Metal complexes

Abstract

The present invention relates to metal complexes of formula (1), ##STR00001##
and to electronic devices, in particular organic electroluminescent devices, comprising these metal complexes, in particular as emitters.

Claims

1. A compound of the formula (1), ##STR00232## where the following applies to the symbols used: M is selected on each occurrence, identically or differently, from the group consisting of platinum, palladium, nickel, rhodium, iridium and gold; X is on each occurrence, identically or differently, CR.sup.1 or N; Y is C═O, BR, SiR.sub.2, NR, PR, P(═O)R, CR═CR, CR.sub.2—CR.sub.2 or CR═N; or Y stands for a group of the formula (2), ##STR00233##  where the dashed bonds indicate the linking of this group; D is on each occurrence, identically or differently, C or N; E is C if the ring in which this E is bonded is an aromatic or heteroaromatic six-membered ring; or is C or N if the ring in which this E is bonded is a heteroaromatic five-membered ring; Ar.sup.1 is on each occurrence, identically or differently, together with D and E, an aryl or heteroaryl group comprising a five or six-membered aromatic ring having D and E as members of the ring, wherein the aryl or heteroaryl group is optionally substituted by one or more radicals R.sup.1; adjacent groups Ar.sup.1 and Ar.sup.2 here may also be linked to one another by two radicals R.sup.1, which are linked to one another, or by a group CR.sup.2═N; Ar.sup.2 is on each occurrence, identically or differently, together with D and E, an aryl or heteroaryl group comprising a five or six-membered aromatic ring having D and E as members of the ring, wherein the aryl or heteroaryl group is optionally substituted by one or more radicals R.sup.1; adjacent groups Ar.sup.2 and Ar.sup.1 here may also be linked to one another by two radicals R.sup.1, which are linked to one another, or by a group CR.sup.2═N; R is on each occurrence, identically or differently, H, D, F, N(R.sup.2).sub.2, CN, C(═O)N(R.sup.2).sub.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, a straight-chain alkyl, alkoxy or thioalkoxy 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, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups is 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 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2; two radicals R here which are bonded to the same C or Si atom may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; 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, OH, COOH, C(═O)N(R.sup.2).sub.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, alkoxy or thioalkoxy 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, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups is 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 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2; two adjacent radicals R.sup.1 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; furthermore, the radicals R.sup.1 which are bonded to adjacent groups Ar.sup.1 and Ar.sup.2 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; furthermore, two radicals R.sup.1 on the two groups Ar.sup.2 may also form a ring system with one another; R.sup.2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.3).sub.2, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, C(═O)R.sup.3, P(═O)(R.sup.3).sub.2, S(═O)R.sup.3, S(═O).sub.2R.sup.3, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy 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, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.3, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.3C═CR.sup.3, C≡C, Si(R.sup.3).sub.2, C═O, NR.sup.3, O, S or CONR.sup.3 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.3, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3; two or more adjacent radicals R.sup.2 here may form a mono- or polycyclic, aliphatic ring system with one another; R.sup.3 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic and/or heteroaromatic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by F; two or more substituents R.sup.3 here may also form a mono- or polycyclic, aliphatic ring system with one another; two groups Ar.sup.2 here may also be bridged to one another by a group Y.

2. The compound according to claim 1, wherein M is selected from the group consisting of Pt(II), Pd(II), Ni(II), Rh(I), Ir(I) and Au(III).

3. The compound according to claim 1, wherein M is Pt(II).

4. The compound according to claim 1, wherein the compound is selected from the structures of the formula (3), (4), (5) or (6), ##STR00234## where the symbols used have the meanings given in claim 1.

5. The compound according to claim 1, wherein the compound is selected from the structures of the formulae (3a), (4a), (5a) and (6a), ##STR00235## where R.sup.1 stands for H.

6. The compound according to claim 1, wherein E stands for C.

7. The compound according to claim 1, wherein all groups Ar.sup.1 are selected identically and are identically substituted and in that all groups Ar.sup.2 are selected identically and are identically substituted.

8. The compound according to claim 1, wherein Ar.sup.1 is selected, identically or differently on each occurrence, from the structures of the formulae (8), (10)-(12), (14), (16)-(17), (19)-(20), (24)-(26h), ##STR00236## ##STR00237## ##STR00238## ##STR00239## and in that Ar.sup.2 is selected, identically or differently on each occurrence, from the structures of the formulae (28)-(30), (32)-(34), (36), (38)-(40) and (43)-(48d), ##STR00240## ##STR00241## ##STR00242## ##STR00243## where the bond to the carbon atom of the bridgehead, to M and to Ar.sup.1 or to Ar.sup.2 is in each case indicated by dashed bonds and X and R.sup.1 having the meaning given in claim 1; V stands on each occurrence, identically or differently, for O, S, NR.sup.1 or C(R.sup.1).sub.2.

9. The compound according to claim 1, wherein adjacent groups Ar.sup.1 and Ar.sup.2 form a ring with one another, where the ring closure takes place via a group CR.sup.2═CR.sup.2, CR.sup.2═N, C(R.sup.2).sub.2—C(R.sup.2).sub.2, C(═O)—O or C(═O)—NR.sup.2.

10. The compound according to claim 1, wherein one or both groups Ar.sup.1-Ar.sup.2 are selected from the groups of the formulae (51) to (59), ##STR00244## ##STR00245## where the bond to the metal or to the bridgehead carbon atom are in each case indicated by dashed bonds, Z stands on each occurrence, identically or differently, for CR.sup.2 or N, where a maximum of one group Z stands for N, and the other symbols have the meanings given in claim 1.

11. A process for the preparation of the compound according to claim 1, which comprises reacting the corresponding ligand with a metal starting material.

12. A formulation comprising at least one compound according to claim 1 and at least one solvent.

13. The formulation according to claim 12, wherein the formulation is a solution or a suspension.

14. An electronic device comprising the compound according to claim 1.

15. The electronic device as claimed in claim 14, wherein the device is selected from the group consisting of an organic electroluminescent device, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, a light-emitting electrochemical cell and an organic laser diode.

16. An organic electroluminescent device which comprises employing the compound according to claim 1 as emitting compound in one or more emitting layers.

17. An electronic device which comprises the compound according to claim 1 employed in combination with one or more matrix materials.

18. The electronic device according to claim 17, wherein said one or more matrix materials, is selected from the group consisting of ketones, phosphine oxides, sulfoxides, sulfones, triarylamines, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazoles, bipolar matrix materials, silanes, azaboroles, boronic esters, diazasilole derivatives, diazaphosphole derivatives, triazine derivatives, zinc complexes, dibenzofuran derivatives and bridged carbazole derivatives.

19. The compound according to claim 1, wherein the compound is uncharged and the following furthermore applies: M is selected from the group consisting of Pt(II), Pd(II), Ni(II), Rh(I), Ir(I) and Au(III); Y is selected from the group consisting of C═O and NR; X is, identically or differently on each occurrence, CR.sup.1 or N, wherein a maximum of two symbols X per ring stand for N and the other symbols X stand for CR.sup.1; Ar.sup.1 is selected, identically or differently on each occurrence, from the structures of the formulae (8), (10)-(12), (14), (16)-(17), (19)-(20), (24)-(26h); ##STR00246## ##STR00247## ##STR00248## Ar.sup.2 is selected, identically or differently on each occurrence, from the structures of the formulae (28)-(30), (32)-(34), (36), (38)-(40) and (43)-(48d); ##STR00249## ##STR00250## ##STR00251## ##STR00252## or Ar.sup.1-Ar.sup.2 is selected, identically or differently on each occurrence, from the structures of the formulae (51) to (59) ##STR00253## ##STR00254## where the bond to the metal or to the bridgehead carbon atom are in each case indicated by dashed bonds, Z stands on each occurrence, identically or differently, for CR.sup.2 or N, where a maximum of one group Z stands for N; R.sup.1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, N(R.sup.2).sub.2, CN, C(═O)R.sup.2, a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, where one or more H atoms is optionally replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2; R stands for an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2 and which contains no condensed aryl or heteroaryl groups.

20. The compound according to claim 1, wherein Ar.sup.1 is selected, identically or differently on each occurrence, from the structures of the formulae (7), (9), (13), (15), (18) and (21)-(23), ##STR00255## and in that Ar.sup.2 is selected, identically or differently on each occurrence, from the structures of the formulae (27), (31), (35), (37), (41), (42), (49) and (50) (41) and (42) ##STR00256## or Ar.sup.1-Ar.sup.2 is selected, identically or differently on each occurrence, from the structures of the formulae (49) and (50) ##STR00257## where the bond to the carbon atom of the bridgehead, to M and to Ar.sup.1 or to Ar.sup.2 is in each case indicated by dashed bonds and X and R.sup.1 having the meaning given in claim 1; V stands on each occurrence, identically or differently, for O, S, NR.sup.1 or C(R.sup.1).sub.2; and Z stands on each occurrence, identically or differently, for CR.sup.2 or N, where a maximum of one group Z stands for N.

Description

EXAMPLES

(1) The following syntheses are, unless indicated otherwise, carried out in dried solvents under a protective-gas atmosphere. The starting materials can be purchased, for example, from Sigma-ALDRICH or ABCR. The numbers in square brackets in the case of the starting materials which are known from the literature refer to the CAS numbers.

A: Synthesis of Synthones

Example 1

(2-Bromophenyl)phenyl-(2,4,6-trimethylphenyl)amine, S1

(2) ##STR00125##

(3) 1.0 g (5 mmol) of tri-tert-butylphosphine and 561 mg (2.5 mmol) of palladium(II) acetate are added to a mixture of 21.1 g (100 mmol) of phenyl-(2,4,6-trimethylphenyl)amine [23592-67-8], 31.1 g (110 mmol) of 1-bromo-2-iodobenzene [583-55-1] and 13.5 g (140 mmol) of sodium tert-butoxide in 600 ml of toluene, and the mixture is then heated under reflux for 20 h. After cooling to 60° C., 500 ml of water are added to the reaction mixture, the organic phase is separated off, washed twice with 300 ml of water each time and dried over magnesium sulfate. After removal of the toluene in vacuo, the residue is recrystallised from methanol with addition of a little ethyl acetate. Yield: 25.7 g (70 mmol), 70%; purity about 96% according to .sup.1H-NMR.

Example 2

Bis(2-bromophenyl)bisphenylmethane, S2

(4) ##STR00126##

(5) 100 ml (100 mmol) of a 1 M phenylmagnesium bromide solution are added dropwise to a solution of 34.0 g (100 mmol) of 2,2′-dibromobenzophenone [25187-01-3] in 500 ml of THF, and the mixture is subsequently stirred at 50° C. for 3 h. After addition of 300 ml of 1 N acetic acid and stirring for 30 min. at room temperature, the organic phase is separated off, diluted with 300 ml of ethyl acetate, washed once with 500 ml of water and once with 500 ml of saturated sodium chloride solution, dried over magnesium sulfate and then evaporated to dryness in vacuo. The foam obtained in this way is dissolved in 300 ml of dichloromethane, 8.0 ml (110 mmol) of thionyl chloride and 2 drops of DMF are added, and the mixture is heated under reflux for 30 min. When the evolution of gas is complete, the mixture is evaporated to dryness in vacuo, the residue is taken up in 27.4 ml (300 mmol) of aniline and heated at 200° C. for 5 min. with stirring. The reaction mixture is allowed to cool to 80° C., a mixture of 150 ml of 2 N HCl and 120 ml of methanol is added, and the mixture is stirred under reflux for a further 30 min. After cooling, the solid is filtered off with suction, washed once with a little methanol, the solid is suspended in a mixture of 200 ml of ethanol and 30 ml of conc. sulfuric acid, the reaction mixture is cooled to −10° C. in an ice/sodium chloride bath, 25 ml (220 mmol) of isoamyl nitrite are added dropwise, and the mixture is stirred for a further 30 min. 50 ml of 50% by weight aqueous hypophosphoric acid are then added, the mixture is slowly warmed and is stirred under reflux for a further 30 min. After cooling, the solid is filtered off with suction, washed three times with 50 ml of ethanol each time and then recrystallised twice from dioxane. Yield: 32.6 g (68 mmol), 68%; purity about 97% according to .sup.1H-NMR.

Example 3

9,9-Bis(6-bromopyridin-2-yl)-9,10-dihydroanthracene, S3

(6) ##STR00127##

(7) Variant A: Via Grignard Reagent

(8) The corresponding Grignard reagent is prepared from 2.7 g (110 mmol) of iodine-activated magnesium turnings and a mixture of 24.7 g (110 mmol) of 2-bromophenylphenylmethane [23450-18-2], 0.8 ml of 1,2-dichloroethane, 30 ml of 1,2-dimethoxyethane and 200 ml of THF with secondary heating using an oil bath at 70° C. When the magnesium has reacted completely, the mixture is allowed to cool to room temperature, and a solution of 34.2 g (100 mmol) of bis(6-bromopyridin-2-yl)methanone [42772-87-2] in 150 ml of THF is then added dropwise, and the mixture is then stirred at room temperature for a further 12 h. 100 ml of water are added, the mixture is then stirred briefly, the organic phase is separated off, and the solvent is removed in vacuo. The residue is suspended in 500 ml of warm glacial acetic acid at 40° C., 50 ml of acetic anhydride and then, dropwise, 10 ml of conc. sulfuric acid are added to the suspension. The solution obtained in this way is stirred at 80° C. for a further 1 h, the solvent is then removed in vacuo, the residue is taken up in 500 ml of dichloromethane, washed once with 500 ml of 2 N NaOH, once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and then dried over magnesium sulfate. After removal of the dichloromethane in vacuo, the residue is recrystallised from 40 ml of ethyl acetate with addition of about 40 ml of ethanol. Yield: 27.6 g (56 mmol), 56%; purity about 98% according to .sup.1H-NMR.

(9) Variant B: Via Lithium Reagent

(10) 40.0 ml (100 mmol) of n-butyllithium (2.5 M in hexane) are added dropwise with stirring to a solution, cooled to −78° C., of 24.7 g (110 mmol) of 2-bromophenylphenylmethane [23450-18-2] in 300 ml of THF. The mixture is stirred for a further 30 min., a solution of 34.2 g (100 mmol) of bis(6-bromopyridin-2-yl)methanone [42772-87-2] in 150 ml of THF is then added dropwise, and the mixture is allowed to warm slowly to room temperature. Further procedure as described in the case of Variant A. Yield: 23.2 g (47 mmol), 47%; purity about 96% according to .sup.1H-NMR.

(11) The following derivatives are prepared analogously:

(12) TABLE-US-00003 Bromide Ex. Variant Product Yield  4 69%  5 0 17%  6 65%  7 69%  8 58%  9 54% 10 0 60% 11 44% 12 30% 13 18% 14 42% 15 0 23%

Example 16

9,9-Bis(6-bromopyridin-2-yl)anthracen-9-one, S16

(13) ##STR00152##

(14) A solution of 20.0 g (200 mmol) of chromium trioxide in 200 ml of water is added dropwise at 100° C. to a vigorously stirred suspension of 49.2 g (100 mmol) of 9,9-bis(6-bromopyridin-2-yl)-9,10-dihydroanthracene, S3, and 300 g of glass beads (diameter 3 mm) in a mixture of 500 ml of acetic acid and 300 ml of water. The reaction mixture is stirred at 100° C. for a further 16 h, allowed to cool, 1000 ml of ethyl acetate are added, the mixture is washed three times with 500 ml of water each time, once with 500 ml of saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate. The ethyl acetate is removed in vacuo, and the residue is recrystallised from toluene/cyclohexane. Yield: 35.4 g (70 mmol), 70%; purity about 96% according to .sup.1H-NMR.

Example 17

9,9-Bis(6-bromopyridin-2-yl)anthracen-9-one, S17

(15) ##STR00153##

(16) 27.1 g (110 mmol) of m-chloroperbenzoic acid, moist, 70%, are added in portions with stirring to a solution of 58.6 g (100 mmol) of 5,5-bis(6-bromopyridin-2-yl)-5,10-dihydro-10-phenylacridophosphine oxide, S11, in 500 ml of dichloromethane. After the mixture has been stirred for a further 16 h, the organic phase is washed once with 500 ml of 1 N NaOH and three times with 300 ml of water and dried over magnesium sulfate. After removal of the dichloromethane in vacuo, the residue is recrystallised from ethyl acetate with addition of ethanol. Yield: 47.1 g (78 mmol), 78%; purity about 97% according to .sup.1H-NMR.

Example 18

9,9-Bis(6-bromopyridin-2-yl)-9,10-dihydroanthracene-10,10-spirobifluorene, S18

(17) ##STR00154##

(18) The corresponding Grignard reagent is prepared from 2.7 g (110 mmol) of iodine-activated magnesium turnings and a mixture of 25.6 g (110 mmol) of 2-bromobiphenyl, 0.8 ml of 1,2-dichloroethane, 50 ml of 1,2-dimethoxyethane, 400 ml of THF and 200 ml of toluene with secondary heating using an oil bath at 70° C. When the magnesium has reacted completely, the mixture is allowed to cool to room temperature, and a solution of 50.6 g (100 mmol) of 9,9-bis(6-bromopyridin-2-yl)anthracen-9-one, S16, in 300 ml of THF is then added dropwise, and the mixture is stirred at room temperature for a further 12 h. 100 ml of water are added, the mixture is then stirred briefly, the organic phase is separated off, and the solvent is removed in vacuo. The residue is suspended in 500 ml of warm glacial acetic acid at 40° C., 0.2 ml of conc. sulfuric acid is added to the suspension, and the mixture is subsequently stirred at 100° C. for a further 2 h. The solvent is then removed in vacuo, the residue is taken up in 1000 ml of dichloromethane, washed once with 500 ml of 2 N NaOH, once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. After removal of the dichloromethane in vacuo, the residue is recrystallised from dioxane. Yield: 48.8 g (76 mmol), 76%; purity about 98% according to .sup.1H-NMR.

Synthesis of Ligands

Example 19

L1

(19) ##STR00155##

(20) 526 mg (2.6 mmol) of tri-tert-butylphosphine and 449 mg (2 mmol) of palladium(II) acetate are added to a vigorously stirred mixture of 49.2 g (100 mmol) of 9,9-bis(6-bromopyridin-2-yl)-9,10-dihydroanthracene, S3, 48.8 g (400 mmol) of phenylboronic acid [98-80-6], 35.0 g (600 mmol) of potassium fluoride, anhydrous, and 700 ml of THF, and the mixture is then heated under reflux for 8 h. After cooling, the solvent is removed in vacuo, the residue is taken up in 500 ml of dichloromethane, washed three times with 300 ml of water each time and then dried over magnesium sulfate. After removal of the dichloromethane in vacuo, the residue is recrystallised from ethyl acetate/cyclohexane, and the solid is subsequently freed from readily volatile and non-volatile components by fractional sublimation (p about 10.sup.−5 mbar, T about 260-280° C.). Yield: 40.4 g (83 mmol), 83%; purity: about 99.0% according to .sup.1H-NMR.

(21) The following derivatives are prepared analogously:

(22) TABLE-US-00004 Bromide/ Ex. boronic acid Ligand Yield 20 80% 21 77% 22 0 74% 23 23% 24 80% 25 77% 26 56% 27 0 73% 28 78% 29 68% 30 75% 31 48% 32 0 65% 33 69% 34 73% 35 76% 36 63% 37 0 34% 38 45% 39 26% 40 67% 41 63% 42 00 01 75% 43 02 03 76% 44 04 05 69% 45 06 07 74%

Example 46

9,9-Bis(benzo[h]quinolin-2-yl)-10,10-dimethyl-9,10-dihydroanthracene, L28

(23) ##STR00208##

(24) a) Bisbenzo[h]quinolin-2-ylmethanone

(25) ##STR00209##

(26) 80.0 ml (200 mmol) of n-butyllithium (2.5 M in n-hexane) are added dropwise to a solution, cooled to −78° C., of 51.6 g (200 mmol) of 2-bromo-benzo[h]quinoline [1097204-18-6] in 1000 ml of THF, and the mixture is stirred for a further 1 h. A mixture of 9.2 g (100 mmol) of N,N-dimethyl-carbamoyl chloride [79-44-7] and 30 ml of THF is then added in one portion with vigorous stirring. The reaction mixture is allowed to warm slowly to room temperature, a mixture of 8 ml of acetic acid and 200 ml of water is added, the mixture is stirred at room temperature for a further 5 h, the aqueous phase is separated off, and the organic phase is evaporated to dryness. The residue is dissolved in about 300 ml of boiling DMF, 10 ml of water and 1 ml of acetic acid are added dropwise to the solution, and the mixture is stirred under reflux for a further 2 h. The mixture is allowed to cool to 80° C., 300 ml of EtOH are added dropwise, the mixture is allowed to cool to room temperature with stirring, the deposited crystals are filtered off with suction, washed twice with about 50 ml of EtOH and dried in vacuo. Yield: 26.2 g (68 mmol), 68%; purity about 97% according to .sup.1H-NMR.

(27) b) L28

(28) Procedure analogous to Example 3, S3, using 30.3 g (110 mmol) of 1-bromo-2-(1-methyl-1-phenylethyl)benzene [796966-97-7] instead of 2-bromophenylphenylmethane and using 38.4 g (100 mmol) of bisbenzo[h]-quinolin-2-yl-methanone instead of bis(6-bromopyridin-2-yl)methanone. The solid is subsequently freed from readily volatile and non-volatile components by fractional sublimation (p about 10.sup.−5 mbar, T about 260-280° C.). Yield: 23.1 g (41 mmol), 41%; purity: about 99.0% according to .sup.1H-NMR.

(29) The following derivatives are prepared analogously:

(30) TABLE-US-00005 Ex. Bromide/Variant Product Yield 47 0 46% 48 43%

Example 59

L31

(31) ##STR00214##

(32) A mixture of 52.0 g (100 mmol) of S4, 31.0 g (250 mmol) of 3-tert-butyl-1H-pyrazole [15802-80-9], 3.8 g (20 mmol) of copper(I) iodide, 200 g of glass beads (diameter 3 mm) and 200 ml of nitrobenzene is heated at 200° C. for 2 h. After cooling, the mixture is diluted with 1000 ml of dichloromethane, the glass beads and the salts are filtered off, and the mixture is evaporated to dryness in vacuo. The residue is taken up in 500 ml of THF, filtered through silica gel in order to remove dark components, then evaporated to about 100 ml, methanol (about 200 ml) is added to the warm mixture until crystallisation commences, the mixture is allowed to cool with stirring, the solid is filtered off with suction, washed three times with about 50 ml of methanol each time and dried in vacuo. The solid is subsequently freed from readily volatile and non-volatile components by fractional sublimation (p about 10.sup.−5 mbar, T about 260-280° C.). Yield: 27.3 g (45 mmol), 45%; purity: about 99.0% according to .sup.1H-NMR.

(33) The following derivative is prepared analogously:

(34) TABLE-US-00006 Ex. Pyrazole Product Yield 50 38%

Synthesis of Metal Complexes

Example 51

Synthesis of Platinum Complexes

(35) Variant A:

(36) A vigorously stirred mixture of 10 mmol of potassium tetrachloroplatinate, 10 mmol of the ligand L, 150 g of glass beads (diameter 3 mm) and 300 ml of glacial acetic acid is heated under reflux for 48 to 60 h until the o-metallation is complete. After dropwise addition of a mixture of 300 ml of water and 300 ml of ethanol to the cooled reaction mixture, the solid is filtered off with suction, washed five times with 25 ml of ethanol each time and dried in vacuo. The solid is suspended in 100 ml of glacial acetic acid, 20 ml of pyridine and 2.0 g of zinc dust are added to the suspension, and the mixture is stirred at 60° C. for 12 h. After cooling, the solid is filtered off with suction, washed three times with 25 ml of ethanol each time and dried in vacuo. The solid obtained in this way is placed on a Celite bed with a depth of 3 cm in a hot extractor and extracted with toluene (initially introduced amount about 200 ml). Metal complexes which have excessively good solubility in the extractant are brought to crystallisation by dropwise addition of 200 ml of ethanol. The solid of the suspensions obtained in this way is filtered off with suction, washed once with about 50 ml of ethanol and dried. After drying, the purity of the metal complex is determined by means of NMR and/or HPLC. If the purity is below 99.5%, the hot-extraction step is repeated; when a purity of 99.5-99.9% has been reached, the Pt complex is sublimed. The sublimation is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 320 to about 380° C., where the sublimation is preferably carried out in the form of a fractional sublimation.

(37) Variant B:

(38) A mixture of 10 mmol of bis(benzonitrile)platinum(II) dichloride and 10 mmol of the ligand L in 100 ml of benzonitrile is heated under reflux for 6 to 48 h until the o-metallation is complete. After dropwise addition of 100 ml of ethanol to the cooled reaction mixture, the solid is filtered off with suction, washed five times with 25 ml of ethanol each time and dried in vacuo. Further procedure as described under variant A.

(39) The following derivatives are prepared analogously:

(40) TABLE-US-00007 Ex. Ligand Pt complex/Variant Yield 52 41% 53 L2  PtL2 38% A 54 L3  PtL3 37% A 55 L4  PtL4 44% B 56 L5  PtL5 13% B 57 L6  PtL6 45% A 58 L7  PtL7 47% B 59 L8  PtL8 46% B 60 L9  PtL9 43% B 61 L10 PtL10 38% B 62 L11 PtL11 28% B 63 L12 PtL12 35% A 64 L13 PtL13 38% A 65 L14 PtL14 41% A 66 L15 PtL15 44% A 67 L16 PtL16 40% B 68 L17 PtL17 36% B 69 L18 PtL18 43% B 70 L19 PtL19 38% A 71 L20 PtL20 35% B 72 L21 PtL21 16% B 73 L22 PtL22 37% B 74 L23 Use of 20 mmol of K.sub.2PtCl.sub.4 23% 75 L24 PtL24 45% A 76 L25 PtL25 46% B 77 L26 PtL26 39% A 78 L27 PtL27 46% B 79 L28 0 40% 80 L29 PtL29 46% B 81 L30 PtL30 41% B 82 L31 36% 83 L32 PtL32 28% B

Example 84

Production of OLEDs

(41) 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).

(42) The results of various OLEDs are presented in the following examples (see Tables 1 and 2). Glass plates coated with structured ITO (indium tin oxide) in a thickness of 150 nm are coated with 20 nm of PEDOT (poly(3,4-ethylenedioxy-2,5-thiophene), applied by spin coating from water; purchased from H. C. Starck, Goslar, Germany) for improved processing. These coated glass plates form the substrates to which the OLEDs are applied. The OLEDs have basically the following layer structure:

(43) Substrate

(44) Hole-injection layer 1: HIL1, 10 nm

(45) Hole-injection layer 2: HIL2, 10 nm

(46) Hole-injection layer 3: HIL1, 200 nm

(47) Hole-injection layer 4: HIL2, 10 nm

(48) Hole-transport layer 1: HTL1, 20 nm

(49) Electron-blocking layer 1: EBL1, optional, see Table 1, 10 nm

(50) Emission layer: see Table 1

(51) Hole-blocking layer 1: M1, 10 nm

(52) Electron-transport layer: ETM1+LiQ, 50%:50%, 30 nm

(53) Cathode: aluminium, 100 nm

(54) For the vacuum-processed OLEDs, 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), which is admixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as M1:M2:PtL (55%:35%:10%) here means that material M1 is present in the layer in a proportion by volume of 55%, M2 is present in the layer in a proportion of 35% and the emitter PtL is present in the layer in a proportion of 10%. Analogously, the electron-transport layer likewise consists of a mixture of two materials. The precise structure of the emission layer is shown in Table 1. The materials used for the production of the OLEDs are shown in Table 3.

(55) 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) are determined from current/voltage/luminance characteristic lines (IUL characteristic lines). 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 certain initial luminous density. The expression LT50 means that the lifetime given is the time at which the luminous density has dropped to 50% of the initial luminous density, i.e. from, for example, 4000 cd/m.sup.2 to 2000 cd/m.sup.2. Depending on the emission colour, different initial luminances were selected. The values for the lifetime can be converted to a figure 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 figure here.

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

(57) The compounds according to the invention can be employed, inter alia, as phosphorescent emitter materials in the emission layer in OLEDs. In the case of the OLEDs, it is evident here that the materials according to the invention result in efficient blue-, green- or red-emitting OLEDs.

(58) TABLE-US-00008 TABLE 1 Use of compounds according to the invention as emitters in phosphorescent OLEDs Ex. EBL EML/thickness 85 — M1:M2:PtL1 (80%:15%:5%) 30 nm 86 — M1:M2:PtL2 (80%:15%:5%) 30 nm 87 — M1:M2:PtL3 (80%:15%:5%) 30 nm 88 10 nm M4:M2:PtL4 (70%:25%:5%) 30 nm 89 — M1:M2:PtL5 (75%:20%:5%) 30 nm 90 — M1:M2:PtL6 (80%:15%:5%) 30 nm 91 10 nm M4:M2:PtL7 (70%:25%:5%) 30 nm 92 — M1:M2:PtL8 (80%:15%:5%) 30 nm 93 10 nm M4:M2:PtL9 (75%:20%:5%) 30 nm 94 10 nm M4:M2:PtL10 (70%:25%:5%) 30 nm 95 10 nm M4:M2:PtL11 (70%:25%:5%) 30 nm 96 — M1:M2:PtL12 (80%:15%:5%) 30 nm 97 — M1:M2:PtL13 (80%:15%:5%) 30 nm 98 — M1:PtL14 (85%:15%) 30 nm 99 — M1:M2:PtL15 (80%:15%:5%) 30 nm 100 — M1:M2:PtL16 (80%:15%:5%) 30 nm 101 10 nm M4:M2:PtL17 (75%:20%:5%) 30 nm 102 10 nm M4:M2:PtL18 (60%:35%:5%) 30 nm 103 — M1:M2:PtL19 (80%:15%:5%) 30 nm 104 — M1:M2:PtL20 (80%:15%:5%) 30 nm 105 — M1:M2:PtL21 (80%:10%:10%) 30 nm 106 — M1:M2:PtL22 (80%:15%:5%) 30 nm 107 — M1:M2:PtL23 (80%:15%:5%) 30 nm 108 10 nm M4:M2:PtL24 (65%:30%:5%) 30 nm 109 10 nm M4:M2:PtL25 (60%:35%:5%) 30 nm 110 10 nm M4:M2:PtL26 (60%:35%:5%) 30 nm 111 — M1:M2:PtL27 (80%:15%:5%) 30 nm 112 — M1:M2:PtL28 (80%:15%:5%) 30 nm 113 — M1:M2:PtL29 (80%:15%:5%) 30 nm 114 — M1:M2:PtL30 (80%:15%:5%) 30 nm 115 10 nm M4:M2:PtL31 (60%:35%:5%) 30 nm 116 10 nm M4:M2:PtL32 (60%:35%:5%) 30 nm

(59) TABLE-US-00009 TABLE 2 Use of compounds according to the invention as emitters in phosphorescent OLEDs EQE [%] CIE x/y at 1000 Voltage (V) at 1000 LT50 (h) Ex. cd/m.sup.2 at 1000 cd/m.sup.2 cd/m.sup.2 at 1000 cd/m.sup.2 85 20.0 3.4 0.32/0.64 800 86 20.3 3.3 0.32/0.64 34000 87 20.7 3.6 0.32/0.64 38000 88 14.0 4.8 0.15/0.24 800 89 18.9 3.5 0.32/0.64 18000 90 20.2 3.6 0.32/0.64 45000 91 14.8 4.3 0.16/0.27 — 92 18.6 3.5 0.27/0.58 27000 93 18.1 4.3 0.16/0.34 — 94 13.5 4.6 0.15/0.26 1600 95 12.9 4.9 0.15/0.24 96 19.6 3.6 0.33/0.63 37000 97 14.8 3.5 0.68/0.32 25000 98 19.9 3.5 0.32/0.64 41000 99 21.0 3.6 0.32/0.64 43000 100 20.4 4.2 0.32/0.64 40000 101 16.2 4.3 0.16/0.27 — 102 13.4 4.8 0.15/0.25 — 103 18.8 3.7 0.32/0.64 29000 104 16.0 4.6 0.29/0.59 — 105 11.2 3.5 0.68/0.32 17000 106 14.5 3.6 0.68/0.32 — 107 21.4 3.5 0.33/0.63 44000 108 20.4 3.5 0.33/0.63 45000 109 11.5 4.5 0.16/0.28 1100 110 18.5 3.7 0.33/0.63 30000 111 20.4 4.0 0.33/0.63 39000 112 20.8 3.6 0.26/0.63 54000 113 21.0 3.7 0.26/0.63 52000 114 20.3 3.4 0.25/0.62 55000 115 12.0 4.6 0.15/0.25 — 116 11.8 5.3 0.15/0.22 —

(60) TABLE-US-00010 TABLE 3 Structural formulae of the materials used HIL1 HIL2 HTL1 EBL1 M1 M2 M3 M4 0 ETM1 LiQ