Metal complexes

Abstract

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

Claims

1. A monometallic compound comprising a hexadentate tripodal ligand wherein three bidentate part-ligands, which may be identical or different, are coordinated to a metal selected from the group consisting of ruthenium, osmium, rhodium and iridium, and the three bidentate part-ligands are linked to one another via a bridge of formula (1): ##STR00513## wherein the dashed bonds are the direct bonds from the bidentate part-ligands to the structure of formula (1); X.sup.1 is on each occurrence, identically or differently, CR.sub.2 or O; X.sup.2 is on each occurrence, identically or differently, CR, P═O, B, or Si, which is optionally substituted, with the proviso that, when X.sup.2 is P═O, B, or Si, which is optionally substituted, X.sup.1 is O; and wherein substituents optionally present on X.sup.1 and X.sup.2 optionally define an aliphatic or heteroaliphatic ring system with themselves or with one another; X.sup.3 is on each occurrence, identically or differently, —CR═CR—, —CR═N—, —CR—NR″—, —C(═O)—O—, —C(═O)—NR″—, —C(═O)—S—, —C(═S)—O—, —C(═S)—S—; 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, 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 in each case is optionally substituted by one or more radicals R.sup.1, wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C═C, Si(R.sup.1).sub.2, C═O, 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 or more radicals R which are bonded to X.sup.1 and/or X.sup.2 optionally define an aliphatic or heteroaliphatic ring system with one another; and wherein two radicals R when X.sup.3 is —CR═CR— optionally define an aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system with one another; and wherein radicals R and R″ when X.sup.3 is —CR—NR″— define a heteroaromatic 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 or an alkenyl group having 2 to 20 C atoms, wherein the alkyl or alkenyl group in each case is 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 in each case is optionally substituted by one or more radicals R′; 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, 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 in each case is optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2, 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.2; wherein a plurality of substituents R.sup.1 optionally define an aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system with one another; furthermore, the groups R or R substituted with R.sup.1 optionally form a ring system, and groups R and R.sup.1 optionally form a ring system with one another; R.sup.2 is on each occurrence, identically or differently, H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by F; and wherein the bidentate part-ligands are selected, identically or differently on each occurrence, from the group consisting of structures of formulae (L-1), (L-2), (L-3), and (L-4): ##STR00514## wherein the dashed bond is the direct bond from the part-ligand to the bridge of formula (1); CyC is, identically or differently on each occurrence, an optionally substituted aryl or heteroaryl group having 5 to 14 aromatic ring atoms, which is coordinated to the metal via a carbon atom and which is connected to CyD via a covalent bond; CyD is, identically or differently on each occurrence, an optionally substituted heteroaryl group having 5 to 14 aromatic ring atoms, which is coordinated to the metal via a nitrogen atom or via a carbene carbon atom and which is connected to CyC via a covalent bond; and wherein a plurality of the optional substituents optionally defines a ring system with one another; and the three bidentate ligands are optionally cyclised by a further bridge, in addition to the bridge of formula (1), to define a cryptate.

2. The monometallic compound of claim 1, wherein the bridge of formula (1) is selected from the group consisting of structures of formulae (2) through (6): ##STR00515## wherein 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′, SR′, COOH, C(═O)N(R.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, 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, where the alkyl, alkenyl, or alkynyl group in each case is optionally substituted by one or more radicals R′, wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, C═O, 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 are optionally substituted by one or more radicals R.sup.1.

3. The monometallic compound of claim 1, wherein the bridge of formula (1) is selected from the structures of the formulae (2a) and (2b) ##STR00516##

4. The monometallic compound of claim 1, wherein the bidentate part-ligands are each monoanionic and wherein the three bidentate part-ligands are either selected identically or two bidentate part-ligands are selected identically and the third bidentate part-ligand is selected differently from the first two bidentate part-ligands and wherein the coordinating atoms of the bidentate part-ligands are selected, identically or differently on each occurrence, from C, and/or N.

5. The monometallic compound of claim 1, wherein the metal is Ir(III) and two of the bidentate part-ligands are coordinated to the iridium in each case via one carbon atom and one nitrogen atom or via two carbon atoms and the third of the bidentate part-ligands is coordinated to the iridium via one carbon atom and one nitrogen atom or via two carbon atoms or via two nitrogen atoms.

6. The monometallic compound of claim 1 wherein CyC is selected from the group consisting of structures of formulae (CyC-1) through (CyC-20): ##STR00517## ##STR00518## ##STR00519## wherein the group is in each case bonded to CyD in (L-1) or (L-2) or to CyC in (L-4) at the position denoted by # and is coordinated to the metal at the position denoted by *; and CyD is selected from the group consisting of structures of formulae (CyD-1) through (CyD-14): ##STR00520## ##STR00521## wherein the group is in each case bonded to CyC in (L-1) or (L-2) or to CyD in (L-3) at the position denoted by # and is coordinated to the metal at the position denoted by *; and wherein 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, 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 in each case is optionally substituted by one or more radicals R.sup.1, wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.1C=CR.sup.1, C═C, Si(R.sup.1).sub.2, C═O, 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 or more radicals R which are bonded to X.sup.1 and/or X.sup.2 optionally define an aliphatic or heteroaliphatic ring system with one another; and wherein two radicals R when X.sup.3 is —CR═CR— optionally define an aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system with one another; and wherein radicals R and R″ when X.sup.3 is —CR—NR″— define a heteroaromatic ring system with one another; and wherein two radicals R optionally define an aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system with one another: X is on each occurrence, identically or differently, CR or N, with the proviso that a maximum of two X per ring are N; W is on each occurrence, identically or differently, NR, O, or S; and wherein the bonding of these groups to the bridge of formula (1) is via the position denoted by “o” and the corresponding X is C.

7. The monometallic compound of claim 1, wherein the bidentate part-ligands are selected from the group consisting of structure of formulae (L-1-1), (L-1-2), (L-2-1), (L-2-2), (L-2-3), and (L-5) through (L-34): ##STR00522## ##STR00523## ##STR00524## ##STR00525## ##STR00526## ##STR00527##

8. The monometallic compound of claim 1, wherein the monometallic compound comprises two substituents R, which are bonded to adjacent carbon atoms and which define a ring of one of formulae (43) through (49) with one another: ##STR00528## wherein the dashed bonds indicate the linking of the two carbon atoms in the ligand; A.sup.1 and A.sup.3 are, identically or differently on each occurrence, C(R.sup.3).sub.2, O, S, NR.sup.3, or C(=0); A.sup.2 is C(R.sup.1).sub.2, 0, S, NR.sup.3, or C(═O); G is an alkylene group having 1, 2, or 3 C atoms, which is optionally substituted by one or more radicals R.sup.2, or is —CR.sup.2═CR.sup.2— or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2; R.sup.3 is, identically or differently on each occurrence, H, D, F, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, wherein the alkyl or alkoxy group in each case is optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.2C═CR.sup.2, C═C, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 24 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2; and wherein two radicals R.sup.3 bonded to the same carbon atom optionally define an aliphatic or aromatic ring system with one another to form a spiro system; and wherein R.sup.3 optionally defines an aliphatic ring system with an adjacent radical R or R.sup.1, with the proviso that no two heteroatoms are bonded directly to one another and no two groups C═O are bonded directly to one another in these groups.

9. A process for preparing the monometallic compound of claim 1, comprising reacting a free ligand with a metal alkoxides of formula (50), a metal ketoketonate of formula (51), a metal halide of formula (52), or a metal carboxylate of formula (53), or with a metal compound which carries both alkoxide and/or halide and/or hydroxyl and also ketoketonate radicals: ##STR00529## wherein M is the metal of the monometallic compound being prepared; n is the valency of the metal M; and Hal is F, Cl, Br, or I; and wherein the metal starting materials are optionally in the form of a corresponding hydrate.

10. An oligomer, polymer, or dendrimer comprising one or more monometallic compounds of claim 1, wherein one or more bonds from the monometallic compound to the polymer, oligomer, or dendrimer are present instead of one or more hydrogen atoms and/or substituents.

11. A formulation comprising at least one monometallic compound of claim 1 and at least one solvent.

12. A formulation comprising at least one oligomer, polymer, or dendrimer of claim 10 and at least one solvent.

13. An electronic device comprising at least one monometallic compound of claim 1.

14. An electronic device comprising at least one oligomer, polymer, or dendrimer of claim 10.

15. The electronic device of claim 13, wherein the electronic device is an organic electroluminescent device and the at least one monometallic compound is employed as an emitting compound in one or more emitting layers or as a hole-blocking material in a hole blocking layer or as an electron-transport material in an electron-transport layer.

Description

EXAMPLES

(1) 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. Ligands containing imine units are depicted pictorially below with respect to their conformation at the imine bond as they are present in the metal complex, irrespective of whether they are obtained from the synthesis as the cis form, trans form or as a mixture.

(2) 1. Preparation of the Organic Synthones:

Example S1

(3) ##STR00072##

(4) Preparation in accordance with G. Markopoulos et al., Angew. Chem., Int. Ed., 2012, 51, 12884.

(5) ##STR00073##

(6) 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 sat. sodium chloride solution each time and dried over magnesium sulfate.

(7) 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.

(8) ##STR00074##

(9) 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 sat. 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.

(10) ##STR00075##

(11) 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 sat. 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.

(12) ##STR00076##

(13) 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.

(14) The following compounds can be prepared analogously.

(15) TABLE-US-00002 Starting materials Yield Ex. if different from S1 Product a) to e) S2 21% S3 0 19% S4 14%

Example S5

(16) ##STR00083##

(17) 801 mg (10 mmol) of nanoscale zinc oxide are added to a vigourously stirred melt, held at a temperature of 40° C., of 18.5 g (100 mmol) of 2-bromobenzaldehyde. After 16 h, 100 ml of toluene are added to the reaction mixture, the zinc oxide is filtered off through Celite, all the toluene is removed in vacuo, and the wax obtained in this way is recrystallised from acetone. Yield: 6.3 g (34 mmol), 34%. Purity: about 95% according to .sup.1H-NMR, cis,cis isomer.

Example S6

(18) ##STR00084##

(19) A mixture of 22.6 g (100 mmol) of (6-methoxy-[1,1′-biphenyl]-3-yl)boronic acid [459423-16-6], 16.6 g (105 mmol) of 2-bromopyridine [109-04-6], 21.2 g (200 mmol) of sodium carbonate, 1.2 g (1 mmol) of tetrakis(triphenylphosphino)palladium [14221-01-3], 300 ml of toluene, 100 mol of ethanol and 300 ml of water is heated under reflux with vigourous stirring for 18 h. After cooling, the org. phase is separated off, washed twice with 300 ml of water each time and once with 300 ml of sat. NaCl solution and dried over magnesium sulfate. The oil obtained after evaporation of the org. phase is dried at 80° C. under an oil-pump vacuum and reacted without further purification. Yield: 25.6 g (98 mmol), 98%; purity: about 95% according to .sup.1H-NMR.

(20) ##STR00085##

(21) A mixture of 26.1 g (100 mmol) of 5-(2-pyridyl)-[1,1′-biphenyl]-2-ol S6a and 81.9 g (700 mmol) of pyridinium hydrochloride are heated at 190° C. for 3 h. After cooling, the reaction mixture is poured into 500 ml of water, extracted five times with 200 ml of dichloromethane each time, the org. phase is washed twice with 200 ml of water and once with 200 ml of sat. NaCl solution, the solvent is removed in vacuo, 300 ml of toluene are added for azeotropic drying, and all of the latter is removed by distillation in vacuo. The viscous oil obtained in this way is reacted without further purification. Yield: 21.0 g (85 mmol) 85%; purity: about 95% according to .sup.1H-NMR.

(22) c) S6

(23) 34 ml (200 mmol) of trifluoromethanesulfonic anhydride [358-23-6] are added dropwise to a solution, cooled to 0° C., of 24.7 g (100 mmol) of S6b in a mixture of 300 ml of dichloromethane and 80 ml of pyridine with vigourous stirring. The reaction mixture is allowed to warm to RT, stirred for a further 16 h, poured into 1000 ml of ice-water with stirring and the latter is then extracted three times with 300 ml of dichloromethane. The combined org. phases are washed twice with 300 ml of ice-water each time and once with 500 ml of sat. NaCl solution and then dried over sodium sulfate. The wax remaining after removal of the dichloromethane in vacuo is recrystallised from acetonitrile. Yield: 32.6 g (86 mmol), 86%; purity: about 95% according to .sup.1H-NMR.

(24) S7 can be obtained analogously, replacing 2-bromopyridine with 2-bromo-4-tert-butylpyridine [50488-34-1]:

(25) ##STR00086##

Example S10: 5-Bromo-2-[1,1,2,2,3,3-hexamethylindan-5-yl]pyridine

(26) ##STR00087##

(27) 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 with vigourous stirring for 16 h. 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.

(28) The following compound can be prepared analogously:

(29) TABLE-US-00003 Boronic acid/ester Ex. Pyridine Product Yield S11 73%

Example S20

(30) ##STR00090##

(31) 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 sat. sodium chloride solution, dried over magnesium sulfate, filtered 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 S21

(32) ##STR00091##

(33) A mixture of 28.3 g (100 mmol) of S20, 12.8 g (105 mmol) of phenylboronic acid, 31.8 g (300 mmol) of sodium carbonate, 787 mg (3 mmol) of triphenylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 300 ml of toluene, 150 ml of ethanol and 300 ml of water is heated under reflux for 48 h. After cooling, the mixture is extended with 300 ml of toluene, die org. phase is separated off, washed once with 300 ml of water, once with 200 ml of sat. 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.

(34) The following compounds can be synthesised analogously:

(35) TABLE-US-00004 Ex. Boronic ester Product Yield S22 56% S23 61% S24 70%

Example S30: 2-[1,1,2,2,3,3-Hexamethylindan-5-yl]-5-(4,4,5,5-tetra-methyl-1,3,2-dioxaborolan-2-yl)pyridine

(36) Variant A:

(37) ##STR00099##

(38) A mixture of 35.8 g (100 mmol) of S10, 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 DCM [95464-05-4], 200 g of glass beads (diameter 3 mm), 700 ml of 1,4-dioxane and 700 ml of toluene is heated under reflux for 16 h. After cooling, the suspension is filtered through a Celite bed, and the solvent is removed in vacuo. The black residue is digested with 1000 ml of hot cyclohexane, filtered through a Celite bed while still hot, then evaporated to about 200 ml, during which the product begins to crystallise. The crystallisation is completed overnight in the refrigerator, and the crystals are filtered off and washed with a little n-heptane. A second product fraction can be obtained from the mother liquor. Yield: 31.6 g (78 mmol), 78%. Purity: about 95% according to .sup.1H-NMR.

(39) Variant B: Reaction of Aryl Chlorides

(40) As for variant A, but replacing 1,1-bis(diphenylphosphino)ferrocenepalladium(II) dichloride complex with DCM with 1.5 mmol of S-Phos [657408-07-6] and 1.0 mmol of palladium(II) acetate.

(41) The following compounds can be prepared analogously, where cyclohexane, toluene, acetonitrile, ethyl acetate or mixtures of the said solvents can also be used instead of n-heptane for the purification:

(42) TABLE-US-00005 Bromide/triflate - Variant A Ex. Chloride - Variant B Product Yield S31 00 01 88% S32 02 03 70% S33 04 05 86% S34 06 07 79% S35 08 09 77% S36 0 64% S37 69% S38 74% S39 83% S40 80% S41 0 36% S42 48% S43 46%

Example S100

(43) ##STR00126##

(44) A mixture of 54.5 g (100 mmol) of S1, 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 org. 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 through 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.

(45) The following compounds can be prepared analogously:

(46) TABLE-US-00006 Starting Ex. materials Product Yield S101 S1  S31 68% S102 S3  S31 60% S103 S3  S32 60% S104 S3  S33 0 69% S105 S3  S34 64% S106 S4  S35 61% S107 S3  S36 63% S108 S3  S37 60% S109 S3  S38 66%

Example S200

(47) ##STR00136##

(48) A mixture of 29.0 g (100 mmol) of S31, 20.2 g (200 mmol) of pivaloyl-amide, 97.8 g (300 mmol) of caesium carbonate, 1157 mg (2 mmol) of Xanthphos, 449 mg (2 mmol) of palladium(II) acetate, 500 ml of dioxane and 200 g of glass beads (diameter 3 mm) is stirred at 100° C. for 12 h. The dioxane is substantially removed in vacuo, the residue is taken up in 500 ml of water and 500 ml of ethyl acetate, the org. phase is washed twice with 300 ml of water and once with 300 ml of sat. sodium chloride solution and then dried over magnesium sulfate. The drying agent is filtered off through a Celite bed which has been pre-slurried with ethyl acetate, and the filtrate is evaporated to dryness. The oily residue is taken up in 200 ml of dioxane, 50 ml conc. HCl are added, and the solution is boiled under reflux for 12 h, the dioxane is then substantially distilled off, during which the product crystallises out. The product is filtered off with suction, washed with ice-cold water and dried in vacuo. Yield: 19.0 g (63 mmol), 63%. Purity: about 95% according to .sup.1H-NMR.

(49) The following compounds can be prepared analogously:

(50) TABLE-US-00007 Starting Ex. material Product Yield S201 S33 66% S202 S37 60% S203 S38 60% S204 S39 0 67%

Example S300

(51) ##STR00141##

(52) A mixture of 24.9 g (100 mmol) of 2-(4-aminophenyl)-5-bromopyridine [1264652-77-8], 26.7 g (105 mmol) of bis(pinacolato)diborane [73183-34-3], 29.5 g (300 mmol) of potassium acetate, anhydrous, 561 mg (2 mmol) of tricyclohexylphosphine, 224 mg (1 mmol) of palladium(II) acetate and 500 ml of dioxane is stirred at 90° C. for 16 h. After removal of the solvent in vacuo, the residue is taken up in 500 ml of ethyl acetate, filtered through a Celite bed, the filtrate is evaporated in vacuo to incipient crystallisation, and finally about 100 ml of methanol are added dropwise in order to complete the crystallisation. Yield: 20.1 g (68 mmol), 68%; purity: about 95% according to .sup.1H-NMR.

(53) The following compounds can be synthesised analogously:

(54) TABLE-US-00008 Ex. Starting material Product Yield S301 63% S302 58%
2. Preparation of Hexadentate Ligands L:

Example L1

(55) ##STR00146##

(56) A mixture of 50.5 g (100 mmol) of S1, 98.4 g (350 mmol) of 2-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine [879291-27-7], 106.0 g (1 mol) of sodium carbonate, 2.1 g (5 mmol) of S-Phos [657408-07-6], 674 mg (3 mmol) of palladium(II) acetate, 750 ml of toluene, 200 ml of dioxane and 500 ml of water is heated at 70° C. with very vigourous stirring for 24 h. The mixture is allowed to cool, the aqueous phase is separated off, and the organic phase is evaporated to dryness. After evaporation of the organic phase from the Suzuki coupling, the brown foam is taken up in 300 ml of dichloromethane:ethyl acetate (1:1, vv) and filtered through a silica-gel bed (diameter 15 cm, length 20 cm) which has been pre-slurried with dichloromethane:ethyl acetate (1:1, vv) in order to remove brown components. After evaporation, the foam which remains is recrystallised from 300 ml of ethyl acetate with addition of 300 ml of boiling methanol and then recrystallised a second time from 250 ml of pure ethyl acetate and subsequently sublimed in a bulb tube in a high vacuum (p about 10.sup.−5 mbar, T 260° C.). Yield: 45.6 g (59 mmol), 59%. Purity: about 99.7% according to .sup.1H-NMR, cis,cis isomer.

(57) The following compounds can be prepared analogously, where the purification can also be carried out by chromatography (e.g. Torrent CombiFlash from Axel Semrau):

(58) TABLE-US-00009 Bromide Boronic Ex. ester Product Yield L2 S3 S30 59% L3 S2 S31 65% L4 S4 S32 60% L5 S3 S33 0 63% L6 S3 S37 58% L7 S3 S38 57% L8 S3 1383803- 71-1 60% L9 S1 1310383- 27-7 55% L10 S3 1146340- 38-6 62% L11 S3 1228267- 13-7 65% L12 S3 S40 67% L13 S3 1312478- 63-9 58% L14 S3 S39 61% L15 S5 S31 0 49% L16 S1 [562098- 24-2] 38% L17 S1 S41 33% L18 S2 S42 41% L19 S3 S43 45% L20 S3 [913836- 11-0] 29%

Example L100

(59) ##STR00166##

(60) A mixture of 65.3 g (100 mmol) of S100, 42.5 g (105 mmol) of S30, 63.7 g (300 mmol) of tripotassium phosphate, 1.23 g (3 mmol) of S-Phos [657408-07-6], 449 mg (2 mmol) of palladium(II) acetate, 500 ml of toluene, 300 ml of dioxane and 300 ml of water is heated under reflux for 6 h.

(61) After cooling, the org. phase is separated off, washed twice with 300 ml of water and once with 200 ml of sat. sodium chloride solution, dried over magnesium sulfate and then filtered through a Celite bed which has been pre-slurried with toluene, and the bed is rinsed with toluene. The filtrate is evaporated to dryness, and the residue is subsequently recrystallised twice from ethyl acetate/methanol. Yield: 56.5 g (63 mmol), 63%. Purity: about 97% according to .sup.1H-NMR.

(62) The following compounds can be synthesised analogously:

(63) TABLE-US-00010 Boronic ester Ex. Bromide Product Yield L101 S100 S32 60% L102 S101 S31 83% L103 S101 S33 66% L104 S101 S34 0 63% L105 S101 S35 60% L106 S101 S36 67% L107 S101 S37 58% L108 S101 S38 70% L109 S102 S33 63% L110 S104 S31 65% L111 S105 S31 68% L112 S106 S31 62% L113 S107 S31 54% L114 S108 S31 0 57% L115 S109 S31 69% L116 S103 S30 70% L117 S101 1383803- 71-1 60% L118 S101 1848992- 66-4 70% L119 S101 1310383- 27-7 65% L120 S102 1146340- 38-6 71% L121 S102 1228267- 13-7 73% L122 S101 S40 67% L123 S101 1312478- 63-9 60% L124 S101 S39 0 65%

Example L200

(64) ##STR00191##
Variant A, for Aldehydes:

(65) Procedure analogous to J. G. Muntaner et al., Org. & Biomol. Chem., 2014, 12, 286. 97 ml of a 2 N sodium ethoxide solution in ethanol are added to a solution of 24.3 g (100 mmol) of 4-(2-pyridyl)anilinium dihydrochloride [856849-12-2] in 200 ml of ethanol. 5.1 g (30 mmol) of cis,cis-1,3,5-cyclohexanetricarboxaldehyde [107354-37-0] is then added, and the mixture is heated under reflux for 3 h. The ethanol is subsequently distilled off virtually to dryness, the oily residue is taken up in 300 ml of DCM, insoluble components are filtered off through a Celite bed which has been pre-slurried with DCM, the DCM is removed in vacuo, and the crude product is recrystallised from acetonitrile/cyclohexane. Yield: 14.4 g (23 mmol), 69%. Purity: about 97% according to .sup.1H-NMR.

Example L201

(66) ##STR00192##
Variant B, for Ketones:

(67) Procedure analogous to P. Sulmon et al., Synthesis 1985, 192. Three drops of methanol and then, in portions, 8.0 g (200 mmol) of sodium hydride, 60% by weight dispersion in mineral oil, are added to a suspension of 24.3 g (100 mmol) of 4-(2-pyridyl)anilinium dihydrochloride in 200 ml of diethyl ether (care: evolution of hydrogen!). After 3 h at room temperature, the evolution hydrogen is complete. 10.1 g (30 mmol) of cis,cis-1,1′,1″-(1,3,5-cyclohexanetriyl)tris[2,2-dimethyl-1-propanone][98013-15-1] are added, and the reaction mixture is cooled to 0° C. in an ice/salt bath. 95 ml of 1 N titanium tetrachloride solution in DCM are then added dropwise, the mixture is allowed to warm to room temperature and is then heated under reflux for 18 h. After cooling, the solid which has precipitated out is filtered off with suction, rinsed three times with 100 ml of DCM, the filtrate is evaporated to dryness, the oily residue is taken up in 300 ml of DCM, washed three times with 100 ml of 2 N aqueous KOH solution each time and then dried over magnesium sulfate. The DCM is removed in vacuo, and the residue is chromatographed on silica gel (deactivated using triethylamine) with cyclohexane:ethyl acetate:triethylamine (90:9:1, vv). Yield: 5.6 g (7 mmol), 23%. Purity: about 97% according to .sup.1H-NMR.

(68) The following compounds can be synthesised analogously:

(69) TABLE-US-00011 Carbonyl component Product Ex. Amine Variant Yield L202 187805-79-4 S200 54% L203 187805-79-4 S201 57% L204 107354-37-0 S202 69% L205 98013-04-8 S203 38% L206 98013-15-1 S204 25% L207 187805-79-4 1246767-56-5 54% L208 187805-79-4 52090-60-5 49% L209 98013-15-1 66728-99-2 00 27% L210 98013-15-1 1110656-27-3 01 24% L211 107354-37-0 1357165-91-3 02 71%

Example L300

(70) ##STR00203##

(71) A mixture of 3.9 g (30 mmol) of cis,cis-1,3,5-triaminocyclohexane [26150-46-9], 18.3 g (100 mmol) of 4-(2-pyridinyl)benzaldehyde [127406-56-8], 951 mg (5 mmol) of 4-toluenesulfonic acid monohydrate [6192-52-5] and 300 ml of mesitylene is heated under reflux until the separation of water is complete. After cooling, the mesitylene is removed in vacuo, and the residue is chromatographed on silica gel (deactivated using triethylamine) with cyclohexane:ethyl acetate:triethylamine (90:9:1, vv). Yield: 15.0 g (24 mmol), 88%. Purity: about 97% according to .sup.1H-NMR.

(72) The following compounds can be synthesised analogously:

(73) TABLE-US-00012 Carbonyl component Product Ex. Amine Variant Yield L301 52199-29-8 478978-03-9 04 64% L302 221910-24-3 478978-03-9 05 60% L303 1138735-13-3 478978-03-9 06 58% L304 1107640-93-6 582312-14-9 07 53% L305 1094356-84-9 478978-03-9 08 55% L306 1401797-64-5 582312-14-9 09 57% L307 64869-17-6 582312-14-9 0 47% L308 30091-51-1 478978-03-9 59% L309 1252578-97-4 478978-03-9 56%

Example L400

(74) ##STR00213##

(75) 28 ml of triethylamine and then, dropwise, a solution of 21.8 g [100 mmol) of 4-(2-pyridinyl)benzoyl chloride [190850-37-4] in 100 ml of dichloromethane are added to a vigourously stirred solution of 4.0 g (30 mmol) of cis,cis-1,3,5-cyclohexanetriol [50409-12-6] in 100 ml of dichloromethane, and the mixture is stirred under reflux for 12 h. After cooling, the volatile constituents are removed in vacuo, the residue is washed by stirring with 300 ml of hot methanol, the product is filtered off with suction, washed three times with 50 ml of methanol each time and finally recrystallised from ethyl acetate/methanol. Yield: 14.0 g (21 mmol), 69%. Purity: about 97% according to .sup.1H-NMR.

(76) The following compounds can be prepared analogously, where the purification of the crude products can be carried out by bulb-tube distillation, recrystallisation or chromatography. If a mixture of alcohols, amines or acid chlorides is employed, ligands containing different bidentate part-ligands can also be obtained in addition to the symmetrical ligands by chromatographic separation (CombiFlash Torrent, Axel Semrau GmbH&Co KG).

(77) TABLE-US-00013 Ex. Starting material Product Yield L401 75% L402   68% L403 0 70% L404   69% L405 68% L406 70% L407 77% L408 0 73% L409 71% L410 73% L411 64% L412 69% L413 0 66% L414 64% L415 65% L416 68% L417 66% L418 0 69% L419 68% L420 70% L421 59% L422 63% L423 0 70% L424 65% L425 67% L426 68% L427 65% L428 0 71% L429 53% L430 68% L431 69% L432 70% L433 0 58% L434 68% L435 69% L436 67% L437 65% L438 0 73% L439 79% L440 73% L441 70% L442 74% L443 00 01 69% L444 02 03 72% L445 04 05 74% L446 06 07 71% L447 08 09 72% L448 0 70% L449 69% L450 65% L451 71% L452 67% L453 0 70% L454 67% L455 74% L456 19% L457 16% L458 0 28% L459 33% L460 147365-19-3 1255636-82-8 70%

Example L500

(78) ##STR00335##

(79) 1.2 g (50 mmol) of sodium hydride are added in portions to a suspension of 6.7 g (10 mmol) of L402 in 150 ml of dimethylacetamide, and the mixture is stirred at room temperature for 30 min. 2.1 ml (33 mmol) of methyl iodide [74-88-4] are then added, and the mixture is warmed at 60° C. for 16 h. 20 ml of conc. ammonia solution are added dropwise, the mixture is stirred for a further 30 min., the solvent is substantially removed 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 sat. 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: 5.0 g (7.0 mmol), 70%. Purity: about 97% according to .sup.1H-NMR.

(80) The following compounds can be prepared analogously, where methyl iodide is replaced by the electrophiles indicated. In the case of the use of secondary alkyl halides, 60 mmol of NaH and 60 mmol of the secondary alkylating agent are used. The crude products can be purified by bulb-tube distillation, recrystallisation or chromatography.

(81) TABLE-US-00014 Starting Ex. materials Product Yield L501 L403 74-88-4 72% L502 L406 74-88-4 76% L503 L407 74-88-4 71% L504 L409 74-88-4 68% L505 L411 865-50-9 0 66% L506 L438 71162-19-1 39% L507 L439 29394-58-9 59% L508 L440 75-03-6 70% L509 L441 15501-33-4 71% L510 L442 74-88-4 24424-99-5 73% L511 L443 24424-99-5 69% L512 L444 865-50-9 68% L513 L445 75-26-3 42% L514 L447 513-38-2 65% L515 L450 15501-33-4 0 63% L516 L451 620-05-3 70% L517 L453 15501-33-4 61% L518 L454 15501-33-4 68% L519 L455 74-88-4 61% L520 L456 75-77-4 41% L521 L457 15501-33-4 72% L522 L458 74-88-4 base Cs.sub.2CO.sub.3 solvent acetone 40%

Example L600

(82) ##STR00358##

(83) A mixture of 6.7 g (10 mmol) of L406, 4.5 ml (40 mmol) of iodobenzene [591-50-4], 12.7 g (60 mmol) of tripotassium phosphate, 292 mg (1.5 mmol) of copper (I) iodide, 553 mg (3 mmol) of 2,2,6,6-tetramethyl-3,5-heptanedione [1118-71-4], 50 g of glass beads (diameter 3 mm) and 150 ml o-xylene is heated at 130° C. for 24 h. After cooling, the solvent is removed in vacuo, the residue is taken up in 500 ml of dichloromethane, the salts are filtered off via a pre-slurried Celite bed, the filtrate is washed three times with 100 ml of 5% by weight ammonia solution and once with 100 ml of water and then dried over magnesium sulfate. The crude product obtained after removal of the solvent is recrystallised from ethyl acetate/methanol. Yield: 6.5 g (7.2 mmol), 72%. Purity: about 97% according to .sup.1H-NMR.

(84) The following compounds can be prepared analogously. The crude products an be purified by bulb-tube distillation, recrystallisation or chromatography.

(85) TABLE-US-00015 Starting Ex. materials Product Yield L601 L446 37055-53-1 51% L602 L448 20442-79-9 0 56% L603 L449 857784-97-5 33% L604 L452 1643766-87-3 61%

Example L700

(86) ##STR00363##

(87) A vigourously stirred mixture of 16.3 g (30 mmol) of 1,3,5-tris(2-bromo-phenyl)benzene [380626-56-2], 31.1 g (100 mmol) of 2-(4-methoxy-phenyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine [1374263-53-2], 42.5 g (200 mol) of tripotassium phosphate, 534 mg (1.3 mmol) of S-Phos [657408-07-6], 224 mg (1.0 mmol) of palladium(II) acetate, 300 ml of toluene, 100 ml of dioxane and 300 ml of water is heated under reflux for 16 h. After cooling, the aqueous phase is separated off, and the organic phase is evaporated to dryness. The brown foam is taken up in 300 ml of ethyl acetate and filtered through a silica-gel bed (diameter 15 cm, length 20 cm) which has been a pre-slurried with ethyl acetate, in order to remove brown components. After evaporation to 100 ml, 300 ml of methanol are added dropwise to the warm solution with very vigourous stirring, during which a beige solid crystallises out. The solid is filtered off with suction, washed twice with 100 ml of methanol each time and dried in vacuo. Yield: 20.5 g (24 mmol), 80%. Purity: about 95% according to .sup.1H-NMR.

(88) The following compounds can be prepared analogously.

(89) TABLE-US-00016 Starting Ex. materials Product Yield L701 S300 54% L702 S301 57% L703 S302 49%
3. Preparation of the Metal Complexes:

Example Ir(L1)

(90) ##STR00367##

(91) A mixture of 7.72 g (10 mmol) of ligand L1, 4.90 g (10 mmol) of tris(acetylacetonato)iridium(11l) [15635-87-7] and 100 g of hydroquinone [123-31-9] is initially introduced in a 500 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. The flask 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 then 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 250-260° C., measured at the Pt-100 temperature sensor, which dips into the molten, stirred reaction mixture, using a laboratory hotplate stirrer. During the next 1.5 h, the reaction mixture is held at 250-260° C., during which little condensate is distilled off and collects in the water separator. The reaction mixture is allowed to cool to 190° C., 50 ml of ethylene glycol are added dropwise, the mixture is allowed to cool to 70° C., and 250 ml of methanol are then added dropwise. After cooling, the beige suspension obtained in this way is filtered through a reverse frit, the beige solid is washed three times with 50 ml of methanol and then dried in vacuo. Crude yield: quantitative. The solid obtained in this way is dissolved in 1000 ml of dichloromethane and filtered through about 800 g 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 substantially evaporated in a rotary evaporator, with MeOH simultaneously being continuously added dropwise to crystallisation. The yellow product is filtered off with suction, washed with a little MeOH and dried in vacuo, then purified further by continuous hot extraction with DCM five times (initially introduced amount in each case about 150 ml, extraction thimble: standard cellulose Soxhlett thimbles from Whatman) with careful exclusion of air and light. Yield: 7.03 g (7.3 mmol), 73%. Purity: >99.9% according to HPLC.

(92) The following compounds can be prepared analogously:

(93) TABLE-US-00017 Product Reaction time* Reaction temperature* Ex. Ligand Extractant* Yield Rh(L1) L1 36% Ir(L2) L2 Ir(L2) 57% Acetonitrile Ir(L3) L3 54% Ir(L4) L4 Ir(L4) 59% Butyl acetate Ir(L5) L5 Ir(L5) 60% Toluene Ir(L6) L6 Ir(L6) 61% Toluene Ir(L7) L7 0 57% Ir(L8) L8 Ir(L8) 27% Toluene Ir(L9) L9 63% Ir(L10) L10 Ir(L10) 65% o-Xylene Ir(L11) L11 Ir(L11) 53% 265° C./2 h Ir(L12) L12 Ir(L12) 57% 265° C./2 h Ir(L13) L13 Ir(L13) 51% Toluene Ir(L14) L14 Ir(L14) 39% Toluene Ir(L15) L15 24% Ir(L100) L100 57% Ir(L101) L101 Ir(L101) 62% DCM Ir(L102) L102 Ir(L102) 65% DCM Ir(L103) L103 61% Ir(L104) L104 Ir(L104) 58% Ir(L105) L105 Ir(L105) 61% Ir(L106) L106 Ir(L106) 65% Ir(L107) L107 Ir(L107) 65% Ir(L108) L108 Ir(L108) 57% o-Xylene Ir(L109) L109 Ir(L109) 70% Ir(L110) L110 Ir(L110) 63% Ir(L111) L111 Ir(L111) 60% Ir(L112) L112 Ir(L112) 62% Ir(L113) L113 Ir(L113) 66% Ir(L114) L114 Ir(L114) 58% Ir(L115) L115 Ir(L115) 55% o-Xylene Ir(L116) L116 Ir(L116) 60% Ir(L117) L117 Ir(L117) 69% Ir(L118) L118 Ir(L118) 55% o-Xylene Ir(L119) L119 Ir(L119) Ir(L120) L120 Ir(L120) 61% Ir(L121) L121 Ir(L121) 54% DCM Ir(L122) L122 Ir(L122) 56% DCM Ir(L123) L123 Ir(L123) 70% Ir(L124) L124 Ir(L124) 67% Ir(L200) L200 23% Ir(L201) L201 34% Ir(L202) L202 Ir(L202) 37% Ir(L203) L203 Ir(L203) 35% Ir(L204) L204 Ir(L204) 28% Ir(L205) L205 Ir(L205) 40% Ir(L206) L206 29% Ir(L207) L207 Ir(L207) 33% Ir(L208) L208 Ir(L208) 36% Ir(L209) L209 Ir(L209) 29% Ir(L210) L210 Ir(L210) 32% Ir(L211) L211 Ir(L211) 39% Ir(L300) L300 27% Ir(L301) L301 Ir(L301) 35% Ir(L302) L302 Ir(L302) 14% Ir(L303) L303 Ir(L303) 28% Ir(L304) L304 Ir(L304) 38% Ir(L305) L305 Ir(L305) 35% Ir(L306) L306 38% Ir(L307) L307 Ir(L307) 24% 265° C./2 h Ir(L308) L308 Ir(L308) 33% Ir(L309) L309 Ir(L309) 31% Ir(L400) L400 0 33% Ir(L401) IrL401 Ir(L401) 29% Ir(L404) IrL404 31% Ir(L405) IrL405 Ir(L405) 30% Ir(L408) IrL408 Ir(L408) 28% Ir(L410) IrL410 Ir(L410) 23% Ir(L411) IrL411 13% Ir(L412) IrL412 Ir(L412) 35% Ir(L413) IrL413 Ir(L413) 34% Ir(L414) IrL414 Ir(L414) 24% Ir(L415) IrL415 Ir(L415) 29% Ir(L416) IrL416 Ir(L416) 21% Ir(L417) IrL417 Ir(L417) 33% Ir(L418) IrL418 Ir(L418) 24% Ir(L419) IrL419 Ir(L419) 30% Ir(L420) IrL420 Ir(L420) 24% Ir(L421) IrL421 Ir(L421) 19% Ir(L422) IrL422 Ir(L422) 23% Ir(L423) IrL423 Ir(L423) 25% 2.5 h Ir(L424) IrL424 Ir(L424) 29% Ir(L425) IrL425 Ir(L425) 18% Ir(L426) IrL426 Ir(L426) 23% Ir(L427) IrL427 Ir(L427) 31% Ir(L428) IrL428 Ir(L428) 36% Ir(L429) IrL429 Ir(L429) 22% Ir(L430) IrL430 Ir(L430) 21% Ir(L431) IrL431 Ir(L431) 31% Ir(L432) IrL432 Ir(L432) 33% Ir(L433) IrL433 Ir(L433) 23% Ir(L434) IrL434 Ir(L434) 24% 2.5 h Ir(L435) IrL435 Ir(L435) 30% Ir(L436) IrL436 Ir(L436) 21% Ir(L437) IrL437 Ir(L437) 19% Ir(L459) IrL459 Ir(L459) 17% Addition of 33 mmol of NaO-t-Bu 250° C. 2 h Toluene Ir(L460) IrL460 Ir(L460) 51% Ir(L500) L500 54% Ir(L501) L501 Ir(L501) 49% Ir(L502) L502 Ir(L502) 55% Ir(L503) L503 Ir(L503) 50% Ir(L504) L504 Ir(L504) 36% Ir(L505) L505 Ir(L505) 48% Ir(L506) L506 Ir(L506) 50% Ir(L507) L507 Ir(L507) 52% Ir(L508) L508 Ir(L508) 33% Ir(L509) L59 Ir(L509) 46% Ir(L510) L510 Ir(L510) 30% Ir(L511) L511 Ir(L511) 53% Ir(L512) L512 Ir(L512) 26% Ir(L513) L513 Ir(L513) 32% Ir(L514) L514 Ir(L514) 50% Ir(L515) L515 Ir(L515) 51% Ir(L516) L516 Ir(L516) 56% Ir(L517) L517 Ir(L517) 38% Ir(L518) L518 Ir(L518) 50% Ir(L519) L519 Ir(L519) 54% Ir(L520) L520 Ir(L520) 19% Ir(L521) L521 Ir(L521) 49% Ir(L522) L522 Ir(L522) 17% Ir(L600) L600 54% Ir(L601) L601 Ir(L601) 23% Ir(L602) L602 Ir(L602) 19% Ir(L603) L603 Ir(L603) 56% Ir(L700) L(700) 85% Ir(L701) L(701) Ir(L701) 56% as for Ir(L700) Ir(L702) L(702) Ir(L702) 49% as for Ir(L700) Ir(L703) L(703) Ir(L703) 46% as for Ir(L700) *Stated if different from general procedure
Metal Complexes of Ligand L16:

(94) ##STR00386##

(95) A solution, held at a temperature of 75° C., of 1 mmol of the corresponding metal salt in 15 ml of EtOH or EtOH/water (1:1 vv) is added dropwise to a solution of 769 mg (1 mmol) of L16 in 10 ml of DMSO at 75° C., and the mixture is stirred for a further 10 h. An anion exchange is optionally carried out with addition of 6 mmol of the corresponding salt (KPF.sub.6, (NH.sub.4)PF.sub.6, KBF.sub.4, etc.) in 10 ml of EtOH or EtOH/water (1:1, vv). After cooling, the microcrystalline precipitate is filtered off with suction, washed with cold MeOH and dried in vacuo. The purification can be carried out by recrystallisation from acetonitrile/methanol.

(96) The following compounds can be prepared analogously:

(97) TABLE-US-00018 Ligand Ex. Metal salt Product Yield M1 L16 [Fe(L16)](ClO.sub.4).sub.2 56% Fe(ClO.sub.4).sub.2 M2 L16 [Fe(L16)](ClO.sub.4).sub.3 64% Fe(ClO.sub.4).sub.3 M3 L16 [Ru(L16)](ClO.sub.4).sub.3 71% Ru(ClO.sub.4).sub.3 M4 L16 [Os(L16)](ClO.sub.4).sub.2 52% Os(ClO.sub.4).sub.2 M5 L16 [Co(L16)](ClO.sub.4).sub.3 43% Co(ClO.sub.4).sub.3 M6 L16 [Rh(L16)](PF.sub.6).sub.3 50% RhCl.sub.3 × H.sub.2O KPF.sub.6 M7 L16 [Ir(L16)](PF.sub.6).sub.3 55% IrCl.sub.3 × H.sub.2O KPF.sub.6 M8 L16 [Zn(L16)](PF.sub.6).sub.2 68% ZnCl.sub.2 KPF.sub.6

(98) Metal Complexes of Ligand L17:

(99) ##STR00387##

(100) A solution, held at a temperature of 75° C., of 1 mmol of the corresponding metal salt in 15 ml of EtOH or EtOH/water (1:1 vv) is added dropwise to a solution of 736 mg (1 mmol) of L17 and 643 mg (6 mmol) of 2,6-dimethylpyridine in 10 ml of DMSO at 75° C., and the mixture is stirred for a further 10 h. An anion exchange is optionally carried out with addition of 6 mmol of the corresponding salt (KPF.sub.6, (NH.sub.4)PF.sub.6, KBF.sub.4, etc.) in 10 ml of EtOH or EtOH/water (1:1, vv). After cooling, the microcrystalline precipitate is filtered off with suction, washed with cold MeOH and dried in vacuo. The purification can be carried out by recrystallisation from acetonitrile/methanol.

(101) The following compounds can be prepared analogously:

(102) TABLE-US-00019 Ligand Ex. Metal salt Product Yield M100 L17 Fe(L17) 70% FeBr.sub.3 hydrate M101 L17 NH.sub.4[Ru(L17)] 54% [Ru(NH.sub.3).sub.6]Cl.sub.2 No 2,6-dimethylpyridine M102 L17 Ru(L17) 66% RuCl.sub.3 hydrate M103 L17 Os(L17) 58% OsCl.sub.3 hydrate M104 L17 Rh(L17) 41% RhCl.sub.3 hydrate M105 L17 Ir(L17) 67% IrCl.sub.3 hydrate M106 L17 [Pt(L17)](PF.sub.6) 71% (NH.sub.4).sub.2[PtCl.sub.6] added as solid NH.sub.4PF.sub.6
Metal Complexes of Ligand L18:

(103) ##STR00388##

(104) A solution, held at a temperature of 75° C., of 1 mmol of the corresponding metal salt in 20 ml of EtOH or EtOH/water (1:1 vv) is added dropwise to a solution of 736 mg (1 mmol) of L18 and 643 mg (6 mmol) of 2,6-dimethylpyridine in 10 ml of DMSO at 75° C., and the mixture is stirred for a further 10 h. An anion exchange is optionally carried out with addition of 6 mmol of the corresponding salt (KPF.sub.6, (NH.sub.4)PF.sub.6, KBF.sub.4, etc.) in 10 ml of EtOH or EtOH/water (1:1, vv). After cooling, the microcrystalline precipitate is filtered off with suction, washed with cold MeOH and dried in vacuo. The purification can be carried out by recrystallisation from acetonitrile/methanol.

(105) The following compounds can be prepared analogously:

(106) TABLE-US-00020 Ligand Ex. Metal salt Product Yield M200 L18 Al(L18) 74% AlCl.sub.3 M201 L18 Ga(L18) 77% GaCl.sub.3 M202 L18 In(L18) 80% InCl.sub.3 M203 L18 La(L18) 46% LaCl.sub.3 M204 L18 Ce(L18) 40% CeCl.sub.3 M205 L18 Fe(L18) 88% FeCl.sub.3 M206 L18 Ru(L18) 90% RuCl.sub.3
Metal Complexes of Ligand L19:

(107) ##STR00389##

(108) A solution, held at a temperature of 75° C., of 1 mmol of the corresponding metal salt in 20 ml of EtOH or EtOH/water (1:1 vv) is added dropwise to a solution of 778 mg (1 mmol) of L19 and 643 mg (6 mmol) of 2,6-dimethylpyridine in 10 ml of DMSO at 80° C., and the mixture is stirred for a further 12 h. An anion exchange is optionally carried out with addition of 6 mmol of the corresponding salt (KPF.sub.6, (NH.sub.4)PF.sub.6, KBF.sub.4, etc.) in 10 ml of EtOH or EtOH/water (1:1, vv). After cooling, the microcrystalline precipitate is filtered off with suction, washed with cold MeOH and dried in vacuo. The purification can be carried out by recrystallisation from acetonitrile/methanol or by hot extraction and subsequent fractional sublimation.

(109) The following compounds can be prepared analogously:

(110) TABLE-US-00021 Ligand Ex. Metal salt Product Yield M300 L19 Ga(L19) 67% GaCl.sub.3 M301 L19 In(L19) 63% InCl.sub.3 M302 L19 Ir(L19) 66% IrCl.sub.3 hydrate M303 L19 La(L19) 48% LaCl.sub.3 M304 L19 Fe(L19) 83% FeCl.sub.3 M305 L19 Ir(L19) 79% IrCl.sub.3 hydrate M306 L19 Ru(L19) 80% RuCl.sub.3
Metal Complexes of Ligand L20:

(111) ##STR00390##

(112) A solution, held at a temperature of 75° C., of 1 mmol of the corresponding metal salt in 15 ml of EtOH or EtOH/water (1:1 vv) is added dropwise to a solution of 736 mg (1 mmol) of L20 and 643 mg (6 mmol) of 2,6-dimethylpyridine in 10 ml of DMSO at 75° C., and the mixture is stirred for a further 12 h. An anion exchange is optionally carried out with addition of 6 mmol of the corresponding salt (KPF.sub.6, (NH.sub.4)PF.sub.6, KBF.sub.4, etc.) in 10 ml of EtOH or EtOH/water (1:1, vv). After cooling, the microcrystalline precipitate is filtered off with suction, washed with cold MeOH and dried in vacuo. The purification can be carried out by recrystallisation from acetonitrile/methanol.

(113) The following compounds can be prepared analogously:

(114) TABLE-US-00022 Ligand Ex. Metal salt Product Yield M400 L20 Al(L20) 72% AlCl.sub.3 M401 L20 Ga(L20) 68% GaCl.sub.3 M402 L20 La(L20) 55% LaCl.sub.3 M403 L20 Ce(L20) 51% CeCl.sub.3 M404 L20 Fe(L20) 78% FeCl.sub.3 M405 L20 Ru(L20) 83% RuCl.sub.3 M406 L20 Ir(L20) 77% IrCl.sub.3 hydrate
4: Functionalisation of the Metal Complexes
4.1 Halogenation of the Iridium Complexes:

(115) A solution or suspension of 10 mmol of a complex which carries A×C—H groups (where A=1, 2, 3) in the para position to the iridium in 500 ml to 2000 ml of dichloromethane, depending on the solubility of the metal complexes, is mixed with A×10.5 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. 100 ml of methanol and 1 ml of hydrazine hydrate are added to the residue, the mixture is stirred briefly, the solid is filtered off with suction, washed three times with 30 ml of methanol and then dried in vacuo, giving the iridium complexes which are brominated 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).fwdarw.Ir(IV)), where the oxidant is bromine, liberated from NBS. This oxidation reaction is evident from a clear green coloration of the otherwise yellow to red solutions/suspensions of the emitters. In such cases, a further equivalent of NBS is added. For work-up, 100-500 ml of methanol and 2 ml of hydrazine hydrate as reducing agent are added, causing the green solutions/suspension to change colour to yellow (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.

(116) Sub-stoichiometric brominations, for example mono- and dibrominations, of complexes having 3 C—H 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).

Example Ir(L1-3Br)

(117) ##STR00391##

(118) 5.6 g (31.5 mmol) of N-bromosuccinimide are added in one portion to a suspension, stirred at 0° C., of 9.6 g (10 mmol) of Ir(L1) in 500 ml of dichloromethane (DCM), and the mixture is then stirred at room temperature for a further 6 h. After removal of about 400 ml of the DCM in vacuo, a mixture of 100 ml of methanol and 1 ml of hydrazine hydrate is added to the yellow suspension, the solid is filtered off with suction, washed three times with about 30 ml of methanol and then dried in vacuo. Yield: 11.2 g (9.5 mmol), 93%; purity: >99.0% according to NMR.

(119) The following complexes can be prepared analogously:

(120) TABLE-US-00023 Starting material > brominated complex Ex. Conditions Yield Tribromination Ir(L3-3Br) 93% Ir(L5-3Br) 95% Ir(L7-3Br) 87% Ir(L7) > Ir(L7-3Br) Ir(L9-3Br) 84% Ir(L101-3Br) 93% Ir(L102-3Br) 95% Ir(L103-3Br) 90% Ir(L108-3Br) 88% Ir(L109-3Br) 00 89% Ir(L110-3Br) 01 90% Ir(L111-3Br) 02 93% Ir(L112-3Br) 03 87% Ir(L115-3Br) 04 84% Ir(L115) > Ir(L115-3Br) Ir(L117-3Br) 05 91% Ir(L120-3Br) 06 85% Ir(L123-3Br) 07 83% Ir(L201-3Br) 08 92% Ir(L203-3Br) 09 90% Ir(L208-3Br) 0 88% Ir(L301-3Br) 85% Ir(L306-3Br) 86% Ir(L400-3Br) 76% Ir(L404-3Br) 90% Ir(L405-3Br) 90% Ir(L500-3Br) 86% Ir(L503-3Br) 93% Dibromination Ir(L100-2Br) 95% Ir(L102-2Br) 26% Ir(L106-2Br) 0 94% Ir(L107-2Br) 96% Ir(L116-2Br) 96% Ir(L121-2Br) 89% Monobromination Ir(L102-1Br) 57% Ir(L113-Br) 92% Ir(L114-Br) 94%
4.2 Borylation of the Metal Complexes Containing a Bromine Function:

(121) A mixture of 10 mmol of the brominated complex, 12 mmol of bis(pinacolato)diborane [73183-34-3] per bromine function, 30 mmol of potassium acetate, anhydrous, per bromine function, 0.2 mmol of tricyclohexylphosphine, 0.1 mmol of palladium(II) acetate (Variant A) or 0.2 mmol of dppfPdCl.sub.2*CH.sub.2Cl.sub.2 [95464-05-4] (Variant B) and 300 ml of solvent (dioxane, DMSO, NMP, toluene, etc.) is stirred at 80-160° C. for 4-16 h. After removal of the solvent in vacuo, the residue is taken up in 300 ml of dichloromethane, THF or ethyl acetate, filtered through a Celite bed, the filtrate is evaporated in vacuo to incipient crystallisation, and finally about 100 ml of methanol are added dropwise in order to complete the crystallisation. The compounds can be recrystallised from dichloromethane, ethyl acetate or THF with addition of methanol or chromatographed on silica gel.

(122) Synthesis of Ir(L1-3BE)-Variant B:

(123) ##STR00427##

(124) Use of 12.0 g (10 mmol) of Ir(L1-3Br) and 9.1 g (36 mmol) of bis(pinacolato)diborane [73183-34-3], dioxane/toluene 1:1 vv, 1200, 16 h, take up and Celite filtration in THF, recrystallisation from THF:methanol. Yield: 7.9 g (5.9 mmol), 59%; purity: about 99.8% according to HPLC.

(125) The following compounds can be prepared analogously:

(126) TABLE-US-00024 Product Ex. Starting material/Variant Yield Triborylation Ir(L3-3BE) 55% Ir(L5-3BE) 52% Diborylation Ir(L107-2BE) 0 66% Monoborylation Ir(L114-BE) 81%
4.3 Suzuki Coupling to the Halogenated Metal Complexes
Variant A, Two-Phase Reaction Mixture:

(127) 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 40-80 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 a silica-gel column. The further purification can be carried by chromatography, recrystallisation or hot extraction. Finally, the metal complex can optionally be heat treated or sublimed. The heat treatment is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 200-300° C. The sublimation is carried out in the case of suitable sublimable complexes in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 300-400° C., where the sublimation is preferably carried out in the form of a fractional sublimation.

(128) Variant B, Single-Phase Reaction Mixture:

(129) 0.6 mmol of tri-o-tolylphosphine and then 0.1 mmol of palladium(II) acetate or 0.3 mmol of tetrakis(triphenylphosphine)palladium(0) 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 the 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 ml-500 ml of an aprotic solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.), and the mixture is stirred with warming (80-130° C.) for 1-24 h. Alternatively, other phosphines, such as triphenylphosphine, tri-tert-butylphosphine, S-Phos, X-Phos, RuPhos, XanthPhos, etc., can be employed, where, in the case of these phosphines, the preferred phosphine:palladium ratio 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.

(130) Synthesis of Ir100:

(131) ##STR00432##
Variant A:

(132) Use of 12.0 g (10.0 mmol) of Ir(L1-3Br) and 9.0 g (60.0 mmol) of 2,5-dimethylphenylboronic acid [85199-06-0], 17.7 g (60 mmol) of tripotassium phosphate (anhydrous), 183 mg (0.6 mmol) of tri-o-tolylphosphine [6163-58-2], 23 mg (0.1 mmol) of palladium(II) acetate, 300 ml of toluene, 100 ml of dioxane and 300 ml of water, reflux, 16 h. Chromatographic separation twice on silica gel with toluene/ethyl acetate (9:1, vv), subsequently hot extraction twice with toluene with addition of 0.5 ml of hydrazine hydrate, then hot extraction five times with butyl acetate. Yield: 6.9 g (5.4 mmol), 54%; purity: about 99.9% according to HPLC.

(133) Variant B:

(134) Use of 12.0 g (10.0 mmol) of Ir(L1-3Br) and 9.0 g (60.0 mmol) of 2,5-dimethylphenylboronic acid pinacolyl ester [356570-53-1], 17.7 g (60 mmol) of tripotassium phosphate monohydrate, 347 mg (0.3 mmol) of tetrakis(triphenylphosphino)palladium(0), 300 ml of DMSO, 90° C., 24 h. Purification as described under Variant A. Yield: 7.3 g (5.7 mmol), 57%; purity: about 99.8% according to HPLC.

(135) The following compounds can be prepared analogously:

(136) TABLE-US-00025 Bromide/Boronic acid/Variant Product Ex. Hot extractant Yield Ir101 Ir(L1-3Br)/5122-95-2/A 57% Butyl acetate, then toluene Ir102 Ir(L1-3Br)/1233200-59-3/A 59% Butyl acetate Ir103 Ir(L3-3Br)/98-80-6/B 64% Toluene Ir104 Ir(L3-3Br)/560132-24-3/B 51% Ethyl acetate/acetonitrile Ir105 Ir(L3-3Br)/197223-39-5/B 55% Ethyl acetate/acetonitrile Ir106 Ir(L3-3Br)/177171-16-3/B 58% Ethyl acetate Ir107 Ir(L3-3Br)/915230-75-0/B 63% Cyclohexane Ir108 Ir(L5-3Br)/162607-19-4/A 67% 0 Toluene Ir109 Ir(L7-3Br)/100124-06-9/A 60% Toluene Ir110 Ir(L9-3Br)/1392146-23-4/B 59% Ethyl acetate/acetonitrile Ir111 Ir(L101-3Br)/854952-58-2/B 65% Toluene Ir112 Ir(L102-3Br)/1392146-23-4/B 60% Toluene Ir113 Ir(L102-3Br)/1313018-07-3/B 67% Toluene Ir114 Ir(L103-3Br)/1809075-56-6/B 58% o-Xylene Ir115 Ir(L108-3Br)/1562418-16-9/A 49% Ethyl acetate/acetonitrile Ir116 Ir(L109-3Br)/1680179-22-9/B 66% Toluene Ir117 Ir(L110-3Br)/1345508-82-8/B 60% Toluene Ir118 Ir(L111-3Br)/5122-95-2/B 63% 0 Toluene Ir119 Ir(L112-3Br)/123324-71-0/B 61% Butyl acetate then toluene Ir120 Ir(L115-3Br)/701261-35-0/B 65% Toluene Ir121 Ir(L117-3Br)/84110-40-7/B 47% Ethyl acetate Ir122 Ir(L120-3Br)/1269508-31-7/B 54% Toluene Ir123 Ir(L123-3Br)/98-80-6/B 59% o-Xylene Ir124 Ir(L201-3Br)/51067-38-0/A 47% Toluene Ir125 Ir(L203-3Br)/4688-76-0/B 57% Toluene Ir126 Ir(L208-3Br)/1245943-60-5/B 50% p-Xylene Ir127 Ir(301-3Br)/400607-32-1/B 62% Toluene Ir128 Ir(L306-3Br)/1421789-05-0/B 60% 0 o-Xylene Ir129 Ir(L100-2Br)/1233200-59-3/B 65% Toluene Ir130 Ir(L102-2Br)/197223-39-5/B 66% Butyl acetate Ir131 Ir(L106-2Br)/5122-95-2/B 70% Toluene Ir132 Ir(L107-2Br)/786071-96-0 68% Toluene Ir133 Ir(L116-2Br)/1416814-68-0/B 67% Butyl acetate Ir134 Ir(L121-2Br)/1423-26-3/B 63% Butyl acetate Ir135 Ir(L102-1Br)/1565126-29-5/B 65% Toluene Ir136 Ir(L113-Br)/1801624-63-4/B 62% Butyl acetate Ir137 Ir(L114-Br)/1000869-26-0/B 71% Toluene Ir138 Ir(L400-3Br)/5122-95-2/B 58% 0 Toluene Ir139 Ir(L404-3Br)/84110-40-7/B 47% Ir140 Ir(L405-3Br)/1056113-44-0/B 54% Toluene Ir141 Ir(L500-3Br)/1801285-73-3/B 49% Ir142 Ir(L503-3Br)/1345508-82-8/B 52%
4.4 Buchwald Coupling to the Ir Complexes
Variant A:

(137) 0.4 mmol of tri-tert-butylphosphine and then 0.3 mmol of palladium(II) acetate are added to a mixture of 10 mmol of the brominated complex, 12-20 mmol of the diarylamine or carbazole per bromine function, 1.1 molar amount of sodium tert-butoxide per amine employed or 80 mmol of tripotassium phosphate (anhydrous) in the case of carbazoles, 100 g of glass beads (diameter 3 mm) and 300-500 ml of toluene or o-xylene in the case of carbazoles, and the mixture is heated under reflux with vigourous stirring for 16-30 h. After cooling, 500 ml of water are added, the aqueous phase is separated off, the organic phase is washed twice with 200 ml of water, 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 or o-xylene, almost all the solvent is removed in vacuo, 300 ml of ethanol are added, the crude product which has precipitated out is filtered off with suction, washed three times with 50 ml of EtOH each time and dried in vacuo. The crude product is purified by chromatography on silica gel and/or by hot extraction. Finally, the metal complex is heat-treated or sublimed. The heat treatment is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 200-300° C. The sublimation is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 300-400° C., where the sublimation is preferably carried out in the form of a fractional sublimation.

(138) Variant B:

(139) A mixture of 10 mmol of the brominated complex, 12-20 mmol of the diarylamine or carbazole per bromine function, 30 mmol of potassium carbonate and 30 mmol of sodium sulfate per bromine function, 10 mmol of copper iodide per bromine function, 50 g of glass beads (diameter 3 mm) and 150 ml of nitrobenzene is heated at 200° C. with vigourous stirring for 16-30 h. After cooling to 100° C., the nitrobenzene is substantially removed in vacuo, 300 ml of MeOH are added, the product which has precipitated out and the salts are filtered off, the latter are rinsed with 50 ml of methanol and dried in vacuo. The residue is taken up in 300 ml of dichloromethane, the salts are filtered off via a silica-gel bed which has been pre-slurried with dichloromethane, the dichloromethane is removed in vacuo, and the product is re-chromatographed on silica gel.

(140) Synthese von Ir200:

(141) ##STR00475##
Variant A:

(142) Use of 12.0 g (10 mmol) of Ir(L1-3Br) and 9.7 g (40 mmol) of 3-phenylcarbazole [103012-26-6]. Chromatography three times on silica gel with DCM, heat treatment. Yield: 6.3 g (3.7 mmol), 37%; purity: about 99.8% according to HPLC.

(143) Variant B:

(144) Use of 12.0 g (10 mmol) of Ir(L1-3Br) and 9.7 g (40 mmol) of 3-phenylcarbazole [103012-26-6]. Chromatography three times on silica gel with DCM, heat treatment. Yield: 7.5 g (4.4 mmol), 44%; purity: about 99.7% according to HPLC.

(145) The following compounds can be prepared analogously:

(146) TABLE-US-00026 Starting material/amine or carbazole Product Ex. Hot extractant Yield Ir201 Ir(L102-3Br)/1257220-47-5 30% Ir202 Ir(L301-3Br)/1421789-16-3 38% Ir203 Ir(L114-Br)/103012-26-6 69%
4.5 Cyanation of the Iridium Complexes:

(147) A mixture of 10 mmol of the brominated complex, 13 mmol of copper(I) cyanide per bromine function and 300 ml of NMP is stirred at 180° C. for 20 h. After cooling, the solvent is removed in vacuo, the residue is taken up in 500 ml of dichloromethane, the copper salts are filtered off via Celite, the dichloromethane is evaporated virtually to dryness in vacuo, 100 ml of ethanol are added, the solid which has precipitated out is filtered off with suction, washed twice with 50 ml of ethanol each time and dried in vacuo. The crude product is purified by chromatography and/or hot extraction.

(148) The heat treatment is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 200-300° C. The sublimation is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 300-400° C., where the sublimation is preferably carried out in the form of a fractional sublimation.

(149) Synthesis of Ir300:

(150) ##STR00479##

(151) Use of 12.0 g (10 mmol) of Ir(L1-3Br) and 3.5 g (39) mmol) of copper(I) cyanide. Chromatography twice on silica gel with dichloromethane, hot extraction with DCM, sublimation. Yield: 4.9 g (4.7 mmol), 47%; purity: about 99.9% according to HPLC.

(152) The following compounds can be prepared analogously:

(153) TABLE-US-00027 Starting material Ex. Cyanation product Ir301 Ir(L123-3Br) 51% 0 Ir302 Ir(L121-2Br) 64% Ir303 Ir(L208-3Br) 47%
4.6 Suzuki Coupling to the Borylated Iridium Complexes:
Variant A, Two-Phase Reaction Mixture:

(154) 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 borylated complex, 12-20 mmol of aryl bromide per (RO).sub.2B function and 80 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, 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, almost all the toluene is removed 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 a silica-gel column twice and/or purified by hot extraction. Finally, the metal complex is heat-treated or sublimed. The heat treatment is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 200-300° C. The sublimation is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 300-400° C., where the sublimation is preferably carried out in the form of a fractional sublimation.

(155) Variant B, Single-Phase Reaction Mixture:

(156) 0.6 mmol of tri-o-tolylphosphine and then 0.1 mmol of palladium(II) acetate or 0.3 mmol of tetrakis(triphenylphosphino)palladium(0) are added to a suspension of 10 mmol of a borylated complex, 12-20 mmol of aryl bromide per (RO).sub.2B function and 60-100 mmol of the base (potassium fluoride, tripotassium phosphate (anhydrous, monohydrate or trihydrate), potassium carbonate, caesium carbonate, etc.) and 100 g of glass beads (diameter 3 mm) in 100 ml-500 ml of an aprotic solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.), and the mixture is heated under reflux for 1-24 h. Alternatively, other phosphines, such as triphenylphosphine, tri-tert-butylphosphine, S-Phos, X-Phos, Ru-Phos, XanthPhos, etc. can be employed, where, in the case of these phosphines, the preferred phosphine:palladium ratio 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.

(157) Synthesis of Ir400:

(158) ##STR00483##

(159) Variant A:

(160) Use of 13.4 g (10.0 mmol) of Ir(L1-3BE) and 7.4 g (40.0 mmol) of 9,9′-spirobifluorene-4-boronic acid pinacolyl ester [1161009-88-6], 17.7 g (60 mmol) of tripotassium phosphate (anhydrous), 183 mg (0.6 mmol) of tri-o-tolylphosphine [6163-58-2], 23 mg (0.1 mmol) of palladium(II) acetate, 300 ml of toluene, 100 ml of dioxane and 300 ml of water, 100° C., 16 h. Chromatographic separation twice on silica gel with toluene/ethyl acetate (9:1, vv), hot extraction three times with o-xylene. Yield: 10.9 g (5.7 mmol), 57%; purity: about 99.9% according to HPLC.

(161) The following compounds can be prepared analogously:

(162) TABLE-US-00028 Starting materials/Variant Product Ex. Hot extractant Yield Ir401 Ir(L3-3BE)/1613576-58-1/A 48% Toluene Ir402 Ir(L5-3BE)/3842-55-5/B 37% Ir403 Ir(L107-2BE)/50548-45-3/B/PPh.sub.3:Pd(ac).sub.2 3:1/ 41% K.sub.3PO.sub.4 * H.sub.2O/DMSO/90° C./18 h
4.7 Alkylation on Iridium Complexes:

(163) 50 ml of a freshly prepared LDA solution, 1 molar in THF, are added to a suspension of 10 mmol of the complex in 1500 ml of THF, and the mixture is stirred at 25° C. for a further 24 h. 200 mmol of the alkylating agent are then added in one portion with vigourous stirring, where liquid alkylating agents are added without dilution, solid ones are added as a solution in THF. The mixture is stirred at room temperature for a further 60 min., the THF is removed in vacuo, and the residue is chromatographed on silica gel. The further purification can be carried out by hot extraction—as described above. Finally, the metal complex is heat-treated or sublimed. The heat treatment is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 200-300° C. The sublimation is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 300-400° C., where the sublimation is preferably carried out in the form of a fractional sublimation.

(164) Synthesis of Ir500:

(165) ##STR00487##

(166) Use of 13.4 g (10.0 mmol) of Ir(L5) and 21.7 ml (200 mmol) of 1-bromo-2-methylpropane [78-77-3]. Chromatographic separation twice on silica gel with toluene, subsequent hot extraction five times with ethyl acetate/acetonitrile. Yield: 4.6 g (3.1 mmol), 31%; purity: about 99.7% according to HPLC.

(167) The following compounds can be prepared analogously:

(168) TABLE-US-00029 Starting material/alkylating agent Ex. Product Yield Ir501 Ir(L103)/1.5 eq of LDA/6 eq of 78-77-3 42% Ir502 Ir(L104)/1.5 eq of LDA/6 eq of 108-85-0 29% Ir503 Ir(L105)/1.5 eq of LDA/6 eq of 630-17-1 35% 0 Ir504 Ir(L110)/3 eq of LDA/9 eq of 74-83-9 32% Ir505 Ir(L203)/5 eq of LDA/20 eq of 78-77-3 27%
4.8 Deuteration of Ir Complexes:

Example: Ir(L5-D9)

(169) ##STR00493##

(170) A mixture of 1.34 g (1.0 mmol) of Ir(L5), 24 mg (1.0 mmol) of sodium hydride, 3 ml of methanol-D4 and 30 ml of DMSO-D6 is heated at 80° C. for 18 h. After cooling, 1.0 ml of 5 M DCl in D.sub.2O is added, the mixture is stirred briefly, and 80 ml of methanol are then added dropwise. The solid which has precipitated out is filtered off with suction, washed three times with 10 ml of methanol each time, dried in vacuo, and the residue is chromatographed on silica gel with DCM. Yield: 1.14 g (0.84 mmol), 84%, degree of deuteration>90%.

(171) The following compounds can be prepared analogously:

(172) TABLE-US-00030 Ex. Starting material/product Yield Ir(L103-D3) Ir(L103)/0.3 mmol of NaH 90% 2 ml of methanol-D4/10 ml of DMSO-D6 Ir(L104-D3) Ir(L104)/0.3 mmol of NaH 87% 2 ml of methanol-D4/10 ml of DMSO-D6 Ir(L105-D3) Ir(L105)/0.3 mmol of NaH 92% 2 ml of methanol-D4/10 ml of DMSO-D6 Ir(110-D6) Ir(L110) )/0.6 mmol of NaH 90% 2 ml of methanol-D4/20 ml of DMSO-D6 Ir(L203-D9) Ir(L203)/1.0 mmol of NaH 93% 4 ml Methanol-D4/30 ml of DMSO-D6
4.9 Separation of the Δ and Λ Enantiomers of the Metal Complexes by Means of Chromatography on Chiral Columns:

(173) The Δ and Λ enantiomers of the complexes can be separated by means of analytical and/or preparative chromatography on chiral columns by standard laboratory methods, for example separation of Ir105 on ChiralPak AZ-H (Chiral Technologies Inc.) with n-hexane/ethanol (90:10), retention times 13.4 min. and 16.8 min. respectively.

(174) 5. Polymers Containing the Metal Complexes:

(175) General Polymerisation Procedure for the Bromides or Boronic Acid

(176) Derivatives as Polymerisable Group, Suzuki Polymerisation

(177) Variant A—Two-Phase Reaction Mixture:

(178) The monomers (bromides and boronic acids or boronic acid esters, purity according to HPLC>99.8%) in the composition indicated in the table are dissolved or suspended in a mixture of 2 parts by volume of toluene:6 parts by volume of dioxane:1 part by volume of water in a total concentration of about 100 mmol/l. 2 mol equivalents of tripotassium phosphate per Br functionality employed are then added, the mixture is stirred for a further 5 min., 0.03 to 0.003 mol equivalent of tri-ortho-tolylphosphine and then 0.005 to 0.0005 mol equivalent of palladium(II) acetate (phosphine to Pd ratio preferably 6:1) per Br functionality employed are then added, and the mixture is heated under reflux with very vigourous stirring for 2-3 h. If the viscosity of the mixture increases excessively, it can diluted with a mixture of 2 parts by volume of toluene:3 parts by volume of dioxane. After a total reaction time of 4-6 h, 0.05 mol equivalent of a monobromoaromatic compound per boronic acid functionality employed and then, 30 min. later, 0.05 mol equivalent of a monoboronic acid or monoboronic acid ester per Br functionality employed are added for end capping, and the mixture is boiled for a further 1 h. After cooling, the mixture is diluted with 300 ml of toluene, the aqueous phase is separated off, the organic phase is washed twice with 300 ml of water each time, dried over magnesium sulfate, filtered through a Celite bed in order to remove palladium and then evaporated to dryness. The crude polymer is dissolved in THF (concentration about 10-30 g/l) and the solution is allowed to run slowly into twice the volume of methanol with very vigourous stirring. The polymer is filtered off with suction and washed three times with methanol. The reprecipitation process is repeated five times, and the polymer is then dried to constant weight in vacuo at 30-50° C.

(179) Variant B—Single-Phase Reaction Mixture:

(180) The monomers (bromides and boronic acids or boronic acid esters, purity according to HPLC>99.8%) in the composition indicated in the table are dissolved or suspended in a solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.) in a total concentration of about 100 mmol/l. 3 mol equivalents of base (potassium fluoride, tripotassium phosphate (anhydrous, monohydrate or trihydrate), potassium carbonate, caesium carbonate, etc., in each case anhydrous) per Br functionality and the weight equivalent of glass beads (diameter 3 mm) are added, the mixture is stirred for a further 5 min., 0.03 to 0.003 mol equivalent of tri-ortho-tolylphosphine and then 0.005 to 0.0005 mol equivalent of palladium(II) acetate (phosphine to Pd ratio preferably 6:1) per Br functionality are then added, and the mixture is heated under reflux with very vigourous stirring for 2-3 h. Alternatively, other phosphines, such as tri-tert-butylphosphine, S-Phos, X-Phos, Ru-Phos, XanthPhos, etc., can be employed, where, in the case of these phosphines, the preferred phosphine:palladium ratio is 2:1 to 1.3:1. After a total reaction time of 4-12 h, 0.05 mol equivalent of a monobromoaromatic compound and then, 30 min. later, 0.05 mol equivalent of a monoboronic acid or monoboronic acid ester are added for end capping, and the mixture is boiled for a further 1 h. The solvent is substantially removed in vacuo, the residue is taken up in toluene, and the polymer is purified as described under Variant A.

(181) Monomers M/End Cappers E:

(182) ##STR00499## ##STR00500##
Polymers:

(183) TABLE-US-00031 Composition of the polymers, mmol: Polymer M1 M2 M3 M4 Ir complex P1 — 30 — 45 Ir(L102-3Br)/10 P2  5 25 — 40 Ir(L107-2Br)/10 P3 10 40 25 20 Ir(L107-2BE)/5

(184) TABLE-US-00032 Molecular weights and yield of the polymers according to the invention: Polymer Mn [gmol.sup.−1] Polydispersity Yield P1 200,000 5.3 70% P2 350,000 2.4 53% P3 240,000 2.2 57%
6. Thermal and Photophysical Properties and Oxidation and Reduction Potentials

(185) Table 1 summarises the thermal and photochemical properties and oxidation and reduction potentials of the comparative materials IrPPy, Ir1 to Ir3 (structures see Table 5) and the selected materials according to the invention. The compounds according to the invention have improved thermal stability and photostability compared with the materials in accordance with the prior art. While materials in accordance with the prior art exhibit brown colorations and ashing after thermal storage at 380° C. for seven days and secondary components in the range >2 mol % can be detected in the 1H-NMR, the complexes according to the invention are inert under these conditions. This thermal robustness is crucial, in particular, for the processing of the materials in a high vacuum (vapour small-molecule devices). 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 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.

(186) TABLE-US-00033 TABLE 1 Therm. stab. PL-max. HOMO Complex Photo. stab. FWHM PLQE LUMO Comparative examples, structures see Table 5 IrPPy Decomposition 509 0.97 — Decomposition  67 Toluene — Ir1 — 513 0.97 −5.09 —  60 Toluene −1.99 Ir2 Decomposition 516 0.97 −5.05 Decomposition  69 Toluene −1.71 Ir3 Decomposition  510* 0.76* — Decomposition — BuCN — Examples according to the invention Ir(L1) No decomp. 523 0.99 −5.09 No decomp.  63 Toluene −2.01 0.91 MeCN Ir(L6) No decomp. 520 0.96 −5.02 No decomp.  56 Toluene −1.96 Ir(L103) No decomp. 528 0.95 −5.04 No decomp.  67 Toluene −1.97 Ir(L400) No decomp. 495 0.97 −5.02 No decomp.  57 Toluene −2.00 Ir(L404) No decomp. 552 0.94 −5.26 No decomp.  62 Toluene −2.21 Ir(L500) No decomp. 512 0.96 −5.03 No decomp.  61 Toluene −1.99 *Data from G. St-Pierre et al., Dalton Trans, 2011, 40, 11726.
Legend
Therm. Stab. (Thermal Stability):

(187) 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.

(188) Photo. Stab. (Photochemical Stability):

(189) Irradiation of approx. 1 mmolar solutions 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 RT.

(190) PL-Max.:

(191) Maximum of the PL spectrum in [nm] of a degassed, approx. 10.sup.−5 molar solution at RT, excitation wavelength 370 nm, solvent: see PLQE column.

(192) FWHM:

(193) Full width at half maximum of the PL spectrum in [nm] at RT.

(194) PLQE:

(195) Abs. photoluminescence quantum efficiency of a degassed, approx. 10.sup.−5 molar solution in the solvent indicated at RT.

(196) HOMO, LUMO:

(197) in [eV] vs. vacuum, determined in dichloromethane solution (oxidation) or THF (reduction) with internal ref. ferrocene (−4.8 eV vs. vacuum).
7. Solubility of Selected Complexes at 25° C.

(198) For the processing of the complexes according to the invention from solution (spin coating, ink-jet printing, nozzle printing, knife coating, etc.), long-term-stable solutions having solids contents of about 5 mg/ml or more are required.

(199) TABLE-US-00034 TABLE 2 Solubilities of selected complexes Complex Solvent Solubility Ir(L4) Toluene >10 mg/ml Ir(L4) 3-Phenoxytoluene >30 mg/ml Ir(L5) Toluene  >5 mg/ml Ir(L7) Toluene >10 mg/ml Ir(L107) Toluene >10 mg/ml Ir(L109) Toluene >15 mg/ml Ir(L115) Toluene >15 mg/ml Ir(L115) Anisole >20 mg/ml Ir(L115) 3-Phenoxytoluene >25 mg/ml Ir(L120) Toluene >10 mg/ml Ir(L120) 3-Phenoxytoluene >20 mg/ml Ir(138) 3-Phenoxytoluene >25 mg/ml Ir(141) 3-Phenoxytolueene >35 mg/ml Ir(142) 3-Phenoxytoluol >30 mg/ml
Production of OLEDs
1) Vacuum-Processed Devices:

(200) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 2004/058911, which is adapted to the circumstances described here (layer-thickness variation, materials used).

(201) In the following examples, the results for various OLEDs are presented. Glass plates with structured ITO (50 nm, indium tin oxide) form the substrates to which the OLEDs are applied. The OLEDs have in principle the following layer structure: substrate/hole-transport layer 1 (HTL1) consisting of HTM doped with 5% of NDP-9 (commercially available from Novaled), 20 nm/hole-transport layer 2 (HTL2)/optional electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm.

(202) Firstly, vacuum-processed OLEDs are described. For this purpose, all materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), with which the matrix material or matrix materials is (are) admixed in a certain proportion by volume by co-evaporation. An expression such as M3:M2:Ir(L1) (55%:35%:10%) here means that material M3 is present in the layer in a proportion by volume of 55%, M2 is present in the layer in a proportion of 35% and Ir(L1) is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials. The precise structure of the OLEDs is shown in Table 1. The materials used for the production of the OLEDs are shown in Table 5.

(203) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A) and the voltage (measured at 1000 cd/m.sup.2 in V), determined from current/voltage/brightness characteristic lines (IUL characteristic lines), are determined. For selected experiments, the lifetime is determined. The lifetime is defined as the time after which the luminous density has dropped to a certain proportion from a particular initial luminous density. The expression LT50 means that the said lifetime is the time at which the luminous density has dropped to 50% of the initial luminous density, i.e. from, for example, 1000 cd/m.sup.2 to 500 cd/m.sup.2. Depending on the emission colour, different initial brightnesses were selected. The values for the lifetime can be converted into a value for other initial luminous densities with the aid of conversion formulae known to the person skilled in the art. The lifetime for an initial luminous density of 1000 cd/m.sup.2 is a usual expression here.

(204) Use of Compounds According to the Invention as Emitter Materials in Phosphorescent OLEDs

(205) The compounds according to the invention can be employed, inter alia, as phosphorescent emitter materials (dopants) in the emission layer in OLEDs and as electron-transport material. As comparison in accordance with the prior art, the iridium compounds shown in Table 5 are used. The results for the OLEDs are summarised in Table 2.

(206) TABLE-US-00035 TABLE 1 Structure of the OLEDs HTL2 EBL EML HBL ETL Ex. Thickness Thickness Thickness Thickness Thickness Green - yellow devices Ref.-D1 HTM — M1:IrPPy ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm Ref.-D2 HTM — M1:Ir2 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm Ref.-D3 HTM — M1:M3:Ir2 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm Ref.-D4 HTM — M1:Ir3 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm Ref.-D5 HTM — M1:M3:Ir3 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D1 HTM — M1:Ir(L1) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D2 HTM — M1:Ir(L3) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D3 HTM — M1:Ir(L102) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D4 HTM — M1:M3:Ir(L1) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D5 HTM — M1:M3:Ir(L102) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D6 HTM — M1:M3:Ir(L103) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D7 HTM — M1:M3:Ir(L102) ETM1 M200 40 nm (60%:30%:10%) 10 nm 30 nm 30 nm D8 HTM — M1:M3:Ir(L400) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D9 HTM — M1:M3:Ir(L500) ETM1 M200 40 nm (60%:30%:10%) 10 nm 30 nm 30 nm Orange - red devices D100 HTM — M1:Ir(L8) ETM1 ETM1:ETM2 40 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm D100 HTM — M2:M3:Ir(L8) ETM1 ETM1:ETM2 40 nm (50%:40%:10%) 10 nm (50%:50%) 30 nm 30 nm D102 HTM — M2:M3:Ir(L404) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm

(207) TABLE-US-00036 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) CIE x/y LT50 (h) Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Green - yellow devices Ref.-D1 15.7 2.8 0.33/0.62 60000 Ref.-D2 18.6 2.9 0.35/0.61 200000 Ref.-D3 18.8 2.9 0.35/0.61 330000 Ref.-D4 18.7 3.0 0.34/0.62 180000 Ref.-D5 18.6 3.0 0.34/0.62 270000 D1 19.7 2.9 0.35/0.61 280000 D2 19.3 2.9 0.34/0.62 260000 D3 20.4 2.9 0.34/0.63 270000 D4 19.5 2.9 0.35/0.61 370000 D5 21.0 3.1 0.34/0.62 360000 D6 20.2 3.0 0.37/0.61 390000 D7 20.9 3.0 0.34/0.62 350000 D8 19.8 2.9 0.22/0.61 260000 D9 20.7 3.1 0.34/0.62 410000 Orange - red devices D100 19.4 2.9 0.45/0.55 270000 D101 19.7 2.9 0.46/0.54 380000 D102 20.1 3.2 0.40/0.58 360000
Solution-Processed Devices:
A: From Soluble Functional Materials

(208) The iridium complexes according to the invention can also be processed from solution, where they result in OLEDs which are significantly simpler from a process engineering point of view compared with vacuum-processed OLEDs, but nevertheless have good properties. The production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in WO 2004/037887). The structure is composed of substrate/ITO/hole-injection layer (60 nm)/interlayer (20 nm)/emission layer (60 nm)/hole-blocking layer (10 nm)/electron-transport layer (40 nm)/cathode. To this end, use is made of substrates from Techno-print (soda-lime glass), to which the ITO structure (indium tin oxide, a transparent, conductive anode) is applied. The substrates are cleaned with deionised water and a detergent (Deconex 15 PF) in a clean room and then activated by UV/ozone plasma treatment. A 60 nm hole-injection layer is then applied by spin coating, likewise in a clean room. The spin rate required depends on the degree of dilution and the specific spin-coater geometry. In order to remove residual water from the layer, the substrates are dried by heating at 200° C. on a hotplate for 30 minutes. The interlayer used serves for hole transport, in this case an HL-X from Merck is used. The interlayer may alternatively also be replaced by one or more layers which merely have to satisfy the condition of not being detached again by the subsequent processing step of EML deposition from solution. For the production of the emission layer, the triplet emitters according to the invention are dissolved in toluene or chlorobenzene together with the matrix materials. The typical solids content of such solutions is between 16 and 25 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 solution-processed devices of type 1 contain an emission layer comprising M4:M5:IrL (25%:55%:20%), those of type 2 contain an emission layer comprising M4:M5:IrLa:IrLb (30%:34%:30%:6%), i.e. they contain two different Ir complexes. The emission layer is applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 160° C. for 10 min. The hole-blocking layer (10 nm of ETM1) and the electron-transport layer (40 nm of ETM1 (50%)/ETM2 (50%)) are applied on top by vapour deposition (vapour-deposition units from Lesker or others, typical vapour-deposition pressure 5×10.sup.−6 mbar). Finally, an aluminium cathode (100 nm) (high-purity metal from Aldrich) is applied by vapour deposition. In order to protect the device against air and atmospheric moisture, the device is finally encapsulated and then characterised. The OLED examples given have not yet been optimised, Table 3 summarises the data obtained.

(209) TABLE-US-00037 TABLE 3 Results with materials processed from solution EQE (%) LT50 (h) Emitter 1000 Voltage (V) 1000 Ex. Device cd/m.sup.2 1000 cd/m.sup.2 CIE x/y cd/m.sup.2 Green and yellow OLEDs Sol-Ref.- Ir1 19.8 5.1 0.34/0.62 200000 D1 Typ1 Sol-D1 Ir(L4) 20.6 5.0 0.36/0.61 240000 Typ1 Sol-D2 Ir(L107) 21.2 5.0 0.34/0.62 270000 Typ1 Sol-D3 Ir(L109) 20.7 5.1 0.37/0.60 280000 Typ1 Sol-D4 Ir(L120) 20.7 5.2 0.35/0.61 260000 Typ1 Sol-D5 Ir139 18.8 5.3 0.24/0.62 180000 Typ1 Sol-D6 Ir142 19.9 5.1 0.33/0.63 260000 Typ1 Orange and red OLEDs Sol-D100 Ir(L7) 16.2 6.1 0.64/0.36 45000 Typ1 Sol-D101 Ir1 17.6 6.0 0.64/0.36 135000 Ir(L7) Typ2 Sol-D102 Ir(L5) 18.0 6.1 0.64/0.36 190000 Ir(L7) Typ2 Sol-D103 Ir(L107) 17.4 6.1 0.66/0.34 270000 Ir(L115) Typ2
B: From Polymeric Functional Materials:

(210) Production of the OLEDs as described under A. For the production of the emission layer, the polymers according to the invention are dissolved in toluene. The typical solids content of such solutions is between 10 and 15 g/l if, as here, the typical layer thickness of 40 nm for a device is to be achieved by means of spin coating. The OLED examples given have not yet been optimised, Table 4 summarises the data obtained.

(211) TABLE-US-00038 TABLE 4 Results with materials processed from solution EQE (%) Voltage (V) CIE x/y Ex. Polymer 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Green OLEDs D-P1 P1 19.8 4.1 0.35/0.61 D-P2 P2 20.3 4.4 0.36/0.60 D-P3 P3 20.1 4.3 0.36/0.60

(212) TABLE-US-00039 TABLE 5 Structural formulae of the materials used 01 HTM 02 M1 03 M2 04 M3 05 M4 06 M5 07 ETM1 08 ETM2 09 IrPPy 0 Ir1 Ir2 Ir3* *G. St-Pierre et al., Dalton Trans, 2011, 40, 11726.