90-95% according to .sup.1H-NMR.

e)

##STR00567##

[0254] A mixture of 25.0 g (50 mmol) of step d), 2 g of Pd/C (10%), 200 ml of methanol and 300 ml of ethyl acetate is charged with 3 bar of hydrogen in a stirred autoclave and hydrogenated at 30 C. until the uptake of hydrogen is complete. The mixture is filtered through a Celite bed which has been pre-slurried with ethyl acetate, the filtrate is evaporated to dryness. The oil obtained in this way is subjected to flash chromatography (Torrent CombiFlash, Axel Semrau). Yield: 17.2 g (34 mmol), 68%. Purity: about 95% according to .sup.1H-NMR, cis,cis isomer.

[0255] The following compounds can be prepared analogously.

TABLE-US-00010 Starting materials Yield Ex. if different from B106 Product a) to e) B107 [00568] [00569] 21% B108 [00570] [00571] 19% B109 [00572] [00573] 14%

Example B110

[0256] ##STR00574##

[0257] 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 B80, 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, the organic phase is separated off, washed once with 500 ml of water, once with 500 ml of saturated sodium chloride solution and dried over magnesium sulfate. After removal of the solvent, the residue is chromatographed on silica gel (n-heptane/ethyl acetate 2:1 vv). Yield: 41.4 g (68 mmol), 68%. Purity: about 95% according to .sup.1H-NMR.

[0258] The following compounds can be prepared analogously, where solvents such as, for example, ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol can be used for the recrystallisation. It is also possible to carry out a hot extraction with these solvents, or the purification can be carried out by chromatography on silica gel on an automated column (Torrent from Axel Semrau).

TABLE-US-00011 Ex. Bromide Product Yield B111 [00575] [00576] 67% B112 [00577] [00578] 62% B113 [00579] [00580] 55% B114 [00581] [00582] 63% B115 [00583] [00584] 60% B116 [00585] [00586] 61% B117 [00587] [00588] 58% B118 [00589] [00590] 56% B119 [00591] [00592] 60% B120 [00593] [00594] 64% B121 [00595] [00596] 60% B202 [00597] [00598] 65%

Example B122

[0259] ##STR00599##

[0260] 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 dichloride, dissolved in 30 ml of dichloromethane, are added dropwise, and the reaction mixture is stirred at room temperature for 14 h. 10 ml of water are subsequently 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 evaporated to dryness. Yield: 18.0 g (38 mmol), 95%. Purity: about 95% according to .sup.1H-NMR.

[0261] The following compounds can be prepared analogously. The amounts of the starting materials employed are indicated if they differ from those described in the procedure for B122:

TABLE-US-00012 Alcohol or amine Acid chloride Ex. Reaction time Product Yield B123 [00600] [00601] 90% B124 [00602] [00603] 96% B125 [00604] [00605] 88% B126 [00606] [00607] 75% B127 [00608] [00609] 82% B128 [00610] [00611] 76% B129 [00612] [00613] 80% B130 [00614] [00615] 73% B131 [00616] [00617] 78%

Example B132

[0262] ##STR00618##

[0263] 2.0 g (50 mmol) of sodium hydride (60% dispersion in paraffin oil) [7646-69-7] are suspended in 300 ml of THF, 5.0 g (10 mmol) of B124 are then added, and the suspension is stirred at room temperature for 30 minutes. 1.2 ml of iodomethane (50 mmol) [74-88-4] are subsequently 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 substantially stripped off in vacuo. The residue is taken up in 300 ml of dichloromethane, washed once with 200 ml of 5% by weight ammonia water, twice with 100 ml of water each time, once with 100 ml of saturated sodium chloride solution and then dried over magnesium sulfate. The dichloromethane is removed in vacuo, and the crude product is recrystallised from ethyl acetate/methanol. Yield: 4.3 g (8 mmol), 80%. Purity: about 98% according to .sup.1H-NMR.

[0264] The following compounds can be prepared analogously:

TABLE-US-00013 Ex. Starting material Product Yield B133 [00619] [00620] 70% B134 [00621] [00622] 75% B135 [00623] [00624] 69% B136 [00625] [00626] 72%

Example B137

[0265] ##STR00627##

[0266] A mixture of 36.4 g (100 mmol) pf 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 B93, 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 solid which has precipitated out is filtered off with suction and washed twice with 20 ml of ethanol. The solid is dissolved in 500 ml of dichloromethane and filtered off via a Celite bed. The filtrate is evaporated to 100 ml, 400 ml of methanol are then added, and the solid which has precipitated out is filtered off with suction. The crude product is recrystallised once from ethyl acetate. Yield: 43.6 g (70 mmol), 70%. Purity: about 96% according to .sup.1H-NMR.

[0267] The following compounds can be prepared analogously, where solvents such as, for example, ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol can be used for the recrystallisation. It is also possible to carry out a hot extraction using these solvents, or the purification can be carried out by chromatography on silica gel on an automated column (Torrent from Axel Semrau).

TABLE-US-00014 B138 [00628] [00629] 64% B139 [00630] [00631] 54% B140 [00632] [00633] 75% B141 [00634] [00635] 71% B142 [00636] [00637] 58% B143 [00638] [00639] 60% B144 [00640] [00641] 66% B145 [00642] [00643] 70% B146 [00644] [00645] 70% B147 [00646] [00647] 63% B148 [00648] [00649] 60% B149 [00650] [00651] 61% B150 [00652] [00653] 58%

Example B151

[0268] ##STR00654##

[0269] A mixture of 57.1 g (100 mmol) of B110, 25.4 g (100 mmol) of bis(pinacolato)diborane [73183-34-3], 49.1 g (500 mmol) of potassium acetate, 2 mmol of S-Phos [657408-07-6] and 1 mmol of palladium(II) acetate, 200 g of glass beads (diameter 3 mm) an 700 ml of 1,4-dioxane is heated under reflux for 16 h with stirring. After cooling, the suspension is filtered through a Celite bed, and the solvent is removed in vacuo. The black residue is digested with 1000 ml of hot ethyl acetate, the mixture is filtered while still hot through a Celite bed, then evaporated to about 200 ml, during which the product begins to crystallise. The crystallisation is completed overnight in the refrigerator, 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% according to 1H-NMR.

[0270] The following compounds can be prepared analogously. Toluene, n-heptane, cyclohexane or acetonitrile can also be used instead of ethyl acetate for the recrystallisation or, in the case of low solubility, used for the hot extraction.

TABLE-US-00015 Ex. Bromide Product Yield B152 [00655] [00656] 80% B153 [00657] [00658] 84% B154 [00659] [00660] 71% B155 [00661] [00662] 80% B156 [00663] [00664] 85% B157 [00665] [00666] 82% B158 [00667] [00668] 77% B159 [00669] [00670] 72% B160 [00671] [00672] 77% B161 [00673] [00674] 80% B162 [00675] [00676] 81% B163 [00677] [00678] 88% B164 [00679] [00680] 55% B165 [00681] [00682] 79% B166 [00683] [00684] 76% B167 [00685] [00686] 89% B168 [00687] [00688] 84% B169 [00689] [00690] 50% B170 [00691] [00692] 79% B171 [00693] [00694] 75% B172 [00695] [00696] 77% B173 [00697] [00698] 80% B174 [00699] [00700] 82% B175 [00701] [00702] 88% B176 [00703] [00704] 90% B177 [00705] [00706] 76% B178 [00707] [00708] 80% B179 [00709] [00710] 81% B180 [00711] [00712] 84% B181 [00713] [00714] 74% B182 [00715] [00716] 73% B183 [00717] [00718] 76% B184 [00719] [00720] 72% B185 [00721] [00722] 75% B203 [00723] [00724] 81%

Example B186

[0271] ##STR00725##

[0272] A mixture of 54.5 g (100 mmol) of B106, 59.0 g (210 mmol) of 2-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine [879291-27-7], 127.4 g (600 mmol) of tripotassium phosphate, 1.57 g (6 mmol) of triphenylphosphine and 449 mg (2 mmol) of palladium(II) acetate in 750 ml of toluene, 300 ml of dioxane and 500 ml of water is heated under reflux for 30 h. After cooling, the organic phase is separated off, washed twice with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The magnesium sulfate is filtered off via a Celite bed which has been pre-slurried with toluene, the filtrate is evaporated to dryness in vacuo, and the foam which remains is recrystallised from acetonitrile/ethyl acetate. Yield: 41.8 g (64 mmol), 64%. Purity: about 95% according to .sup.1H-NMR.

[0273] The following compounds can be prepared analogously

TABLE-US-00016 Starting Ex. materials Product Yield B187 [00726] [00727] 68% B188 B108 B70 [00728] 60% B189 B108 B59 [00729] 60% B190 B108 B77 [00730] 69% B191 B109 B79 [00731] 61% B192 B107 B102 [00732] 65%

Example B193

[0274] ##STR00733##

[0275] A mixture of 42.1 g (100 mmol) of B30, 66.3 g (100 mmol) of B151, 31.8 g (300 mmol) of sodium carbonate, 580 mg (2.6 mmol) of triphenylphosphine, 200 mg (0.88 mmol) of palladium(II) acetate, 500 ml of toluene, 250 ml of ethanol and 500 ml of water is heated under reflux for 26 h. After cooling, the solid which has precipitated out is filtered off with suction and washed twice with 30 ml of ethanol each time. The crude product is dissolved in 300 ml of dichloromethane and filtered through a silica-gel bed. The silica-gel bed is rinsed three times with 200 ml of dichloromethane/ethyl acetate 1:1 each time. The filtrate is washed twice with water and once with saturated sodium chloride solution and dried over sodium sulfate. The dichloromethane is substantially stripped off in a rotary evaporator. During removal of the dichloromethane in the rotary evaporator, a solid precipitates out of the ethyl acetate which remains and is filtered off with suction and washed with ethyl acetate. The crude product is recrystallised again from ethyl acetate. Yield: 61.5 g (70 mmol), 70%. Purity: about 95% according to .sup.1H-NMR.

Example B194

[0276] ##STR00734##

[0277] Procedure analogous to that from Example B193, using building block B31 instead of B30. Yield: 66%.

Example B195

[0278] ##STR00735##

[0279] A mixture of 87.7 g (100 mmol) of B193, 25.4 g (100 mmol) of bis(pinacolato)diborane [73183-34-3], 49.1 g (500 mmol) of potassium acetate, 2 mmol of S-Phos [657408-07-6], 1 mmol of palladium(II) acetate, 100 g of glass beads (diameter 3 mm) and 700 ml of 1,4-dioxane is heated under reflux for 16 h. After cooling, the suspension is filtered through a Celite bed, the Celite is rinsed 3 with 200 ml of dioxane each time, and the solvent is removed in vacuo. The black residue is digested with 1000 ml of ethyl acetate, the mixture is filtered while still hot through a Celite bed, then evaporated to about 200 ml, during which the product begins to crystallise. The crystallisation is completed overnight in the refrigerator, the crystals are filtered off and washed with a little ethyl acetate. A second product fraction can be obtained from the mother liquor. Yield: 72.7 g (75 mmol), 75%. Purity: about 97% according to .sup.1H-NMR.

Example B196

[0280] ##STR00736##

[0281] Procedure analogous to that from Example B195. B194 is employed instead of B193. Yield: 80%.

Example B197

[0282] ##STR00737##

[0283] A mixture of 48.5 g (50 mmol) of B195, 14.1 g (50 mmol) of 1-bromo-2-iodobenzene [583-55-1], 31.8 g (300 mmol) of sodium carbonate, 2.3 g (2 mmol) of tetrakis(triphenylphosphine)palladium(0) [14221-01-3], 500 ml of 1,2-dimethoxyethane and 250 ml of water is heated under reflux for 60 h. After cooling, the solid which has precipitated out is filtered off with suction and washed three times with 100 ml of ethanol. The crude product is dissolved in 300 ml of dichloromethane and filtered through a silica-gel bed which has been pre-slurried with dichloromethane. The silica gel is rinsed three times with 200 ml of ethyl acetate each time. The dichloromethane is removed in a rotary evaporator to 500 mbar at a bath temperature of 50 C. During removal of the dichloromethane in the rotary evaporator, a solid precipitates out of the ethyl acetate which remains and is filtered off with suction and washed with ethyl acetate. The solid obtained is recrystallised again from boiling ethyl acetate. Yield 31.9 g (32 mmol), 64%. Purity: 95% according to .sup.1H-NMR.

Example B198

[0284] Procedure analogous to Example B197. Yield: 60%.

##STR00738##

B: Synthesis of the Ligands:

Example L1

[0285] ##STR00739##

[0286] A mixture of 7.9 g (14.5 mmol) of B20, 20.2 g (30.5 mmol) of B152, 63.7 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 solid which has precipitated out is filtered off with suction and washed twice with 30 ml of ethanol each time. The crude product is dissolved in 300 ml of dichloromethane and filtered through a silica-gel bed. The silica-gel bed is rinsed three times with 200 ml of dichloromethane/ethyl acetate 1:1 each time. The filtrate is washed twice with water and once with saturated sodium chloride solution and dried over sodium sulfate. The dichloromethane is substantially stripped off in a rotary evaporator. During removal of the dichloromethane in the rotary evaporator, a solid precipitates out of the ethyl acetate which remains and is filtered off with suction and washed with ethyl acetate. Yield: 12.5 g (8.6 mmol), 59%. Purity: about 98% according to .sup.1H-NMR.

[0287] The following compounds can be prepared analogously, where solvents such as, for example, ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol, DMF, DMAC or methanol can be used for the recrystallisation. It is also possible to carry out a hot extraction with these solvents, or the purification can be carried out by chromatography on silica gel on an automated column (Torrent from Axel Semrau).

TABLE-US-00017 Starting Product/ Ex. materials reaction conditions, if different Yield L2 B157 + B20 [00740] 56% L3 B161 + B20 [00741] 50% L4 B162 + B20 [00742] 48% L5 B165 + B20 [00743] 52% L6 B167 + B20 [00744] 43% L8 B170 + B20 [00745] 41% L9 B172 + B20 [00746] 45% L10 B173 + B20 [00747] 55% L11 B174 + B20 [00748] 41% L12 B177 + B20 [00749] 44% L13 B164 + B82 4.4 equiv. of B82, 12 eq. of base, 10 mol %, catalyst [00750] 28% L14 B169 + B100 4.4 equiv. of B100, 12 equiv. of base, 10 mol %, catalyst [00751] 32% L15 B181 + B20 [00752] 56% L16 B21 + B151 [00753] 55% L17 B21 + B152 [00754] 52% L18 B21 + B182 [00755] 46% L19 B21 + B178 [00756] 48% L20 S 8 + B159 [00757] 45% L21 B21 + B163 [00758] 50% L22 B21 + B171 [00759] 52% L23 B22 + B152 [00760] 55% L24 B22 + B162 [00761] 58% L25 B22 + B173 [00762] 48% L26 B22 + B180 [00763] 46% L27 B22 + B177 [00764] 55% L28 B22 + B165 [00765] 54% L29 B22 + B167 [00766] 49% L30 B22 + B183 [00767] 56% L31 B22 + B158 [00768] 60% L32 B22 + B161 [00769] 57% L33 B22 + B151 [00770] 62% L34 B23 + B151 [00771] 65% L35 B23 + S176 [00772] 62% L36 B23 + B154 [00773] 58% L37 B23 + B159 [00774] 49% L38 B23 + B152 [00775] 60% L39 B23 + B163 [00776] 51% L40 B23 + 159 [00777] 50% L41 B23 + B153 [00778] 57% L42 B23 + B175 [00779] 50 L43 B24 + B151 [00780] 62% L44 B24 + B152 [00781] 65% L45 B24 + B157 [00782] 55% L46 B24 + B160 [00783] 48% L47 B24 + B183 [00784] 53% L48 B24 + B174 [00785] 52% L49 B24 + S167 [00786] 62% L50 B24 + 152 [00787] 57% L51 B24 + B181 [00788] 53% L52 B25 + B151 [00789] 39% L53 B25 + B152 [00790] 41% L54 B25 + S176 [00791] 36% L55 B25 + B172 [00792] 41% L56 B25 + B183 [00793] 35% L57 B25 + B161 [00794] 43% L58 B20 + B185 [00795] 40% L59 B197 + 1 equiv. of B152 [00796] 65% L60 B198 + 1 equiv. of B152 [00797] 59% L61 B26 + B155 [00798] 32% L62 B27 + B151 [00799] 42% L63 B28 + B155 [00800] 38% L64 B29 + B151 [00801] 44% L65 B155 + B20 [00802] 45% L75 B203 + B20 [00803] 50% L76 B152 + B206 [00804] 48%

Example L66

[0288] ##STR00805##

[0289] A mixture of 13.7 g (21 mmol) of B187, 4.8 g (10 mmol) of B8, 12.7 g (60 mmol) of tripotassium phosphate, 250 mg (0.6 mmol) of S-Phos [657408-07-6], 90 mg (4 mmol) of palladium(II) acetate, 100 ml of toluene, 60 ml of dioxane and 60 ml of water is heated under reflux for 6 h. After cooling, the organic phase is separated off, washed twice with 50 ml of water and once with 30 ml of saturated sodium chloride solution, dried over magnesium sulfate and filtered through a Celite bed which has been pre-slurried with toluene. The Celite bed is rinsed with toluene. The filtrate is evaporated to dryness, and the residue is subsequently recrystallised twice from ethyl acetate. Yield: 56.5 g (4.5 mmol), 45%. Purity: about 97% according to .sup.1H-NMR.

[0290] The following compounds can be prepared analogously, where solvents such as, for example, ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol, DMF, DMAC or methanol can be used for the recrystallisation. It is also possible to carry out a hot extraction with these solvents, or the purification can be carried out by chromatography on silica gel on an automated column (Torrent from Axel Semrau).

TABLE-US-00018 Starting Product/ Ex. materials reaction conditions, if different Yield L67 B186 + B9 [00806] 40% L68 B188 + B10 [00807] 42% L69 B187 + B13 [00808] 27% L70 B12 + B187 [00809] 39% L71 B190 + B8 [00810] 47% L72 B191 + B8 [00811] 38% L73 B192 + B11 [00812] 45% L74 B189 + B8 [00813] 43%

C: Synthesis of the Metal Complexes

Example of Isomer 1-Ir.SUB.2.(L1) and Isomer 2-Ir.SUB.2.(L1) (Abbreviated to I1-Ir.SUB.2.(L1) and I2-Ir.SUB.2.(L1) Below)

[0291] ##STR00814##

[0292] A mixture of 14.5 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 introduced in a 1000 ml two-necked round-bottomed flask with a glass-clad magnetic stirrer bar. The flask is provided with a water separator (for media of lower density than water) and an air condenser with argon blanketing and is placed in a metal heating dish. The apparatus is flushed with argon from above via the argon blanketing for 15 min., during which the argon is allowed to stream out of the side neck of the two-necked flask. A glass-clad Pt-100 thermocouple is introduced into the flask via the side neck of the two-necked flask and the end is positioned just above the magnetic stirrer bar. The apparatus is thermally insulated by means of several loose coils of household aluminium foil, where the insulation is run as far as the centre of the riser tube of the water separator. The apparatus is then quickly heated to 250 C., measured at the Pt-100 temperature sensor, which dips into the molten, stirred reaction mixture, using a laboratory hotplate stirrer. During the next 2 h, the reaction mixture is held at 250 C., during which little condensate is distilled off and collects in the water separator. The reaction mixture is allowed to cool to 190 C., and 100 ml of ethylene glycol are then added dropwise. The mixture is allowed to cool further to 80 C., and 500 ml of methanol are then added dropwise, and the mixture is heated under reflux for 1 h. The suspension obtained in this way is filtered through a reverse frit, the solid is washed twice with 50 ml of methanol and then dried in vacuo. The solid obtained in this way is dissolved in 200 ml of dichloromethane and filtered through about 1 kg of silica gel which has been pre-slurried with dichloromethane (column diameter about 18 cm) with exclusion of air and light, where dark components remain at the start. The core fraction is cut out and evaporated in a rotary evaporator, with MeOH simultaneously being continuously added dropwise to crystallisation. The diastereomeric product mixture is filtered off with suction, washed with a little MeOH and dried in vacuo, then subjected to further purification.

[0293] The diastereomeric metal complex mixture comprising and isomers (racemic) and isomer (meso) in the molar ratio 1:1 (determined by .sup.1H-NMR) is dissolved in 300 ml of dichloromethane, adsorbed onto 100 g of silica gel and separated by chromatography on a silica-gel column which has been pre-slurried with toluene/ethyl acetate 95:5 (amount of silica gel about 1.7 kg). The front spot is eluted first, and the amount of ethyl acetate is then increased stepwise to a toluene/ethyl acetate ratio of 6:1, giving 7.0 g (3.8 mmol, purity 99%) of the isomer eluting earlier, called isomer 1 (I1) below, and 7.7 g (4.2 mmol, purity 98%) of the isomer eluting later, called isomer 2 (12) below. Isomer 1 (I1) and isomer 2 (12) are purified further separately from one another by hot extraction four times with ethyl acetate for isomer 1 and dichloromethane for isomer 2 (initially introduced amount in each case about 150 ml, extraction thimble: standard cellulose Soxhlett thimbles from Whatman) with careful exclusion of air and light. Finally, the products are heated at 280 C. in a high vacuum. Yield: isomer 1 (I1) 5.3 g of red solid (2.9 mmol), 29%, based on the amount of ligand employed. Purity: >99.9% according to HPLC; isomer 2 (12) 4.9 g of red solid (2.7 mmol), 27%, based on the amount of ligand employed. Purity 99.8% according to HPLC.

[0294] The metal complexes shown below can in principle be purified by chromatography (typical use of an automated column (Torrent from Axel Semrau), recrystallisation or hot extraction. Residual solvents can be removed by heating in vacuo/high vacuum at typically 250-330 C. or by sublimation/fractional sublimation. The yields indicated for isomer 1 (I1) and isomer 2 (12) always relate to the amount of ligand employed.

[0295] The pictures of the complexes shown below usually show only one isomer. The isomer mixture can be separated, but can also be employed as an isomer mixture in the OLED device. However, there are also ligand systems in which for steric reasons only one diastereomer pair forms.

[0296] The following compounds can be synthesised analogously. The reaction conditions are indicated by way of example for isomer 1 (I1). The chromatographic separation of the diastereomer mixture usually formed is carried out on flash silica gel on an automated column (Torrent from Axel Semrau).

TABLE-US-00019 Starting Product/reaction conditions/hot Ex. material extractant (HE) Yield* I1-Rh.sub.2 (L1) L1 Rh(acac).sub.3 [14284- 92-5] instead of Ir(acac).sub.3 [00815] 22% I1-Rh.sub.2(L1) 250 C.; 2 h Hot extraction: toluene I2-Rh.sub.2 (L1) L1 Rh(acac).sub.3 [14284- 92-5] instead of Ir(acac).sub.3 [00816] 20% I2-Rh.sub.2(L1) Hot extraction: toluene I1-Ir.sub.2 (L2) L2 [00817] 32% I1-Ir.sub.2(L2) 250 C.; 2 h Hot extraction: ethyl acetate I2-Ir.sub.2 L2 I2-Ir.sub.2(L2) 34% (L2) Hot extraction: toluene I1-Ir.sub.2 (L3) L3 [00818] 29% I1-Ir.sub.2(L3) 230 C.; 1 h Hot extraction: ethyl acetate I2-Ir.sub.2 L3 I2-Ir.sub.2(L3) 30% (L3) Hot extraction: ethyl acetate Ir.sub.2 (L4) L4 [00819] 52% Ir.sub.2(L4) 250 C.; 2 h Hot extraction: ethyl acetate Only the racemate of and isomers forms. Rh.sub.2 (L4) L4 Rh(acac).sub.3 [14284- 92-5] instead of Ir(acac).sub.3 [00820] 40% Rh.sub.2(L4) 250 C.; 2 h Hot extraction: ethyl acetate Only the racemate of and isomers forms. I1-Ir.sub.2 (L5) L5 [00821] 30%% I1-Ir.sub.2(L5) 250 C.; 3 h Hot extraction: n-butyl acetate I2-Ir.sub.2 L5 I2-Ir.sub.2(L5) 28%% (L5) Hot extraction: n-butyl acetate I1-Ir.sub.2 (L6) L6 [00822] 21% I1-Ir.sub.2(L6) 220 C.; 5 h Hot extraction: butyl acetate I2-Ir.sub.2 L6 I2-Ir.sub.2(L6) 24% (L6) Hot extraction: ethyl acetate I1-Ir.sub.2 (L8) L8 [00823] 25% I1-Ir.sub.2(L8) 220 C.; 5 h Hot extraction: toluene I2-Ir.sub.2 L8 I2-Ir.sub.2(L8) 25% (L8) Hot extraction: toluene I1-Ir.sub.2 (L9) L9 [00824] 32% I1-Ir.sub.2(L9) 250 C.; 3 h Hot extraction: o-xylene I2-Ir.sub.2 L9 I2-Ir.sub.2(L9) 26% (L9) Hot extraction: toluene Ir.sub.2 (L10) L10 [00825] 58% I1-Ir.sub.2(L10) 250 C.; 1.5 h Hot extraction: ethyl acetate/acetonitrile 4:1 Only the racemate of and isomers forms. I1-Ir.sub.2 (L11) L11 [00826] 27% I1-Ir.sub.2(L11) 260 C.; 2 h Hot extraction: m-xylene I2-Ir.sub.2 L11 I2-Ir.sub.2(L11) 30% (L11) Hot extraction: o-xylene I1-Ir.sub.2 (L12) L12 [00827] 31% I1-Ir.sub.2(L12) 265 C.; 2 h Hot extraction: toluene I2-Ir.sub.2 L12 I2-Ir.sub.2(L12) 33% (L12) Hot extraction: toluene I1-Ir.sub.2 (L13) L13 [00828] 30% I1-Ir.sub.2(L13) 250 C.; 3 h Hot extraction: butyl acetate I2-Ir.sub.2 L13 I1-Ir.sub.2(L13) 30% (L13) Hot extraction: butyl acetate I1-Ir.sub.2 (L14) L14 [00829] 26% I1-Ir.sub.2(L14) 250 C.; 3 h Hot extraction: ethyl acetate I2-Ir.sub.2 L14 I2-Ir.sub.2(L14) 23% (L14) Hot extraction: ethyl acetate I1-Ir.sub.2 (L15) L15 [00830] 27% I1-Ir.sub.2(L15) 250 C.; 2 h Hot extraction: cyclohexane I2-Ir.sub.2 L15 I2-Ir.sub.2(L15) 33% (L15) Hot extraction: toluene/heptane 3:1 I1-Ir.sub.2 (L16) L16 [00831] 33% I1-Ir.sub.2(L16) 270 C.; 2 h Hot extraction: dichloromethane I2-Ir.sub.2 L16 I2-Ir.sub.2(L16) 30% (L16) Hot extraction: dichloromethane I1-Ir.sub.2 (L17) L17 [00832] 29% I1-Ir.sub.2(L17) 265 C.; 3 h Hot extraction: toluene I2-Ir.sub.2 L17 I2-Ir.sub.2(L17) 34% (L17) Hot extraction: n-butyl acetate I1-Ir.sub.2 (L18) L18 [00833] 27% I1-Ir.sub.2(L18) 265 C.; 3.5 h Hot extraction: ethyl acetate I2-Ir.sub.2 L18 I2-Ir.sub.2(L18) 25% (L18) Hot extraction: ethyl acetate/acetonitrile 4:1 I1-Ir.sub.2 (L19) L19 [00834] 35% I1-Ir.sub.2(L19) 270 C.; 3 h Hot extraction: dichloromethane I2-Ir.sub.2 L19 I2-Ir.sub.2(L19) 30% (L19) Hot extraction: o-xylene I1-Ir.sub.2 (L20) L20 [00835] 29% I1-Ir.sub.2(L20) 265 C.; 5 h Hot extraction: dichloromethane I2-Ir.sub.2 L20 I2-Ir.sub.2(L20) 31% (L20) Hot extraction: dichloromethane I1-Ir.sub.2 (L21) L21 [00836] 25% I1-Ir.sub.2(L21) 255 C.; 3 h Hot extraction: ethyl acetate I2-Ir.sub.2 L21 I2-Ir.sub.2(L21) 30% (L21) Hot extraction: ethyl acetate I1-Ir.sub.2 (L22) L22 [00837] 21% I1-Ir.sub.2(L22) 235 C.; 3 h Recrystallisation from DMF I-Ir.sub.2 L22 I2-Ir.sub.2(L22) 23% (L22) Hot extraction: n-butyl acetate I1-Ir.sub.2 (L23) L23 [00838] 31% I1-Ir.sub.2(L23) 250 C.; 2 h Hot extraction: toluene I2-Ir.sub.2 L23 I2-Ir.sub.2(L23) 38% (L23) Hot extraction: o-xylene I1-Ir.sub.2 (L24) L24 [00839] 28% I1-Ir.sub.2(L24) 250 C.; 2 h Hot extraction: toluene I2-Ir.sub.2 L24 I2-Ir.sub.2(L24) 27% (L24) Hot extraction: toluene I1-Ir.sub.2 (L25) L25 [00840] 29% I1-Ir.sub.2(L25) 250 C.; 2 h Hot extraction: ethyl acetate I2-Ir.sub.2 L25 I2-Ir.sub.2(L25) 30% (L25) Hot extraction: ethyl acetate I1-Ir.sub.2 (L26) L26 [00841] 25% I1-Ir.sub.2(L26) 250 C.; 3.5 h Hot extraction: p-xylene I2-Ir.sub.2 L26 I2-Ir.sub.2(L26) 25% (L26) Hot extraction: toluene I1-Ir.sub.2 (L27) L27 [00842] 28% I1-Ir.sub.2(L27) 260 C.; 3 h Hot extraction: toluene I2-Ir.sub.2 L27 I2-Ir.sub.2(L27) 32% (L27) Hot extraction: o-xylene I1-Ir.sub.2 (L28) L28 [00843] 35% I1-Ir.sub.2(L28) 250 C.; 3 h Recrystallisation from DMSO I2-Ir.sub.2 L28 I2-Ir.sub.2(L28) 31% (L28) Recrystallisation from DMF I1-Ir.sub.2 (L29) L29 [00844] 23% I1-Ir.sub.2(L29) 235 C.; 2 h Hot extraction: ethyl acetate I2-Ir.sub.2 L29 I2-Ir.sub.2(L29) 26% (L29) Hot extraction: ethyl acetate I1-Ir.sub.2 (L30) L30 [00845] 31% I1-Ir.sub.2(L30) 250 C.; 2 h Recrystallisation from 1,4-dioxane I2-Ir.sub.2 L30 I2-Ir.sub.2(L30) 31% (L30) Recrystallisation from DMSO I1-Ir.sub.2 (L31) L31 [00846] 30% I1-Ir.sub.2(L31) 250 C.; 2 h Hot extraction: n-butyl acetate I2-Ir.sub.2 L31 I2-Ir.sub.2(L31) 27% (L31) Hot extraction: n-butyl acetate I1-Ir.sub.2 (L32) L32 [00847] 37% I1-Ir.sub.2(L32) 230 C.; 2 h Hot extraction: ethyl acetate I2-Ir.sub.2 L32 I2-Ir.sub.2(L32) 33% (L32) Hot extraction: n-butyl acetate I1-Ir.sub.2 (L33) L33 [00848] 30% I1-Ir.sub.2(L33) 250 C.; 2 h Hot extraction: o-xylene I2-Ir.sub.2 L33 I2-Ir.sub.2(L33) 24% (L33) Hot extraction: o-xylene I1-Ir.sub.2 (L34) L34 [00849] 26% I1-Ir.sub.2(L34) 270 C.; 3 h Hot extraction: toluene I2-Ir.sub.2 L34 I2-Ir.sub.2(L34) 28% (L34) Hot extraction: p-xylene I1-Ir.sub.2 (L35) L35 [00850] 29% I1-Ir.sub.2(L35) 270 C.; 3 h Hot extraction: n-butyl acetate I2-Ir.sub.2 L35 I2-Ir.sub.2(L35) 29% (L35) Hot extraction: n-butyl acetate I1-Ir.sub.2 (L36) L36 [00851] 33% I1-Ir.sub.2(L36) 270 C.; 3 h Hot extraction: toluene I2-Ir.sub.2 L36 I2-Ir.sub.2(L36) 31% (L36) Hot extraction: toluene I1-Ir.sub.2 (L37) + I2-Ir.sub.2 (L37) L37 [00852] 60% I1-Ir.sub.2(L37) + I2-Ir.sub.2(L37) 270 C.; 4 h Column: separation not possible, employed as isomer mixture. Hot extraction: xylene I1-Ir.sub.2 (L38) L38 [00853] 30% I1-Ir.sub.2(L38) 270 C.; 3 h Hot extraction: toluene I2-Ir.sub.2 L38 I2-Ir.sub.2(L38) 26% (L38) Hot extraction: dichloromethane I1-Ir.sub.2 (L39) L39 [00854] 32% I1-Ir.sub.2(L39) 260 C.; 3 h Recrystallisation from DMF I2-Ir.sub.2 L39 I2-Ir.sub.2(L39) 24% (L39) Recrystallisation from DMF I1-Ir.sub.2 (L40) L40 [00855] 22% I1-Ir.sub.2(L40) 250 C.; 3 h Recrystallisation from DMSO I2-Ir.sub.2 L40 I2-Ir.sub.2(L40) 30% (L40) Hot extraction: ethyl acetate I1-Ir.sub.2 (L41) L41 [00856] 27% I1-Ir.sub.2(L41) 270 C.; 2 h Hot extraction: toluene I2-Ir.sub.2 L41 I2-Ir.sub.2(L41) 32% (L41) Hot extraction: n-butyl acetate I1-Ir.sub.2 (L42) L42 [00857] 30% I1-Ir.sub.2(L42) 270 C.; 6 h Hot extraction: o-xylene I2-Ir.sub.2 L42 I2-Ir.sub.2(L42) 35% (L42) Hot extraction: o-xylene I1-Ir.sub.2 (L43) L43 [00858] 30% I1-Ir.sub.2(L43) 260 C.; 2 h Hot extraction: butyl acetate I2-Ir.sub.2 L43 I2-Ir.sub.2(L43) 28% (L43) Hot extraction: toluene I1-Ir.sub.2 (L44) L44 [00859] 27% I1-Ir.sub.2(L44) 260 C.; 2 h Hot extraction: toluene I2-Ir.sub.2 L44 I2-Ir.sub.2(L44) 33% (L44) Hot extraction: toluene I1-Ir.sub.2 (L45) L45 [00860] 27% I1-Ir.sub.2(L45) 260 C.; 2 h Hot extraction: ethyl acetate I2-Ir.sub.2 L45 I2-Ir.sub.2(L45) 28% (L45) Hot extraction: n-butyl acetate I1-Ir.sub.2 (L46) L46 [00861] 32% I1-Ir.sub.2(L46) 260 C.; 2 h Hot extraction: ethyl acetate I2-Ir.sub.2 L46 I2-Ir.sub.2(L46) 26% (L46) Hot extraction: ethyl acetate I1-Ir.sub.2 (L47) L47 [00862] 25% I1-Ir.sub.2(L47) 250 C.; 2 h Recrystallisation: DMF I2-Ir.sub.2 L47 I2-Ir.sub.2(L47) 28% (L47) Recrystallisation: DMF I1-Ir.sub.2 (L48) L48 [00863] 23% I1-Ir.sub.2(L48) 270 C.; 2 h Hot extraction: butyl acetate I2-Ir.sub.2 L48 I2-Ir.sub.2(L48) 21% (L48) Hot extraction: ethyl acetate I1-Ir.sub.2 (L49) L49 [00864] 32% I1-Ir.sub.2(L49) 270 C.; 2 h Hot extraction: o-xylene I2-Ir.sub.2 L49 I2-Ir.sub.2(L49) 30% (L49) Hot extraction: toluene I1-Ir.sub.2 (L50) L50 [00865] 27% I1-Ir.sub.2(L50) 240 C.; 2 h Hot extraction: ethyl acetate/acetonitrile 1:1 I2-Ir.sub.2 L50 I2-Ir.sub.2(L50) 25% (L50) Hot extraction: ethyl acetate/acetonitrile 1:1 I1-Ir.sub.2 (L51) L51 [00866] 24% I1-Ir.sub.2(L51) 260 C.; 2 h Hot extraction: cyclohexane I2-Ir.sub.2 L51 I2-Ir.sub.2(L51) 23% (L51) Hot extraction: cyclohexane Ir.sub.3 (L52) L52 [00867] 33% Ir.sub.2(L52) 3 equiv. of Ir(acac).sub.3, 260 C.; 7 h Only the racemate of and isomers forms Hot extraction: toluene Ir.sub.3 (L53) L53 [00868] 30% Ir.sub.2(L53) 3 equiv. of Ir(acac).sub.3, 260 C.; 7 h Hot extraction: o-xylene Only the racemate of and isomers forms. Ir.sub.3 (L54) L54 [00869] 29% Ir.sub.2(L54) 3 equiv. of Ir(acac).sub.3, 270 C.; 6 h Hot extraction: n-butyl acetate Only the racemate of and isomers forms. Ir.sub.3 (L55) L55 [00870] 28% Ir.sub.2(L55) 3 equiv. of Ir(acac).sub.3, 270 C.; 6 h Hot extraction: p-xylene Only the racemate of and isomers forms. Ir.sub.3 (L56) L56 [00871] 26% Ir.sub.2(L56) 3 equiv. of Ir(acac).sub.3, 265 C.; 6 h Recrystallisation: dimethylacetamide Only the racemate of and isomers forms. Ir.sub.3 (L57) L57 [00872] 33% Ir.sub.2(L57) 3 equiv. of Ir(acac).sub.3, 245 C.; 6 h Hot extraction: n-butyl acetate Only the racemate of and isomers forms. I1-Ir.sub.2 (L58) L58 [00873] 24% I1-Ir.sub.2(L58) 250 C., 2 h Hot extraction: toluene I2-Ir.sub.2 L58 I2-Ir.sub.2(L58) 27% (L58) Hot extraction: toluene Ir.sub.2 (L59) L59 [00874] 52% Ir.sub.2(L59) 265 C., 4 h A mixture of 8 isomers forms, which is not separated, but instead is used as a mixture. Hot extraction: toluene Ir.sub.2 (L60) L60 [00875] 29% Ir.sub.2(L60) 260 C., 4 h A mixture of 8 isomers forms, which is not separated, but instead is used further as a mixture Hot extraction: ethyl acetate Ir.sub.2 (L61) L61 [00876] 50% Ir.sub.2(L61) 250 C., 8 h The steric reasons, only the enantiomer pair of and forms. I1-Ir.sub.2 (L62) L62 [00877] 24% I1-Ir.sub.2(L62) 265 C., 6 h Hot extraction: dichloromethane I1-Ir.sub.2 L62 I2-Ir.sub.2(L62) 26% (L62) Hot extraction: dichloromethane I1-Ir.sub.2 (L63) L63 [00878] 30% I1-Ir.sub.2(L63) 260 C., 4 h Hot extraction: ethyl acetate I2-Ir.sub.2 (L63) L63 [00879] 28% I2-Ir.sub.2(L63) Hot extraction: toluene I1-Ir.sub.2 (L64) L64 [00880] 25% I1-Ir.sub.2(L64) 260 C., 4 h Hot extraction: toluene I2-Ir.sub.2 L64 I2-Ir.sub.2(L64) 26% (L64) Hot extraction: toluene Ir.sub.2 (L65) L65 [00881] 58% Ir.sub.2(L65) 250 C., 2 h Hot extraction: ethyl acetate For steric reasons, only the and enantiomer pair forms. I1-Ir.sub.2 (L66) L66 [00882] 25% I1-Ir.sub.2(L66) 250 C., 2 h Hot extraction: toluene I1-Ir.sub.2 L66 I2-Ir.sub.2(L66) 25% (L66) Hot extraction: toluene I1-Ir.sub.2 (L67) L67 [00883] 23% I1-Ir.sub.2(L67) 250 C., 2 h Hot extraction: ethyl acetate I2-Ir.sub.2 L67 I2-Ir.sub.2(L67) 24% (L67) Hot extraction: n-butyl acetate I1-Ir.sub.2 (L68) L68 [00884] 21% I1-Ir.sub.2(L68) 250 C., 2 h Hot extraction: ethyl acetate I2-Ir.sub.2 L68 I2-Ir.sub.2(L68) 24% (L68) Hot extraction: ethyl acetate Ir.sub.3 (L69) L69 [00885] 17% Ir.sub.2(L69) 3 equiv. of Ir(acac).sub.3, 260 C.; 5 h Hot extraction: toluene Only the racemate of and isomers forms. I1-Ir.sub.2 (L70) L70 [00886] 26% I1-Ir.sub.2(L70) 250 C.; 2 h Hot extraction: ethyl acetate I2-Ir.sub.2 L70 I2-Ir.sub.2(L70) 28% (L70) Hot extraction: ethyl acetate I1-Ir.sub.2 (L71) L71 [00887] 22% I1-Ir.sub.2(L71) 250 C., 2 h Hot extraction: ethyl acetate I2-Ir.sub.2 L71 I2-Ir.sub.2(L71) 21% (L71) Hot extraction: ethyl acetate/acetonitrile 3:1 I1-Ir.sub.2 (L72) L72 [00888] 20% I1-Ir.sub.2(L72) 250 C., 2 h Hot extraction: toluene I2-Ir.sub.2 L72 I2-Ir.sub.2(L72) 25% (L72) Hot extraction: toluene I1-Ir.sub.2 (L73) L73 [00889] 23% I1-Ir.sub.2(L73) 250 C., 2 h Hot extraction: cyclohexane I2-Ir.sub.2 L73 I2-Ir.sub.2(L73) 19% (L73) Hot extraction: ethyl acetate/acetonitrile 1:1 I1-Ir.sub.2 (L74) L74 [00890] 21% I1-Ir.sub.2(L74) 250 C., 2 h Hot extraction: ethyl acetate I2-Ir.sub.2 L74 I2-Ir.sub.2(L74) 24% (L74) Hot extraction: n-butyl acetate I1-Ir.sub.2 (L75) L75 [00891] 22% I1-Ir.sub.2(L75) 265 C., 4 h Hot extraction: ethyl acetate/acetonitrile 2:1 I2-Ir.sub.2 L75 I2-Ir.sub.2(L75) 16% (L75) Hot extraction: n-butyl acetate I1-Ir.sub.2 (L76) L76 [00892] 21% I1-Ir.sub.2(L76) 250 C., 3 h Hot extraction: toluene I2-Ir.sub.2 L76 I2-Ir.sub.2(L76) 19% (L76) Hot extraction: toluene

D: Functionalisation of the Metal Complexes

[0297] 1) Halogenation of the Iridium Complexes:

[0298] A solution or suspension of 10 mmol of a complex which carries ACH groups (where A=1-6) in the para position to the iridium in 500 ml to 2000 ml of dichloromethane (DCM), depending on the solubility of the metal complex, is mixed with A10.5 mmol of N-halosuccinimide (halogen: Cl, Br, I) at 30 to +30 C. with exclusion of light and air, and the mixture is stirred for 20 h. Complexes which have low solubility in DCM can also be reacted in other solvents (TCE, THF, DMF, chlorobenzene, etc.) and at elevated temperature. The solvent is subsequently substantially removed in vacuo. The residue is boiled with 100 ml of methanol, the solid is filtered off with suction, washed three times with 30 ml of methanol and dried in vacuo, giving the iridium complexes which are halogenated in the para position to the iridium. Complexes having an HOMO (CV) of about 5.1 to 5.0 eV or lower tend towards oxidation (Ir(III)-Ir(IV)), where the oxidant is bromine, liberated from NBS. This oxidation reaction is evident from a clear green coloration or brown coloration of the otherwise yellow to red solution/suspension of the complexes. In such cases, 1-2 further equivalents of NBS are added. For work-up, 300-500 ml of methanol and 4 ml of hydrazine hydrate as reducing agent are added, causing the green or brown solution/suspension to change colour to yellow or red (reduction Ir(IV)-Ir(III)). The solvent is then substantially stripped off in vacuo, 300 ml of methanol are added, the solid is filtered off with suction, washed three times with 100 ml of methanol each time and dried in vacuo.

[0299] Sub-stoichiometric brominations, for example mono- and dibrominations, of complexes having 3 CH groups in the para position to the iridium 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 I1-Ir.SUB.2.(L1-6Br)

[0300] ##STR00893##

[0301] 8.9 g (80 mmol) of N-bromosuccinimide (NBS) are added in one portion to a suspension of 18.3 g (10 mmol) of I1-Ir.sub.2(L1) in 2000 ml of DCM, and the mixture is then stirred for 20 h. 4 ml of hydrazine hydrate and subsequently 300 ml of MeOH are added. The dichloromethane is substantially stripped off in vacuo. During removal of the dichloromethane in the rotary evaporator, a red solid precipitates out of the methanol which remains and is filtered off with suction and washed three times with about 50 ml of methanol and dried in vacuo. Yield: 21.9 g (9.5 mmol) 95%; purity: >99.0% according to NMR.

[0302] The following compounds can be synthesised analogously

TABLE-US-00020 Starting Product Ex. material Amount of halosuccinimide Yield* I2-Ir.sub.2 I1-Ir.sub.2 0.02 equiv. of HBr (aq), 10 equiv. 90% (L1-6Br) (L1) of NBS I2-Ir.sub.2(L1-6Br): I1-Ir.sub.2 I1-Ir.sub.2 0.02 equiv. of HBr (aq), 8 equiv. 92% (L2-6Br) (L2) of NBS I2-Ir.sub.2(L2-6Br) I2-Ir.sub.2 I2-Ir.sub.2 0.02 equiv. HBr (aq), 8 equiv. 91% (L2-6Br) (L2) of NBS I2-Ir.sub.2(L2-6Br) I1-Ir.sub.2 (L3-6Br) I1-Ir.sub.2 (L3) [00894] 88% I1-Ir.sub.2(L3-6Br) 6.6 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L3-6Br) 85% (L3-6Br) (L3) 8 equiv. of NBS Ir.sub.2 (L4-6Br) Ir.sub.2 (L4) [00895] 93% Ir.sub.2(L4-6Br) 8 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L5-6Br) 80% (L5-6Br) (L5) 6.6 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L5-6Br) 82% (L5-6Br) (L5) 7.5 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L6-6Br) 81% (L6-6Br) (L6) 6.6 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L6-6Br) 77% (L6-6Br) (L6) 8 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L8-6Br) 78% (L8-6Br) (L8) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L8-6Br) 82% (L8-6Br) (L8) 0.02 equiv. of HBr (aq), 7 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L9-6Br) 90% (L9-6Br) (L9) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L9-6Br) 86% (L9-6Br) (L9) 8 equiv. of NBS Ir.sub.2 (L10-6Br) Ir.sub.2 (L10) [00896] 96%% Ir.sub.2(L10-6Br) 6.6 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L11-6Br) 88% (L11-6Br) (L11) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L11-6Br) 88% (L11-6Br) (L11) 0.02 equiv. of HBr (aq), 7 equiv. of NBS I1-Ir.sub.2 (L12-6Br) I1-Ir.sub.2 (L12) [00897] 92% I1-Ir.sub.2(L12-6Br) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L12-6Br) 90% (L12-6Br) (L12) 8 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L13-6Br) 90% (L13-6Br) (L13) 10 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I1-Ir.sub.2(L13-6Br) 94% (L13-6Br) (L13) 0.02 equiv. of HBr (aq), 10 equiv. of NBS I1-Ir.sub.2 (L15-2Br) I1-Ir.sub.2 (L15) [00898] 90% I1-Ir.sub.2(L15-2Br) 2.2 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L15-2Br) 83% (L15-2Br) (L15) 2.2 equiv. of NBS I1-Ir.sub.2 (L16-4Br) I1-Ir.sub.2 (L16) [00899] 89% I1-Ir.sub.2(L16-4Br) 5 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L16-4Br) 87% (L16-4Br) (L16) 4.5 equiv. of NBS I1-Ir.sub.2 (L17-4Br) I1-Ir.sub.2 (L17) [00900] 80% I1-Ir.sub.2(L17-4Br) 4.4 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L17-4Br) 82% (L17-4Br) (L17) 4.4 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L21-4Br) 75% (L21-4Br) (L21) 5 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L21-4Br) 72% (L21-4Br) (L21) 5 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L22-4Br) 81% (L22-4Br) (L22) 4.4 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L22-4Br) 79% (L22-4Br) (L22) 4.4 equiv. of NBS I1-Ir.sub.2 (L23-6Br) I1-Ir.sub.2 (L23) [00901] 91% I1-Ir.sub.2(L23-6Br) 7 equiv. of NBS I2-Ir.sub.2 (L23-6Br) I2-Ir.sub.2 (L23) [00902] 89% I2-Ir.sub.2(L23-6Br) 6.6 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L24-6Br) 84% (L24-6Br) (L24) 7 equiv. of NBS, 0.02 equiv. of HBr (aq) I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L24-6Br) 80% (L24-6Br) (L24) 7 equiv. of NBS, 0.02 equiv. of HBr (aq) I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L25-6Br) 90% (L25-6Br) (L25) 7 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L25-6Br) 97% (L25-6Br) (L25) 7 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L27-6Br) 82% (L27-6Br) (L27) 7 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L27-6Br) 83% (L27-6Br) (L27) 7 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L28-6Br) 81% (L28-6Br) (L28) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L28-6Br) 77% (L28-6Br) (L28) 7.5 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L29-6Br) 84% (L29-6Br) (L29) 10 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L29-6Br) 86% (L29-6Br) (L29) 10 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L30-6Br) 81% (L30-6Br) (L30) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L30-6Br) 76% (L30-6Br) (L30) 8 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L31-6Br) 92% (L31-6Br) (L31) 8 equiv. of NBS, 0.02 equiv. of HBr (aq) I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L31-6Br) 95% (L31-6Br) (L31) 8 equiv. of NBS, 0.05 equiv. of HBr (aq) I1-Ir.sub.2 (L32-6Br) I1-Ir.sub.2 (L32) [00903] 77% I1-Ir.sub.2(L32-6Br) 6.6 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L32-6Br) 72% (L32-6Br) (L32) 6.6 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L33-6Br) 91% (L33-6Br) (L33) 8 equiv. of NBS, 0.01 equiv. of HBr (aq) I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L33-6Br) 94% (L33-6Br) (L33) 8 equiv. of NBS, 0.01 equiv. of HBr (aq) I1-Ir.sub.2 (L34-4Br) I1-Ir.sub.2 (L34) [00904] 82% I1-Ir.sub.2(L34-4Br) 4.4 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L34-4Br) 86% (L34-4Br) (L34) 4.4 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L36-4Br) 93% (L36-4Br) (L36) 5 equiv. of NBS, 0.02 equiv. of HBr (aq) I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L36-4Br) 91% (L36-4Br) (L36) 4.4 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L38-4Br) 85% (L38-4Br) (L38) 4.4 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L38-4Br) 91% (L38-4Br) (L38) 4.4 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L39-4Br) 75% (L39-4Br) (L39) 4.4 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L39-4Br) 74% (L39-4Br) (L39) 4.4 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L40-4Br) 78% (L40-4Br) (L40) 5 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L40-4Br) 77% (L40-4Br) (L40) 5 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L41-4Br) 85% (L41-4Br) (L41) 5 equiv. of NBS, 0.01 equiv. of HBr (aq) I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L41-4Br) 88% (L41-4Br) (L41) 6 equiv. of NBS, 0.01 equiv. of HBr (aq) I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L42-4Br) 90% (L42-4Br) (L42) 4.4 equiv. of NBS, 0.01 equiv. of HBr (aq) I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L42-4Br) 86% (L42-4Br) (L42) 4.4 equiv. of NBS, 0.01 equiv. of HBr (aq) I1-Ir.sub.2 (L43-6Br) I1-Ir.sub.2 (L43) [00905] 90% I1-Ir.sub.2(L43-6Br) 8 equiv. of NBS, 0.01 equiv. of HBr (aq) I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L43-6Br) 85% (L43-6Br) (L43) 8 equiv. of NBS, 0.01 equiv. of HBr (aq) I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L44-6Br) 89% (L44-6Br) (L44) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L44-6Br) 93% (L44-6Br) (L44) 8 equiv. of NBS, 0.01 equiv. of HBr (aq) I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L47-6Br) 82% (L47-6Br) (L47) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L47-6Br) 81% (L47-6Br) (L47) 8 equiv. of NBS, 0.01 equiv. of HBr (aq) I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L50-6Br) 82% (L50-6Br) (L50) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L50-6Br) 81% (L50-6Br) (L50) 8 equiv. of NBS, 0.01 equiv. of HBr (aq) I1-Ir.sub.2 (L66-6Br) I1-Ir.sub.2 (L66) [00906] 94% I1-Ir.sub.2(L66-6Br) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L66-6Br) 94% (L66-6Br) (L66) 8 equiv. of NBS, 0.1 equiv. of HBr (aq) I1-Ir.sub.2 (L91-4Br) I1-Ir.sub.2 (L91) [00907] 90% I1-Ir.sub.2(L91-4Br) 5 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L91-4Br) 92% (L91-4Br) (L91) 5 equiv. of NBS I1-Ir.sub.2 (L92-6Br) [00908] 88% I1-Ir.sub.2(L92) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2(L92-6Br) 86% (L92-6Br) 8 equiv. of NBS I1-Ir.sub.2 (L70-6Br) I1-Ir.sub.2 (L70) [00909] 81% I1-Ir.sub.2(L70-6Br) 10 equiv. of NBS, 0.02 equiv. of HBr (aq) I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L70-6Br) 78% (L70-6Br) (L70) 10 equiv. of NBS I1-Ir.sub.2 (L71-6Br) I1-Ir.sub.2 (L71) [00910] 96% I1-Ir.sub.2(L71-6Br) 6.6 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L71-6Br) 96% (L71-6Br) (L71) 6.6 equiv. of NBS I1-Ir.sub.2 I1-Ir.sub.2 I1-Ir.sub.2(L72-6Br) 91% (L72-6Br) (L72) 8 equiv. of NBS I2-Ir.sub.2 I2-Ir.sub.2 I2-Ir.sub.2(L72-6Br) 92% (L72-6Br) (L72) 8 equiv. of NBS

2) Suzuki Coupling to the Brominated Iridium Complexes Variant a, Two-Phase Reaction Mixture:

[0303] 0.6 mmol of tri-o-tolylphosphine and then 0.1 mmol of palladium(II) acetate are added to a suspension of 10 mmol of a brominated complex, 12-20 mmol of boronic acid or boronic acid 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, 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 separated off, 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, the latter is rinsed with toluene, the toluene is removed virtually completely in vacuo, 300 ml of methanol are added, the crude product which has precipitated out is filtered off with suction, washed three times with 50 ml of methanol each time and dried in vacuo. The crude product is passed through an automated silica-gel column (Torrent from Semrau). The complex is subsequently purified further by hot extraction in solvents such as ethyl acetate, toluene, dioxane, acetonitrile, cyclohexane, ortho- or para-xylene, n-butyl acetate, etc. Alternatively, the complex can be recrystallised from these solvents and high-boiling solvents, such as dimethylformamide, dimethyl sulfoxide or mesitylene. The metal complex is finally heated or sublimed. The heating is carried out in a high vacuum (p about 10.sup.6 mbar) in the temperature range of about 200-300 C.

Variant B, Single-Phase Reaction Mixture:

[0304] 0.2 mmol of tetrakis(triphenylphosphine)palladium(0) [14221-01-3] is added to a suspension of 10 mmol of a brominated complex, 12-20 mmol of boronic acid or boronic acid ester per Br function and 100-180 mmol of a base (potassium fluoride, tripotassium phosphate (anhydrous or monohydrate or trihydrate), potassium carbonate, caesium carbonate, etc.) and 100 g of glass beads (diameter 3 mm) in 100-500 ml of an aprotic solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.), and the mixture is heated under reflux for 24 h. Alternatively, other phosphines, such as triphenylphosphine, tri-tert-butylphosphine, S-Phos, X-Phos, RuPhos, XanthPhos, etc. can be employed in combination with Pd(OAc).sub.2, where the preferred phosphine:palladium ratio in the case of these phosphines is 3:1 to 1.2:1. The solvent is removed in vacuo, the product is taken up in a suitable solvent (toluene, dichloromethane, ethyl acetate, etc.) and purified as described under Variant A.

Synthesis of Ir.SUB.2.100

[0305] ##STR00911##

Variant B:

[0306] Use of 23.1 g (10.0 mmol) of I1-Ir(L1-6Br) and 38.0 g (120.0 mmol) of 2-(3,5-di-tert-butylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1071924-13-4], 17.7 g (180 mmol) of tripotassium phosphate monohydrate, 231 mg of tetrakis(triphenylphosphine)palladium(0), 500 ml of dry dimethyl sulfoxide, reflux, 16 h. Chromatographic separation twice on silica gel with toluene/heptane (automated column, Torrent from Axel Semrau), subsequently hot extraction five times with ethyl acetate/acetonitrile 1:1. Yield: 15.4 g (5.2 mmol) 52%; purity: about 99.9% according to HPLC.

[0307] The following compounds can be prepared analogously:

TABLE-US-00021 Ex. Starting material Variant/reaction conditions Boronic acid Product/hot extractant (HE) or Recrystallisation agent Yield Ir.sub.2101 [00912] [00913] 30% Ir.sub.2102 [00914] [00915] 50% HE: ethyl acetate Ir.sub.2103 [00916] [00917] 49% Ir.sub.2104 [00918] [00919] 35% Ir.sub.2105 [00920] [00921] 39% Ir.sub.2107 [00922] [00923] 44% Ir.sub.2108 [00924] [00925] 40% Ir.sub.2109 [00926] [00927] 23% Ir.sub.2110 [00928] [00929] 45% Ir.sub.2111 [00930] [00931] 50% Ir.sub.2112 [00932] [00933] 52% Ir.sub.2113 [00934] [00935] 36% Ir.sub.2115 [00936] [00937] 40% Ir.sub.2116 [00938] [00939] 36% Recrystallisation: DMF Ir.sub.2117 [00940] [00941] 40% HE: butyl acetate Ir.sub.2118 [00942] [00943] 55% Ir.sub.2119 [00944] [00945] 60% Ir.sub.2120 [00946] [00947] 52% Hot extraction: toluene/heptane 3:1 Ir.sub.2121 [00948] [00949] 51% Ir.sub.2122 [00950] [00951] 57% Ir.sub.2123 [00952] [00953] 51% Ir.sub.2124 [00954] [00955] 56% Ir.sub.2125 [00956] [00957] 46% Ir.sub.2126 [00958] [00959] 44% Ir.sub.2127 [00960] [00961] 51% Ir.sub.2128 [00962] [00963] 46% Ir.sub.2129 [00964] [00965] 42% Hot extraction: toluene Ir.sub.2130 [00966] [00967] 49% Hot extraction: n-butyl acetate Ir.sub.2131 [00968] [00969] 52% Hot extraction: toluene Ir.sub.2132 [00970] [00971] 24% HE: ethyl acetate/acetonitrile 3:1 Ir.sub.2133 [00972] [00973] 45% HE: n-butyl acetate Ir.sub.2134 [00974] [00975] 22% Ir.sub.2135 [00976] [00977] 35% Ir.sub.2136 [00978] [00979] 50% Ir.sub.2137 [00980] [00981] 41% Ir.sub.2138 [00982] [00983] 48% Ir.sub.2139 [00984] [00985] 51% Ir.sub.2140 [00986] [00987] 57% Hot extraction: n-butyl acetate Ir.sub.2141 [00988] [00989] 26% Hot extraction: ethyl acetate Ir.sub.2142 [00990] [00991] 45% Hot extraction: toluene Ir.sub.2143 [00992] [00993] 38% Recrystallisation: DMF Ir.sub.2144 [00994] [00995] 22% Recrystallisation: dimethylacetamide Ir.sub.2145 [00996] [00997] 53% Hot extraction: toluene Ir.sub.2146 [00998] [00999] 42% Hot extraction: toluene Ir.sub.2147 [01000] [01001] 55% I2-Ir.sub.2(L42-4Br) Hot extraction: toluene Ir.sub.2148 [01002] [01003] 22% Ir.sub.2149 [01004] [01005] 24% Ir.sub.2150 [01006] [01007] 40% Ir.sub.2151 [01008] [01009] 20% Ir.sub.2152 [01010] [01011] 43% Ir.sub.2153 [01012] [01013] 40% Ir.sub.2154 [01014] [01015] 50% Hot extraction: ethyl acetate Ir.sub.2155 [01016] [01017] 44% Hot extraction: n-butyl acetate Ir.sub.2156 [01018] [01019] 25% I1-Ir.sub.2(L92) Hot extraction: ethyl acetate Ir.sub.2157 [01020] [01021] 24% Ir.sub.2158 [01022] [01023] 33% Hot extraction: n-butyl acetate Ir.sub.2159 [01024] [01025] 36% Hot extraction: toluene Ir.sub.2160 [01026] [01027] 49% Hot extraction: toluene Ir.sub.2161 [01028] [01029] 29% Hot extraction: ethyl acetate Ir.sub.2162 [01030] [01031] 38% Hot extraction: cyclohexane Ir.sub.2163 [01032] [01033] 55% Hot extraction: n-butyl acetate

[0308] General synthetic scheme for the preparation of further metal complexes P1 to P240:

##STR01034## ##STR01035## ##STR01036##

[0309] The metal complexes depicted in the table below can be prepared by the synthetic scheme depicted above starting from the starting materials indicated:

TABLE-US-00022 Starting Ex. materials P1 [01037] [01038] P2 [01039] [01040] P3 [01041] [01042] P4 [01043] [01044] P5 [01045] [01046] P6 [01047] [01048] P7 [01049] [01050] P8 [01051] [01052] P9 [01053] [01054] P10 [01055] [01056] P11 [01057] [01058] P12 [01059] [01060] P13 [01061] [01062] P14 [01063] [01064] P15 [01065] [01066] P16 [01067] [01068] P17 [01069] [01070] P18 [01071] [01072] P19 [01073] [01074] P20 [01075] [01076] P21 [01077] [01078] P22 [01079] [01080] P23 [01081] [01082] P24 [01083] [01084] P25 [01085] [01086] P26 [01087] [01088] P27 [01089] [01090] P28 [01091] [01092] P29 [01093] [01094] P30 [01095] [01096] P31 [01097] [01098] P32 [01099] [01100] P33 [01101] [01102] P34 [01103] [01104] P35 [01105] [01106] P36 [01107] [01108] P37 [01109] [01110] P38 [01111] [01112] P39 [01113] [01114] P40 [01115] [01116] P41 [01117] [01118] P42 [01119] [01120] P43 [01121] [01122] P44 [01123] [01124] P45 [01125] [01126] P46 [01127] [01128] P47 [01129] [01130] O48 [01131] [01132] P49 [01133] [01134] P50 [01135] [01136] P51 [01137] [01138] P52 [01139] [01140] P53 [01141] [01142] P54 [01143] [01144] P55 [01145] [01146] P56 [01147] [01148] P57 [01149] [01150] P58 [01151] [01152] P59 [01153] [01154] P60 [01155] [01156] P61 [01157] [01158] P62 [01159] [01160] P63 [01161] [01162] P64 [01163] [01164] P65 [01165] [01166] P66 [01167] [01168] P67 [01169] [01170] P68 [01171] [01172] P69 [01173] [01174] P70 [01175] [01176] P71 [01177] [01178] P72 [01179] [01180] P73 [01181] [01182] P74 [01183] [01184] P75 [01185] [01186] P76 [01187] [01188] P77 [01189] [01190] P78 [01191] [01192] P79 [01193] [01194] P80 [01195] [01196] P81 [01197] [01198] P82 [01199] [01200] P83 [01201] [01202] P84 [01203] [01204] P85 [01205] [01206] P86 [01207] [01208] P87 [01209] [01210] P88 [01211] [01212] P89 [01213] [01214] P90 [01215] [01216] P91 [01217] [01218] P92 [01219] [01220] P93 [01221] [01222] P94 [01223] [01224] P95 [01225] [01226] P96 [01227] [01228] P97 [01229] [01230] P98 [01231] [01232] P99 [01233] [01234] P100 [01235] [01236] P101 [01237] [01238] P102 [01239] [01240] P103 [01241] [01242] P104 [01243] [01244] P105 [01245] [01246] P106 [01247] [01248] P107 [01249] [01250] P108 [01251] [01252] P109 [01253] [01254] P110 [01255] [01256] P111 [01257] [01258] P112 [01259] [01260] P113 [01261] [01262] P114 [01263] [01264] P115 [01265] [01266] P116 [01267] [01268] P117 [01269] [01270] P118 [01271] [01272] P119 [01273] [01274] P120 [01275] [01276] P121 [01277] [01278] P122 [01279] [01280] P123 [01281] [01282] P124 [01283] [01284] P125 [01285] [01286] P126 [01287] [01288] P127 [01289] [01290] P128 [01291] [01292] P129 [01293] [01294] P130 [01295] [01296] P131 [01297] [01298] P132 [01299] [01300] P133 [01301] [01302] P134 [01303] [01304] P135 [01305] [01306] P136 [01307] [01308] P137 [01309] [01310] P138 [01311] [01312] P139 [01313] [01314] P140 [01315] [01316] P141 [01317] [01318] P142 [01319] [01320] P143 [01321] [01322] P144 [01323] [01324] P145 [01325] [01326] P146 [01327] [01328] P146 [01329] [01330] P147 [01331] [01332] P148 [01333] [01334] P149 [01335] [01336] P150 [01337] [01338] P151 [01339] [01340] P152 [01341] [01342] P153 [01343] [01344] P154 [01345] [01346] P155 [01347] [01348] P156 [01349] [01350] P157 [01351] [01352] P158 [01353] [01354] P159 [01355] [01356] P160 [01357] [01358] P161 [01359] [01360] P162 [01361] [01362] P163 [01363] [01364] P164 [01365] [01366] P165 [01367] [01368] P166 [01369] [01370] P167 [01371] [01372] P168 [01373] [01374] P169 [01375] [01376] P170 [01377] [01378] P171 [01379] [01380] P172 [01381] [01382] P173 [01383] [01384] P174 [01385] [01386] P175 [01387] [01388] P176 [01389] [01390] P177 [01391] [01392] P178 [01393] [01394] P179 [01395] [01396] P180 [01397] [01398] P181 [01399] [01400] P182 [01401] [01402] P183 [01403] [01404] P184 [01405] [01406] P185 [01407] [01408] P186 [01409] [01410] P187 [01411] [01412] P188 [01413] [01414] P189 [01415] [01416] P190 [01417] [01418] P191 [01419] [01420] P192 [01421] [01422] P193 [01423] [01424] P194 [01425] [01426] P195 [01427] [01428] P196 [01429] [01430] P197 [01431] [01432] P198 [01433] [01434] P199 [01435] [01436] P200 [01437] [01438] P201 [01439] [01440] [01441] P202 [01442] [01443] P203 [01444] [01445] P204 [01446] [01447] P205 [01448] [01449] P206 [01450] [01451] P207 [01452] [01453] P208 [01454] [01455] P209 [01456] [01457] P210 [01458] [01459] P211 [01460] [01461] P212 [01462] [01463] P213 [01464] [01465] P214 [01466] [01467] P215 [01468] [01469] P216 [01470] [01471] P217 [01472] [01473] P218 [01474] [01475] P219 [01476] [01477] P220 [01478] [01479] P221 [01480] [01481] P222 [01482] [01483] P223 [01484] [01485] P224 [01486] [01487] P225 [01488] [01489] P226 [01490] [01491] P227 [01492] [01493] P228 [01494] [01495] P229 [01496] [01497] P230 [01498] [01499] P231 [01500] [01501] P232 [01502] [01503] P233 [01504] [01505] P234 [01506] [01507] P235 [01508] [01509] P236 [01510] [01511] P237 [01512] [01513] P238 [01514] [01515] P239 [01516] [01517] P240 [01518] [01519]

[0310] Entirely analogously to Example is P1 to P240, it is also possible to employ the following boronic acids or esters of the di-, tri- and oligophenylenes, -fluorenes, -dibenzofurans, -dibenzothiophenes and -carbazoles: [0311] CAS: [439120-88-4], [881912-24-9], [952586-63-9], [797780-74-3], [875928-51-1], [1056044-60-0], [1268012-82-3], [1356465-28-5], [1860030-34-7], [2007912-81-2], [1343990-89-5], [1089154-61-9].

[0312] In the syntheses of ligands L1 to L76, the boronic acids or esters of Examples P1 to P240 can be employed and the derived metal complexes can be obtained from the resultant ligands, by the process described for the synthesis of I1-Ir.sub.2(L1) and I2-Ir.sub.2(L1).

General Synthesis Scheme the Preparation of Further Metal Complexes:

[0313] Starting from 2-bromo-4-R.sup.1-5-methoxypyridines, tetra-methoxy-substituted metal complexes, for example P234, are obtained analogously to the reaction sequence shown above. These can be demethylated using pyridinium hydrochloride in the melt at 200 C. or using BBr.sub.3 in dichloromethane by generally known standard methods. The tetrahydroxy complexes obtained in this way can be reacted with trifluoromethanesulfonic acid in the presence of a base (for example triethylamine) in dichloromethane by standard methods to give tetratriflates, which can be coupled to boronic acids or boronic acid esters by standard methods (Suzuki coupling) to give compounds according to the invention. The tetratriflates can in addition be functionalised with alkyl, silyl, germanyl, stannyl, aryl, heteroaryl, alkoxy, amino or carbazolyl radicals in further transition-metal-promoted coupling reactions, for example Negisgi, Yamamoto, Stille, Sonogashira, Glaser, Ullmann, Grignard-Cross or Buchwald couplings.

##STR01520## ##STR01521##

Deuteration of the Complexes:

Example P1-D25

[0314] ##STR01522##

[0315] A mixture of 1.95 g (1 mmol) of P1, 68 mg (1 mmol) of sodium ethoxide, 3 ml of ethanol-D1 and 50 ml of DMSO-D6 is heated at 120 C. for 8 h. After cooling, a mixture of 0.5 ml of DCI in D20, 5 molar, and 3 ml of ethanol-D1 is added, the solvent is then removed in vacuo, and the residue is chromatographed on silica gel with DCM. Yield: 1.78 g (0.9 mmol), 90%, degree of deuteration >95%.

[0316] The following compounds can be prepared analogously:

TABLE-US-00023 Starting Ex. material Product P4- D21 P4 [01523] P6- D17 P6 [01524] P7- D21 P7 [01525] P14- D13 P14 [01526] P15- D13 P15 [01527] P34- D13 P34 [01528] P50- D13 P50 [01529] P77- D13 P77 [01530] P104- D13 P104 [01531] P160- D13 P160 [01532] P198- D9 P198 [01533] P222- D33 P222 [01534]

Synthesis of the Complexes by Sequential Ortho-Metallation:

1) Sequential Ortho-Metallation for the Preparation of Bimetallic Complexes

[0317] The bimetallic complexes can also be obtained by sequential ortho-metallation. In this process, a monometallic complex Ir(L1) or Rh(L1) can firstly be isolated specifically. The subsequent reaction with a further equivalent of Ir(acac).sub.3 or Rh(acac).sub.3 gives the bicyclic homo- or heterometallic complexes Ir.sub.2(L1), Rh2(L1) or IrRh(L1). The bimetallic complexes are likewise formed here as a mixture of and isomers and and isomers. and isomers form an enantiomer pair, as do the and isomers. The diastereomer pairs can be separated using conventional methods, for example by chromatography or fractional crystallisation. Depending on the symmetry of the ligands, stereocentres may also coincide, so that meso forms are also possible. Thus, for example in the case of the ortho-metallation of ligands having C.sub.2v Or C.sub.s symmetry, and isomers (racemate, C.sub.2 symmetry) and a isomer (meso compound, C.sub.s symmetry) form.

Step 1: Monometallic Complexes

[0318] For the preparation of the monometallic complexes, 25 g (11 mmol) of ligand L1, 4.9 g (11 mmol) of tris(acetylacetonato)iridium(III) [15635-87-7] and 200 g of hydroquinone [123-31-9] are introduced into a 1000 ml two-necked round-bottomed flask with a glass-clad magnetic stirrer bar. The flask is provided with a water separator (for media of lower density than water) and an air condenser with argon blanket and is placed in a metal heating dish. The apparatus is flushed with argon from above via the argon blanket for 15 min, during which the argon is allowed to flow out of the side neck of the two-necked flask. A glass-clad Pt-100 thermocouple is introduced into the flask via the side neck of the two-necked flask and the end is positioned just above the magnetic stirrer bar. The apparatus is then thermally insulated by means of several loose coils of household aluminium foil, with the insulation extending as far as the centre of the riser tube of the water separator. The apparatus is then quickly heated to 250 C., measured at the Pt-100 temperature sensor, which dips into the molten, stirred reaction mixture, using a laboratory hotplate stirrer. During the next 2 h, the reaction mixture is held at 250 C., during which little condensate distils off and collects in the water separator. The reaction mixture is allowed to cool to 190 C., and 100 ml of ethylene glycol are then added dropwise. The mixture is allowed to cool further to 80 C., and 500 ml of methanol are then added dropwise, and the mixture is heated under reflux for 1 h. The suspension obtained in this way is filtered through a reverse frit, and the solid is washed twice with 50 ml of methanol and then dried in vacuo. The solid obtained in this way is dissolved in 200 ml of dichloromethane and filtered through about 1 kg of silica gel which has been pre-slurried with dichloromethane (column diameter about 18 cm) with exclusion of air and light, with dark components remaining at the start. The core fraction is cut out and evaporated in a rotary evaporator, during which MeOH is simultaneously continuously added dropwise until crystallisation occurs. After suction filtration, washing with a little MeOH and drying in vacuo, the monometallated complex Ir(L1) is obtained. The rhodium complex Rh(L1) can be prepared analogously starting from Rh(acac).sub.3 [14284-92-5].

[0319] All ligands shown in this invention can be converted into monometallic complexes of the Ir(L1) or Rh(L1) type through the use of 1 equivalent of Ir(acac).sub.3 or Rh(acac).sub.3. Just a few examples are shown below.

TABLE-US-00024 Starting Product/reaction conditions/ Comp. material hot extractant (HE) Yield* Ir(L1) L1 Ir(acac).sub.3 [15635- 87-7] [01535] 48% Rh(L1) L1 Rh(acac).sub.3 [14284- 92-5] [01536] 43% Ir(L57) L1 Ir(acac).sub.3 [15635- 87-7] [01537] 40% Rh(L57) L1 Rh(acac).sub.3 [14284- 92-5] [01538] 45%

[0320] The complexes Ir(L1) and Rh(L1) can now be reacted with a further equivalent of Ir(acac).sub.3 or Rh(acac).sub.3 to give the bimetallic complexes I1-Ir.sub.2(L1), I2-Ir.sub.2(L1), I1-Rh2(L1), 12-Rh(L1), I1-IrRh(L1) and 12-IrRh(L1). It is unimportant here which metal is introduced first.

Step 2: Bimetallic Complex

[0321] For the preparation of the bimetallic complexes from the monometallic complexes, 24.5 g (10 mmol) of the complex Ir1(L1), 4.9 g (10 mmol) of tris(acetylacetonato)iridium(III) [15635-87-7] and 200 g of hydroquinone [123-31-9] are introduced into a 1000 ml two-necked round-bottomed flask with a glass-clad magnetic stirrer bar. The flask is provided with a water separator (for media of lower density than water) and an air condenser with argon blanket and is placed in a metal heating dish. The apparatus is flushed with argon from above via the argon blanket for 15 min, during which the argon is allowed to flow out of the side neck of the two-necked flask. A glass-clad Pt-100 thermocouple is introduced into the flask via the side neck of the two-necked flask and the end is positioned just above the magnetic stirrer bar. The apparatus is then thermally insulated by means of several loose coils of household aluminium foil, with the insulation extending as far as the centre of the riser tube of the water separator. The apparatus is then quickly heated to 250 C., measured at the Pt-100 temperature sensor, which dips into the molten, stirred reaction mixture, using a laboratory hotplate stirrer. During the next 2 h, the reaction mixture is held at 250 C., during which little condensate distils off and collects in the water separator. The reaction mixture is allowed to cool to 190 C., and 100 ml of ethylene glycol are then added dropwise. The mixture is allowed to cool further to 80 C., and 500 ml of methanol are then added dropwise, and the mixture is heated under reflux for 1 h. The suspension obtained in this way is filtered through a reverse frit, and the solid is washed twice with 50 ml of methanol and then dried in vacuo. The solid obtained in this way is dissolved in 200 ml of dichloromethane and filtered through about 1 kg of silica gel which has been pre-slurried with dichloromethane (column diameter about 18 cm) with exclusion of air and light, with dark components remaining at the start. The core fraction is cut out and evaporated in a rotary evaporator, during which MeOH is simultaneously continuously added dropwise until crystallisation occurs. After suction filtration, washing with a little MeOH and drying in vacuo, the diastereomeric product mixture is purified further.

[0322] The bimetallic complexes obtained by sequential ortho-metallation are likewise formed as a mixture of and isomers and and isomers. and isomers form an enantiomer pair, as do the and isomers. The diastereomer pairs can be separated using conventional methods, for example by chromatography or fractional crystallisation. Depending on the symmetry of the ligands, stereocentres may also coincide, so that meso forms are also possible. Thus, for example in the case of the ortho-metallation of ligands having C.sub.2v or C.sub.s symmetry, and isomers (racemate, C.sub.2 symmetry) and a isomer (meso compound, C.sub.s symmetry) form.

[0323] All complexes of the ligands shown herein which are shown in this invention for two iridium or rhodium atoms can also be prepared by sequential ortho-metallation. Likewise, heterometallic complexes of the IrRh(L) type can be prepared from all ligands shown in this invention by sequential ortho-metallation.

[0324] The sequential ortho-metallation can also be carried out as a one-pot reaction. To this end, firstly step 1 is carried out to give the monometallic complexes. After a reaction time of 2 h, a further equivalent of Ir(acac).sub.3 or Rh(acac).sub.3 is added. After a reaction time of a further 2 h at 250 C., the mixture is worked up as described above in step 2, and the crude products obtained in this way are purified.

[0325] Just a few selected examples are shown below. The drawings of complexes usually show only one isomer. The isomer mixture can be separated, but can equally well be employed as an isomer mixture in the OLED device. However, there are also ligand systems in the case of which, for steric reasons, only one diastereomer pair forms.

TABLE-US-00025 Starting Product/reaction conditions/ Ex. material hot extractant (HE) Yield* I1- IrRh(L1) Ir(L1) or Rh(L1) Rh(acac).sub.3 or Ir(acac).sub.3 [14284- 92-5] or [15635- 87-7] [01539] 20% I2- IrRh(L1) Ir(L1) or Rh(L1) Rh(acac).sub.3 or Ir(acac).sub.3 [14284- 95-5] or [15635- 87-7] [01540] 20% IrRh(L57) Ir(L1) or Rh(L1) Rh(acac).sub.3 or Ir(acac).sub.3 [14284- 92-5] or [15635- 87-7] [01541] 20% IrRh(L57) Ir(L1) or Rh(L1) Rh(acac).sub.3 or Ir(acac).sub.3 [14284- 92-5] or [15635- 87-7] [01542] 20%

2) Sequential Ortho-Metallation for the Preparation of Trimetallic Complexes

Introduction of the First Metal

[0326] The sequential ortho-metallation can also be utilised to build up trimetallic complexes of the Ir.sub.3(L52), IrRh2(L52), Ir.sub.2Rh(L52) or Rh3(L52) type. To this end, 22 g (10 mmol) of the complex Ir1(L1), 4.9 g (10 mmol) of tris-(acetylacetonato)iridium(III) [15635-87-7] and 200 g of hydroquinone [123-31-9] are introduced into a 1000 ml two-necked round-bottomed flask with a glass-clad magnetic stirrer bar. The flask is provided with a water separator (for media of lower density than water) and an air condenser with argon blanket and is placed in a metal heating dish. The apparatus is flushed with argon from above via the argon blanket for 15 min, during which the argon is allowed to flow out of the side neck of the two-necked flask. A glass-clad Pt-100 thermocouple is introduced into the flask via the side neck of the two-necked flask and the end is positioned just above the magnetic stirrer bar. The apparatus is then thermally insulated by means of several loose coils of household aluminium foil, with the insulation extending as far as the centre of the riser tube of the water separator. The apparatus is then quickly heated to 260 C., measured at the Pt-100 temperature sensor, which dips into the molten, stirred reaction mixture, using a laboratory hotplate stirrer. During the next 2 h, the reaction mixture is held at 260 C., during which little condensate distils off and collects in the water separator. The reaction mixture is allowed to cool to 190 C., and 100 ml of ethylene glycol are then added dropwise. The mixture is allowed to cool further to 80 C., and 500 ml of methanol are then added dropwise, and the mixture is heated under reflux for 1 h. The suspension obtained in this way is filtered through a reverse frit, and the solid is washed twice with 50 ml of methanol and then dried in vacuo. The solid obtained in this way is dissolved in 400 ml of toluene and filtered through about 1 kg of silica gel which has been pre-slurried with dichloromethane (column diameter about 18 cm) with exclusion of air and light, with dark components remaining at the start. The core fraction is cut out and evaporated in a rotary evaporator, during which MeOH is simultaneously continuously added dropwise until crystallisation occurs. After suction filtration, washing with a little MeOH and drying in vacuo, the monometallic complex Ir(L52) is obtained.

Introduction of the Second Metal

[0327] The complex Ir(L52) together with 4.9 g (10 mmol) of tris(acetylacetonato)-iridium(III) [15635-87-7] and 200 g of hydroquinone [123-31-9] are introduced into a 1000 ml two-necked round-bottomed flask with a glass-clad magnetic stirrer bar. The flask is provided with a water separator (for media of lower density than water) and an air condenser with argon blanket and is placed in a metal heating dish. The apparatus is flushed with argon from above via the argon blanket for 15 min, during which the argon is allowed to flow out of the side neck of the two-necked flask. A glass-clad Pt-100 thermocouple is introduced into the flask via the side neck of the two-necked flask and the end is positioned just above the magnetic stirrer bar. The apparatus is then thermally insulated by means of several loose coils of household aluminium foil, with the insulation extending as far as the centre of the riser tube of the water separator. The apparatus is then quickly heated to 260 C., measured at the Pt-100 temperature sensor, which dips into the molten, stirred reaction mixture, using a laboratory hotplate stirrer. During the next 2 h, the reaction mixture is held at 260 C., during which little condensate distils off and collects in the water separator. The reaction mixture is allowed to cool to 190 C., and 100 ml of ethylene glycol are then added dropwise. The mixture is allowed to cool further to 80 C., and 500 ml of methanol are then added dropwise, and the mixture is heated under reflux for 1 h. The suspension obtained in this way is filtered through a reverse frit, and the solid is washed twice with 50 ml of methanol and then dried in vacuo. The solid obtained in this way is dissolved in 400 ml of toluene and filtered through about 1 kg of silica gel which has been pre-slurried with dichloromethane (column diameter about 18 cm) with exclusion of air and light, with dark components remaining at the start. The core fraction is cut out and evaporated in a rotary evaporator, during which MeOH is simultaneously continuously added dropwise until crystallisation occurs. After suction filtration, washing with a little MeOH and drying in vacuo, the bimetallic complex Ir.sub.2(L52) is obtained.

Introduction of the Third Metal

[0328] The complex Ir.sub.2(L52) together with 4.9 g (10 mmol) of tris(acetyl-acetonato)iridium(III) [15635-87-7] and 200 g of hydroquinone [123-31-9] are introduced into a 1000 ml two-necked round-bottomed flask with a glass-clad magnetic stirrer bar. The flask is provided with a water separator (for media of lower density than water) and an air condenser with argon blanket and is placed in a metal heating dish. The apparatus is flushed with argon from above via the argon blanket for 15 min, during which the argon is allowed to flow out of the side neck of the two-necked flask. A glass-clad Pt-100 thermocouple is introduced into the flask via the side neck of the two-necked flask and the end is positioned just above the magnetic stirrer bar. The apparatus is then thermally insulated by means of several loose coils of household aluminium foil, with the insulation extending as far as the centre of the riser tube of the water separator. The apparatus is then quickly heated to 260 C., measured at the Pt-100 temperature sensor, which dips into the molten, stirred reaction mixture, using a laboratory hotplate stirrer. During the next 2 h, the reaction mixture is held at 260 C., during which little condensate distils off and collects in the water separator. The reaction mixture is allowed to cool to 190 C., and 100 ml of ethylene glycol are then added dropwise. The mixture is allowed to cool further to 80 C., and 500 ml of methanol are then added dropwise, and the mixture is heated under reflux for 1 h. The suspension obtained in this way is filtered through a reverse frit, and the solid is washed twice with 50 ml of methanol and then dried in vacuo. The solid obtained in this way is dissolved in 400 ml of toluene and filtered through about 1 kg of silica gel which has been pre-slurried with dichloromethane (column diameter about 18 cm) with exclusion of air and light, with dark components remaining at the start. The core fraction is cut out and evaporated in a rotary evaporator, during which MeOH is simultaneously continuously added dropwise until crystallisation occurs. After suction filtration, washing with a little MeOH and drying in vacuo, the trimetallic complex Ir.sub.3(L52) is obtained.

[0329] The trimetallic complex is purified further by hot extraction. The trimetallic complex Ir.sub.3(L52) shown below can be prepared by sequential metallation in accordance with the above reaction sequence or by reaction of L52 with 3 equivalents of Ir(acac).sub.3 or Rh(acac).sub.3.

[0330] For the preparation of a heterotrimetallic complex, such as, for example, IrRh2(L52) or Ir.sub.2Rh(L52), Rh(acac).sub.3 is used instead of Ir(acac).sub.3 in one or two steps in accordance with the above reaction sequence. The sequence in which the metals are introduced is unimportant here.

TABLE-US-00026 Starting Product/reaction conditions/ Ex. material hot extractant (HE) Yield* Ir.sub.3(L52) L52 Ir(acac).sub.3 [15635- 87-7] [01543] 33% Ir.sub.3(L52) 3 equiv. of Ir(acac).sub.3, 260 C.; 7 h Only the racemate of the and isomers is formed Hot extraction: toluene Rh.sub.3(L52) L52 Rh(acac).sub.3 [14284- 92-5] [01544] 32% Ir.sub.3(L52) 3 equiv. of Rh(acac).sub.3, 260 C.; 7 h Only the racemate of the and isomers is formed Hot extraction: toluene Ir.sub.3(L53) L53 Ir(acac).sub.3 [15635- 87-7] [01545] 29% Ir.sub.3(L53) 3 equiv. of Ir(acac).sub.3, 260 C.; 7 h Only the racemate of the and isomers is formed Hot extraction: toluene Rh.sub.3(L53) L53 Rh(acac).sub.3 [14284- 92-5] [01546] 33% Rh.sub.3(L53) 3 equiv. of Rh(acac).sub.3, 260 C.; 7 h Only the racemate of the and isomers is formed Hot extraction: toluene Ir.sub.2Rh (L53) L53 Rh(acac).sub.3 or Ir(acac).sub.3 [14284- 92-5] or [15635- 87-7] [01547] 30% Ir.sub.2Rh(L53) Sequentially 2 equiv. of Ir(acac).sub.3, 1 equiv. of Rh(acac).sub.3, 260 C.; 7 h Hot extraction: o-xylene Only the racemate of the and isomers is formed IrRh.sub.2 (L53) L53 Rh(acac).sub.3 or Ir(acac).sub.3 [14284- 92-5] or [15635- 87-7] [01548] 29% IrRh.sub.2(L53) Sequentially 1 equiv. of Ir(acac).sub.3, 2 equiv. of Rh(acac).sub.3, 260 C.; 7 h Hot extraction: o-xylene Only the racemate of the and isomers is formed Ir.sub.2Rh (L54) L54 Rh(acac).sub.3 or Ir(acac).sub.3 [14284- 92-5] or [15635- 87-7] [01549] 20% Ir.sub.2Rh(L54) Sequentially 2 equiv. of Ir(acac).sub.3, 1 equiv. of Rh(acac).sub.3, 260 C.; 7 h Hot extraction: n-butyl acetate Only the racemate of the and isomers is formed IrRh.sub.2 (L54) L54 Rh(acac).sub.3 or Ir(acac).sub.3 [14284- 92-5] or [15635- 87-7] [01550] 18% Ir.sub.2Rh(L54) Sequentially 1 equiv. of Ir(acac).sub.3, 2 equiv. of Rh(acac).sub.3, 260 C.; 7 h Hot extraction: n-butyl acetate Only the racemate of the and isomers is formed Ir.sub.2Rh (L55) L55 Rh(acac).sub.3 or Ir(acac).sub.3 [14284- 92-5] or [15635- 87-7] [01551] 21% Ir.sub.2Rh(L55) Sequentially 2 equiv. of Ir(acac).sub.3, 1 equiv. of Rh(acac).sub.3, 260 C.; 7 h Hot extraction: toluene Only the racemate of the and isomers is formed IrRh.sub.2 (L55) L55 Rh(acac).sub.3 or Ir(acac).sub.3 [14284- 92-5] or [15635- 87-7] [01552] 19% IrRh.sub.2(L55) Sequentially 1 equiv. of Ir(acac).sub.3, 2 equiv. of Rh(acac).sub.3, 260 C.; 7 h Hot extraction: toluene Only the racemate of the and isomers is formed

Example 1: Thermal and Photophysical Properties and Oxidation and Reduction Potentials

[0331] Table 1 summarises the thermal and photochemical properties and oxidation and reduction potentials of the comparative materials and the selected materials according to the invention. The compounds according to the invention have improved thermal stability and photostability compared with the non-polypodal materials in accordance with the prior art. While non-polypodal materials in accordance with the prior art exhibit brown colora-tions and ashing after thermal storage at 380 C. for seven days and secon-dary components in the range >2 mol % can be detected in the 1H-NMR, the complexes according to the invention are inert under these conditions. In addition, the compounds according to invention have very good photostability in anhydrous C.sub.6D.sub.6 solution on irradiation with light having a wavelength of about 455 nm. In particular, in contrast to non-polypodal complexes in accordance with the prior art which contain bidentate ligands, facial-meridional isomerisation is not evident in the .sup.1H-NMR. As is evident from Table 1, the compounds according to the invention are all distinguished by very high PL quantum efficiencies in solution.

Structures in Photoluminescence of Investigated Complexes According to the Invention and Associated Comparative Complexes

[0332] (the numbers in square brackets indicate the corresponding CAS numbers; the synthesis of complexes without CAS numbers is described in the patent applications cited). Synthesis of Ref15 and Ref16 analogous to the synthetic procedure for complexes Ref13 and Ref14 described in US 2003/0152802. Starting from the following starting materials:

##STR01553##

[0333] A mixture of 2.3 g (10 mmol) of 4,6-diphenylpyrimidine [3977-48-8] and 12.0 g (20 mmol) of (acetylacetonato)bis(2-phenylpyridinato-N,C2)iridium [945028-21-7] is suspended in 500 ml of glycerol, degassed by passing argon through for 30 min and then stirred at 180 C. for 3 h. After cooling, 1000 ml of methanol are added to the reaction mixture, and the solid which has precipitated out is filtered off with suction. The diastereomers are separated by column chromatography on an automated column from Axel Semrau on flash silica gel with toluene/ethyl acetate as eluent mixture. The compounds Ref15 and Ref16 are subsequently purified further separately by hot extraction. For Ref15 hot extraction five times from ethyl acetate, for Ref16 hot extraction 3 times from n-butyl acetate. Finally, the compounds are heated a high vacuum. Yield of Ref15: 1.2 g (1.0 mmol), 10%. Yield of Ref16: 1.5 g (1.2 mmol), 12%. The yield is based on the amount of ligand employed

TABLE-US-00027 Complex [01554] Ref1 [1870013-87-8] [01555] Ref2 see WO 2016/124304 [01556] Ref3 [1202823-72-0] [01557] Ref4 [1935740-05-8] [01558] Ref5 see WO 2016/124304 [01559] Ref6* [1859110-77-2] [01560] Ref7* [1859924-65-4] [01561] Ref8 [1904599-30-9] [01562] Ref9* [1562104-35-1] [01563] Ref10* [1562395-58-7] [01564] Ref11 see WO 2016/124304 [01565] Ref12 see WO 2016/124304 [01566] Ref13 see compound 166 in US 2003/0152802 [01567] Ref14 [501097-40-1] [01568] Ref15 [01569] Ref16 *Ref6 and Ref7 form a diastereomer pair, as do Ref9 and Ref10.

TABLE-US-00028 TABLE 1 HOMO PL-max Therm. [eV] [nm] stability LUMO FWHM PLQE Decay time Photochem. Complex [eV] [nm] Solvent .sub.T [S] stab. Comparative examples, structures see Table 13 Ref1 4.96 619 0.80 0.71 Decomposition 2.60 48 Toluene Decomposition Ref2 5.21 605 0.84 0.70 No decomp. 2.80 49 Toluene No decomp. Ref 3 5.18 595 0.82 0.72 Decomposition 2.70 63 Toluene Decomposition Ref 4 5.00 615 0.86 1.38 Decomposition 2.32 55 Toluene Decomposition Ref5 5.17 599 0.86 0.75 No decomp. 2.70 51 Toluene No decomp. Ref6*.sup.1 5.25 606 0.61 0.18 2.59 DCM Ref7*.sup.1 5.30 607 0.49 0.18 2.64 DCM Ref8*.sup.1 5.45 525 0.99 1.02 2.51 DCM Ref9*.sup.2 622 0.65 0.75 DCM Ref10*.sup.2 625 0.65 0.73 DCM Ref11 520 0.98 1.65 No decomp. 64 Toluene No decomp. Ref12 5.11 528 0.81 1.6 No decomp. 2.24 70 Toluene No decomp. Ref13 570 Decomp. 69 Decomp. Ref14* 651 0.67 Decomp. 52 Toluene Decomp. Ref15 5.12 607 0.84 Decomp. 2.52 65 Toluene Decomp. Ref16 5.10 603 0.85 Decomp. 2.55 67 Toluene Decomp. Examples according to the invention I1-Ir.sub.2(L1) 5.12 608 0.91 0.43 No decomp. 2.56. 58 Toluene No decomp. I2-Ir.sub.2(L1) 5.11 609 0.92 0.41 No decomp. 2.63 56 Toluene No decomp. I1-Ir.sub.2(L75) 5.08 626 0.90 0.53 No decomp. 2.48 49 Toluene I2-Ir.sub.2(L75) 614 0.85 0.49 No decomp. 52 Toluene Ir.sub.2100 5.09 612 0.93 0.39 2.53 45 Toluene I1-Ir.sub.2(L16) 576 61 I1-Ir.sub.2(L44) 601 54 Ir.sub.3(L53) 626 43 I2-Ir.sub.2(L23) 672 41 Ir.sub.2101 617 44 I1-Ir.sub.2(L66) 602 49 Ir.sub.2(L59) 613 48 Ir.sub.2(L60) 682 62 I1-Ir.sub.2(L76) 621 71 I2-Ir.sub.2(L76) 619 66 *.sup.1Values from Inorg. Chem., 2016, 55, 1720-1727. *.sup.2Values from Chem. Commun, 2014, 50, 6831. Legend: Therm. stab. (thermal stability): Storage in ampules sealed in vacuo, 7 days at 380 C. Visual assessment for colour change/brown coloration/ashing and analysis by means of .sup.1H-NMR spectroscopy. Photo. stab. (photochemical stability): Irradiation of approx. 1 mmolar solution in anhydrous C.sub.6D.sub.6 (degassed and sealed NMR tubes) with blue light (about 455 nm, 1.2 W Lumispot from Dialight Corporation, USA) at room temperature. PL-max.: Maximum of the PL spectrum in nm of a degassed, approx. 10.sup.5 molar solution at room temperature, excitation wavelength 370 nm, solvent: see PLQE column. FWHM: Full width at half maximum of the PL spectrum in nm at room temperature. PLQE: Absolute photoluminescence quantum efficiency of a degassed, approx. 10.sup.5 molar solution in the solvent indicated at room temperature, measured as absolute value via Ulbricht sphere. Decay time: Determination of the T.sub.1 lifetime by time correlated single photon counting of a degassed 10.sup.5 molar solution in toluene at room temperature. HOMO, LUMO: Value in eV vs. vacuum, determined in dichloromethane solution (oxidation) or THF (reduction) with internal ref. ferrocene (4.8 eV vs. vacuum).

Device Examples

Example 1: Production of OLEDs

[0334] The complexes according to the invention can be processed from solution. The production of fully solution-based OLEDs has already been described many times in the literature, for example in WO 2004/037887 by means of spin coating. The production of vacuum-based OLEDs has likewise already been described many times, inter alia in WO 2004/058911. In the examples discussed below, layers applied on a solution basis and layers applied on a vacuum basis are combined within an OLED, so that the processing up to and including the emission layer is carried out from solution and the processing in the subsequent layers (hole-blocking layer and electron-transport layer) is carried out from vacuum. For this purpose, the general processes described previously are adapted to the circumstances described here (layer-thickness variation, materials) and combined. The general structure is as follows: substrate/ITO (50 nm)/hole-injection layer (HIL)/hole-transport layer (HTL)/emission layer (EML)/hole-blocking layer (HBL)/electron-transport layer (ETL)/cathode (aluminium, 100 nm). The substrate used is glass plates which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm. For better processing, these are coated with PEDOT:PSS (poly(3,4-ethylenedioxy-2,5-thiophene): polystyrene sulfonate, purchased from Heraeus Precious Metals GmbH & Co. KG, Germany). PEDOT:PSS is applied by spin-coating from water in air and subsequently dried by heating in 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 having the structures depicted below is used, which can be synthesised in accordance with WO 2010/097155 or WO 2013/156130:

##STR01570##

[0335] The hole-transport polymer is dissolved in toluene. The typical solids content of such solutions is approx. 5 g/I if, as here, the typical layer thickness of 20 nm for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried at 180 C. for 60 minutes.

[0336] The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). Furthermore, mixtures of a plurality of matrix materials and co-dopants can be used. An expression such as TMM-A (92%): dopant (8%) here means that the material TMM-A is present in the emission layer in a proportion by weight of 92% and the dopant is present in the emission layer 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 approx. 17 g/l if, as here, the typical layer thickness of 60 nm for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 150 C. for 10 minutes. The materials used in the present case are shown in Table 2.

TABLE-US-00029 TABLE 2 EML materials used [01571] A-1 [01572] A-2 [01573] B-1 [01574] B-2 [01575] B-3 [01576] B-4 [01577] C-1 [01578] C-2 [01579] C-3

[0337] The materials for the hole-blocking layer and electron-transport layer are applied by thermal vapour deposition in a vacuum chamber. The electron-transport layer here may, for example, consist of more than one material which are admixed with one another in a certain proportion by volume by co-evaporation. An expression such as ETM1:ETM2 (50%:50%) here means that the materials ETM1 and ETM2 are present in the layer in a proportion by volume of 50% each. The materials used in the present case are shown in Table 3.

TABLE-US-00030 TABLE 3 HBL and ETL materials used [01580] ETM1 [01581] ETM2 [01582] ETM3

[0338] The cathode is formed by thermal evaporation of a 100 nm aluminium layer. The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, current/voltage/luminous density characteristic lines (IUL characteristic lines), assuming Lambert emission characteristics, and the (operating) lifetime are determined. The IUL characteristic lines are used to determine characteristic numbers such as the operating voltage (in V) and the efficiency (cd/A) at a certain brightness. The electroluminescence spectra are measured at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The EML mixtures and structures of the OLED components investigated are shown in Table 4 and Table 5. The associated results can be found in Table 6.

TABLE-US-00031 TABLE 4 EML mixtures of the OLED components investigated Matrix A Co-matrix B Co-dopant C Dopant D Further co-matrix B Ex. Material % Material % Material % Material % Material % V1 A-2 30 B-1 47 C-1 17 Ref1 6 V2 A-2 30 B-1 45 C-1 17 Ref1 8 V3 A-2 30 B-1 34 C-1 30 Ref2 6 E-1 A-2 30 B-1 47 C-1 17 I1-Ir.sub.2(L1) 6 E-2 A-2 30 B-1 45 C-1 17 I1-Ir.sub.2(L1) 8 E-3 A-2 30 B-1 47 C-1 17 I2-Ir.sub.2(L1) 6 E-4 A-2 30 B-1 47 C-1 17 Ir.sub.2100 6 E-5 A-2 30 B-1 47 C-1 17 I1-Ir.sub.2(L44) 6 E-6 A-2 30 B-1 47 C-2 17 Ir.sub.3(L53) 6 E-7 A-2 30 B-1 45 C-1 17 Ir.sub.2101 8 E-8 A-2 30 B-1 47 C-2 17 I1-Ir.sub.2(L66) 6 E-9 A-2 30 B-1 47 C-1 17 Ir.sub.2(L59) 6 V4 A-1 40 B-1 45 Ref1 15 V5 A-1 40 B-1 55 Ref2 5 E-10 A-1 40 B-1 45 I1-Ir.sub.2(L1) 15 E-11 A-1 40 B-1 45 I2-Ir.sub.2(L1) 15 E-12 A-1 40 B-1 45 Ir.sub.2100 15 E-13 A-1 40 B-1 55 I1-Ir.sub.2(L44) 5 E-14 A-1 40 B-1 45 I1-Ir.sub.2(L16) 15 E-15 A-1 40 B-1 45 I1-Ir.sub.2(L66) 15 E-16 A-1 40 B-1 45 Ir.sub.2(L59) 15 E-17 A-2 30 B-1 47 C-3 17 I1-Ir.sub.2(L1) 6 E-18 A-2 30 B-1 47 C-1 17 Ref14 6 E-19 A-1 40 B-1 45 Ref13 15 E-20 A-2 40 B-1 40 Ir2(100) 20 E-21 A-2 40 B-1 40 I1-Ir.sub.2(L75) 20 E-22 A-2 30 B-1 47 I2-Ir.sub.2(L75) 6 E-23 A-2 30 B-1 37 C-1 25 I1-Ir.sub.2(L75) 8 E-24 A-2 30 B-1 40 C-1 22 I1-Ir.sub.2(L75) 8 E-25 A-2 30 B-1 32 C-1 20 I1-Ir.sub.2(L75) 8 B-3 10 E-26 A-2 30 B-1 27 C-1 20 I1-Ir.sub.2(L75) 8 B-4 15

TABLE-US-00032 TABLE 5 Structure of the OLED components investigated HIL HTL EML HBL ETL Ex. (thickness) (thickness) thickness (thickness) (thickness) V1 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) V2 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) V3 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-1 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-2 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-3 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-4 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-5 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-6 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-7 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (80 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-8 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-9 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) V4 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (70 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) V5 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (70 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-10 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (70 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-11 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (70 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-12 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (70 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-13 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (70 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-14 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (70 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-15 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (70 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-16 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (70 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-17 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-18 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-19 PEDOT HTL1 60 nm ETM-1 ETM-1(50%): (70 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-20 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-21 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-22 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-23 PEDOT HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-24 PEDOT HTL2 60 nm ETM-3 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-25 PEDOT HTL2 60 nm ETM-3 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (60 nm) E-26 PEDOT HTL2 60 nm ETM-3 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm)

TABLE-US-00033 TABLE 6 Results of solution-processed OLEDs (measured at a bright- ness of 1000 cd/m.sup.2) EQE LT90 Ex. [%] CIE x CIE y @60 mA/cm.sup.2 V1 16.2 0.66 0.34 276 V2 15.7 0.67 0.33 123 V3 18.2 0.64 0.36 298 E-1 20.0 0.65 0.35 359 E-2 19.9 0.66 0.34 317 E-3 18.6 0.66 0.34 315 E-4 18.6 0.64 0.35 304 E-5 20.1 0.63 0.37 277 E-6 19.8 0.68 0.32 221 E-7 18.7 0.68 0.32 298 E-8 19.7 0.63 0.37 248 E-9 18.4 0.67 0.33 199 V4 15.0 0.68 0.33 70 V5 8.6 0.65 0.35 34 E-10 19.1 0.67 0.33 171 E-11 18.9 0.67 0.33 165 E-12 18.8 0.67 0.33 154 E-13 16.7 0.65 0.35 93 E-14 18.5 0.55 0.45 137 E-15 19.4 0.65 0.35 133 E-16 18.8 0.68 0.32 85 E-17 19.8 0.65 0.35 348 E18 10.2 0.71 0.28 112 E-19 14.8 0.55 0.44 84 E-20 18.2 0.68 0.32 16 E-21 18.0 0.70 0.31 92 E-22 13.3 0.65 0.35 111 E-23 21.6 0.68 0.32 569 E-24 24.6 0.68 0.32 493 E-25 23.6 0.68 0.32 93 E-26 23.8 0.68 0.32 236

[0339] All compounds P1 to P234 shown above and the deuterated compounds shown above can be employed analogously and lead to comparable results.

[0340] As an alternative to production by means of spin coating, the solution-processed layers can also be produced, inter alia, by means of ink-jet printing. In the examples discussed below, layers applied on a solution basis and layers applied on a vacuum basis are again combined within an OLED, so that the processing up to and including the emission layer is carried out from solution and the processing in the subsequent layers (hole-blocking layer and electron-transport layer) is carried out from vacuum. The general structure is furthermore as follows: substrate/ITO (50 nm)/hole-injection layer (HIL)/hole-transport layer (HTL)/emission layer (EML)/hole-blocking layer (HBL)/electron-transport layer (ETL)/cathode (aluminium, 100 nm). The substrate used is glass plates which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm and pixelated bank material.

[0341] The hole-injection layer is printed onto the substrate, dried in vacuo and subsequently heated at 180 C. in air for 30 minutes. The hole-transport layer is printed onto the hole-injection layer, dried in vacuo and subsequently heated at 230 C. in a glove box for 30 minutes. The emission layer is subsequently printed, dried in vacuo and heated at 160 C. in a glove box for 10 minutes. All printing steps are carried out in air under yellow light. The hole-injection material used is a composition comprising a polymer (for example polymer P2) and a salt (for example salt D1) in accordance with PCT/EP2015/002476. It is dissolved in 3-phenoxytoluene and diethylene glycol butyl methyl ether in the ratio 7:3. The hole-transport material is processed from the same solvent mixture. The emission layer is printed from pure 3-phenoxytoluene.

[0342] The EML mixtures and structures of the OLED components investigated are shown in Table 7 and Table 8. The associated results can be found in Table 9. Good pixel homogeneities are achieved.

TABLE-US-00034 TABLE 7 EML mixtures of the OLED components investigated Matrix A Co-matrix B Co-dopant C Dopant D Further co-matrix B Ex. Material % Material % Material % Material % Material % E-28 A-2 30 B-1 47 C-1 17 I1-Ir2(L1) 6 E-29 A-2 40 B-1 40 I1-Ir2(L1) 20 E-30 A-2 30 B-1 40 C-1 22 I1-Ir.sub.2(L75) 8

TABLE-US-00035 TABLE 8 Structure of the OLED components investigated HIL HTL EML HBL ETL Ex. (thickness) (thickness) thickness (thickness) (thickness) E-28 HIL HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-29 HIL HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm) E-30 HIL HTL2 60 nm ETM-1 ETM-1(50%): (60 nm) (20 nm) (10 nm) ETM-2(50%) (40 nm)

TABLE-US-00036 TABLE 9 Results of solution-processed OLEDs (measured at a brightness of 1000 cd/m.sup.2) EQE LT90 Ex. [%] CIE x CIE y @60 mA/cm.sup.2 E-28 21.0 0.66 0.34 503 E-29 19.4 0.67 0.33 64 E-30 20.8 0.68 0.32 156

DESCRIPTION OF THE FIGURES

[0343] FIG. 1: Single-crystal structure of compound I2-Ir.sub.2(L1) (ORTEP representation with 50% probability level)

[0344] a) Side view of the ligand bridging the iridium centres.

[0345] b) Top view of the ligand bridging the iridium centres.

[0346] For better clarity, the hydrogen atoms are not shown.

[0347] FIG. 2: Single-crystal structure of compound Ir.sub.2100 (ORTEP representation with 50% probability level)

[0348] a) Side view of the ligand bridging the iridium centres.

[0349] b) Top view of the ligand bridging the iridium centres.

[0350] For better clarity, the hydrogen atoms are not shown.

[0351] FIG. 3: Single-crystal structure of compound I1-Ir.sub.2(L75) (ORTEP representation with 50% probability level)

[0352] a) Side view of the ligand bridging the iridium centres.

[0353] b) Top view of the ligand bridging the iridium centres.

[0354] For better clarity, the hydrogen atoms are not shown.