Triphenylene-based materials for organic electroluminescent devices

Abstract

The present invention relates to compounds of the formula (1) and (2) which are suitable for use in electro¬nic devices, in particular organic electroluminescent devices.

Claims

1. A neutral compound of the formula (2), ##STR00199## where the following applies to the symbols and indices used: Z is on each occurrence, identically or differently, CR″ or N, with the proviso that a maximum of two groups Z per ring stand for N; R is selected on each occurrence, identically or differently, from the group consisting of N(Ar.sup.1).sub.2, C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2 and 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.1; Ar.sup.1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R.sup.3; two radicals Ar.sup.1 here which are bonded to the same N atom or P atom may also be bridged to one another by a single bond or a bridge selected from N(R.sup.4), C(R.sup.4).sub.2, O or S; R.sup.1 is hydrogen; R″ is selected on each occurrence, identically or differently, from the group consisting of H or where two or more adjacent substituents R″ which are bonded to the same benzene ring may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system; R.sup.3 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(R.sup.4).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.4, P(═O)(Ar.sup.1).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, where the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group is optionally substituted by one or more radicals R.sup.4, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.4C═CR.sup.4, C═C, Si(R.sup.4).sub.2, C═O, C═NR.sup.4, P(═O)(R.sup.4), SO, SO.sub.2, NR.sup.4, O, S or CONR.sup.4 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, 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.4, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.4, or a combination of these systems, where two or more adjacent substituents R.sup.3 may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which is optionally substituted by one or more radicals R.sup.4; R.sup.4 is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or an alkyl group having 1 to 5 C atoms, where two or more adjacent substituents R.sup.4 may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; with the proviso that the following compounds are excluded from the invention: ##STR00200## ##STR00201##

2. The compound according to claim 1, wherein the compound is selected from the compounds of the formula (7), ##STR00202## where symbols used have the meanings given in claim 1.

3. The compound according to claim 1, wherein the compound is selected from the compounds of the formula (7a), ##STR00203## where the symbols used have the meanings given in claim 1.

4. The compound according claim 1, wherein, and in that in compounds of the formula (2) the two radicals R are identical.

5. The compound according claim 2, wherein, and in that in compounds of the formula (7) the two radicals R are identical.

6. The compound according claim 3, wherein, and in that in compounds of the formula (7a), the two radicals R are identical.

7. A process for the preparation of the compound according to claim 1 which comprises reacting 1,12-dilithiotriphenylene derivatives with electrophiles or by reaction of halogen- or amino-substituted triphenylene derivatives in a metal-catalyzed coupling reaction.

8. An oligomer, polymer or dendrimer containing one or more of the compounds according to claim 1, where one or more bonds are present from the compound to the polymer, oligomer or dendrimer.

9. An electronic device which comprises the compound according to claim 1.

10. An electronic device which comprises the oligomer, polymer or dendrimer according to claim 8.

11. The electronic device as claimed in claim 9, wherein the device is selected from the group consisting of organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic plasmon emitting devices.

12. An organic electroluminescent device which comprises the compound according to claim 1 is employed as matrix material for fluorescent or phosphorescent emitters and/or as fluorescent emitter and/or in a hole-blocking layer and/or in an electron-transport layer and/or in an electron-blocking or exciton-blocking layer and/or in a hole-transport or hole-injection layer and/or in an optical coupling-out layer.

13. An organic electroluminescent device which comprises the compound according to claim 1 is used as matrix material for phosphorescent emitters and where the group Ar.sup.1 or the radicals on Ar.sup.1 or the aromatic or heteroaromatic ring system or the radicals R.sup.3 on the aromatic or heteroaromatic ring system contains no condensed aryl groups having more than 10 C atoms and no condensed heteroaryl groups in which more than two aryl or 6-membered heteroaryl groups are condensed directly onto one another; and/or in that, in the compound of the formula (2) or formula (7) or formula (7a), R stands, identically or differently on each occurrence, for N(Ar.sup.1).sub.2, C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2 or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, where the group Ar.sup.1 or the radicals on Ar.sup.1 or the aromatic or heteroaromatic ring system contains no condensed aryl groups having more than 10 C atoms and no condensed heteroaryl groups in which more than two aryl or 6-membered heteroaryl groups are condensed directly onto one another.

14. The organic electroluminescent device according to claim 13, wherein at least one radical R is selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, ortho-, meta- or para-terphenyl, ortho-, meta-, para- or branched quaterphenyl, fluorene or spirobifluorene, each of which is optionally substituted by one or more radicals R.sup.3, and at least one radical R is selected from the structures of the formulae (8) to (38), ##STR00204## ##STR00205## ##STR00206## ##STR00207## ##STR00208## wherein R.sup.3 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(R.sup.4).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.4, P(═O)(Ar.sup.1).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, where the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group is optionally substituted by one or more radicals R.sup.4, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.4C═CR.sup.4, C═C, Si(R.sup.4).sub.2, C═O, C═NR.sup.4, P(═O)(R.sup.4), SO, SO.sub.2, NR.sup.4, O, S or CONR.sup.4 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, 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.4, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.4, or a combination of these systems, where two or more adjacent substituents R.sup.3 may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which is optionally substituted by one or more radicals R.sup.4; R.sup.4 is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or an alkyl group having 1 to 5 C atoms, where two or more adjacent substituents R.sup.4 may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; Ar.sup.1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R.sup.3; two radicals Ar.sup.1 here which are bonded to the same N atom or P atom may also be bridged to one another by a single bond or a bridge selected from N(R.sup.4), C(R.sup.4).sub.2, O or S; and the dashed bond represents the bond to the triphenylene skeleton; and at least one radical R selected from the structures of the formulae (39) to (41) and/or in that at least one radical R.sup.2 is selected from the structures of the formula (40), ##STR00209## Ar.sup.2 is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3; the sum of the aromatic ring atoms of all groups Ar.sup.2 together is not greater than 60; and E is selected from the group consisting of C(R.sup.4).sub.2, NR.sup.4, O or S.

15. An organic electroluminescent device which comprises the compound according to claim 1 is used as electron-transport material and at least one radical R stands for C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2 or for an electron-deficient heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3.

16. The organic electroluminescent device according to claim 15, wherein the electron-deficient heteroaromatic ring system R contains, as heteroaryl group, triazine, pyrimidine, pyrazine, pyridazine, pyridine, imidazole, pyrazole, oxazole, oxadiazole, triazole, thiazole, thiadiazole, benzimidazole, quinoline, isoquinoline or quinoxaline and in particular is selected from the structures of the formulae (8) to (11) or from the formulae (42) to (45), ##STR00210## ##STR00211## R.sup.3 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(R.sup.4).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.4, P(═O)(Ar.sup.1).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, where the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group is optionally substituted by one or more radicals R.sup.4, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.4C═CR.sup.4, Si(R.sup.4).sub.2, C═O, C═NR.sup.4, P(═O)(R.sup.4), SO, SO.sub.2, NR.sup.4, O, S or CONR.sup.4 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, 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.4, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.4, or a combination of these systems, where two or more adjacent substituents R3 may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which is optionally substituted by one or more radicals R.sup.4; R.sup.4 is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or an alkyl group having 1 to 5 C atoms, where two or more adjacent substituents R.sup.4 may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; Ar.sup.1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R3; two radicals Ar1 here which are bonded to the same N atom or P atom may also be bridged to one another by a single bond or a bridge selected from N(R.sup.4), C(R.sup.4).sub.2, O or S; and the dashed bond represents the bond to the triphenylene skeleton.

17. An organic electroluminescent device which comprises the compound according to claim 1 is used as hole-transport material or as emitting compound and at least one radical R stands for N(Ar.sup.1).sub.2, for a triarylamino group or for an electron-rich heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3.

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

19. A formulation comprising at least one or more polymers, oligomers or dendrimers according to claim 8 and at least one solvent.

20. An organic electroluminescent device which comprises the compound according to claim 1 is used as an electron transport material.

Description

EXAMPLES

A) Synthesis Examples

(1) The following syntheses are carried out, unless indicated otherwise, in dried solvents under a protective-gas atmosphere. The metal complexes are additionally handled with exclusion of light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The CAS numbers of the starting materials are in each case indicated in square brackets.

Example 1: 4-(2,4,6-Trimethylphenyl)-4H-4-boracyclopenta[def]-triphenylene

(2) ##STR00115##

A: 1,12-Dilithiotriphenylene*2 TMEDA

(3) 58.1 g (500 mmol) of N,N-tetramethylethylenediamine are added dropwise to 312.5 ml (500 mmol) of n-butyllithium (1.6 M in n-hexane), and the mixture is stirred at room temperature for 1 h. A solution of 22.8 g (100 mmol) of triphenylene in 150 ml of n-hexane is added dropwise to the mixture, which is subsequently heated under reflux for 5 h. After about 250 ml of n-hexane have been distilled off, the reaction mixture is allowed to cool and is then cooled at −30° C. for 24 h, during which a brown solid deposits. The brown solid is filtered off with suction, washed three times with 100 ml of ice-cold n-hexane each time and dried in vacuo. Yield: 134.7 g (285 mmol), 57%. Care: 1,12-dilithiotriphenylene*2 TMEDA is pyrophoricl

B: 4-(2,4,6-Trimethylphenyl)-4H-4-boracyclopenta[def]triphenylene

(4) A solution of 20.1 g (100 mmol) of dichloro-2,4,6-trimethylphenylborane [69464-76-2] in 500 ml of THF is added dropwise to a solution of 47.2 g (100 mmol) of 1,12-dilithiotriphenylene*2 TMEDA in 1500 ml of THF, and the mixture is stirred at room temperature for 16 h. After removal of the solvent in vacuo, the residue is taken up in 500 ml of dichloromethane and washed three times with 200 ml of water each time. After drying over sodium sulfate, the organic phase is evaporated, the residue is recrystallised five times from dioxane and subsequently subjected to fractional sublimation in vacuo twice (p about 10.sup.−6 mbar, T about 300° C.). Yield 13.2 g (37 mmol), 37%. Purity: 99.9% according to HPLC.

(5) The following compounds are accessible analogously by reaction of 1,12-dilithiotriphenylene*2 TMEDA with the corresponding electrophiles:

(6) TABLE-US-00002 Ex. Electrophile Product Yield 2 38% 3 32% 4 0 26% 5 SiCl.sub.4 [10026-04-7] 14% 6 17% 7   [824-72-6] 41%

Example 8: 1,10-Bis-(N-phenylcarbazol-2-yl)-4H-4-thiacyclopenta[def]-triphenylene

(7) ##STR00127##

A) Triphenyleno[1,12-bcd]thiophene-2,11-diboronic acid

(8) ##STR00128##

(9) 48.8 g (420 mmol) of N,N-tetramethylethylenediamine are added to a suspension of 25.8 g (100 mmol) of triphenyleno[1,12-bcd]thiophene [68558-73-6] in 2000 ml of n-hexane, and 250 ml (400 mmol) of n-butyllithium (1.6 M in n-hexane) are then added dropwise, and the mixture is subsequently stirred at 60° C. for 4 h. After the mixture has been allowed to cool and cooled to −60° C., 46.8 g (450 mmol) of trimethyl borate are added in one portion with vigorous stirring. The mixture is stirred at −60° C. for a further 30 min., then allowed to warm to room temperature, the n-hexane is removed in vacuo, the residue is taken up in 300 ml of THF, a mixture of 300 ml of water and 30 ml of glacial acetic acid is added, the mixture is stirred for a further 2 h, the precipitated solid is filtered off with suction, washed twice with 200 ml of water each time and dried in vacuo. Yield: 30.7 g. Purity: about 90.0% according to NMR, the crude product is subsequently used without further purification.

B) 1,10-Bis-(N-phenylcarbazol-2-yl)-4H-4-thiacyclopenta[def]-triphenylene

(10) 913 mg (3 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added with stirring to a mixture of 17.3 g (50 mmol) of triphenyleno[1,12-bcd]thiophene-2,11-diboronic acid, 41.9 g (130 mmol) of 2-bromo-9-phenylcarbazole [94994-62-4] and 31.8 g (150 mmol) of tripotassium phosphate in a mixture of 200 ml of toluene, 100 ml of ethanol and 300 ml of water, and the mixture is heated under reflux for 16 h. After cooling, the precipitated solid is filtered off with suction, washed three times with 100 ml of a mixture of water and ethanol (1:1, v:v) each time and then three times with 100 ml of ethanol each time and dried in vacuo. The solid is subjected to hot-vapour extraction with toluene over aluminium oxide (basic, activity grade 1) five times and then subjected to fractional sublimation in vacuo twice (p about 10.sup.−6 mbar, T about 350° C.). Yield 12.6 g (34 mmol), 34%. Purity: 99.9% according to HPLC.

(11) The following compounds are accessible analogously by reaction of triphenyleno[1,12-bcd]thiophene-2,11-diboronic acid with the corresponding bromides:

(12) TABLE-US-00003 Ex. Bromide Product Yield  9 0 43% 10 31%

Example 11: 4-Biphenyl-4-yl-4H-4-azacyclopenta[def]triphenylene

(13) ##STR00133##

(14) 235 mg (1.3 mmol) of di-tert-butyichlorophosphine and then 225 g (1 mmol) of palladium(II) acetate are added to a vigorously stirred suspension of 12.1 g (50 mmol) of 4H-4-azacyclopenta[def]triphenylene [109606-75-9], 14.0 g (60 mmol) of 4-bromobiphenyl and 9.0 g (65 mmol) of potassium carbonate in 150 ml of toluene, and the mixture is heated under reflux for 16 h. After cooling to 60° C., water is added, the mixture is stirred for a further 30 min., the precipitated solid is then filtered off with suction, washed three times with 100 ml of a mixture of water and ethanol (1:1, v:v) each time and then three times with 100 ml of ethanol each time and dried in vacuo. The solid is subjected to hot-vapour extraction with toluene over aluminium oxide (basic, activity grade 1) five times and then subjected to fractional sublimation in vacuo twice (p about 10.sup.−6 mbar, T about 320° C.). Yield: 7.3 g (19 mmol), 37%. Purity: 99.9% according to HPLC.

(15) The following compounds are accessible analogously by reaction 4H-4-azacyclopenta[def]triphenylene with the corresponding bromides:

(16) TABLE-US-00004 Ex. Bromide Product Yield 12 52% 13 44% 28 38% 29 0 41% 30 26% 31 35% 32 42% 33 33% 34 0 24% 35 28% 36 31% 37 40% 38 30% 39 0 22% 40 41% 41 44% 42 38% 43 22% 44 0 34% 45 19% 46 27%

Example 14: 1,12-(Dibenzothiophen-2-yl)triphenylene

(17) ##STR00176##

(18) 304 mg (1 mmol) of tri-o-tolylphosphine and then 45 mg (0.2 mmol) of palladium(II) acetate are added with stirring to a mixture of 9.6 g (20 mmol) of 1,12-diiodotriphenylene [130197-34-1], 11.4 g (50 mmol) of 2-dibenzothiopheneboronic acid [108847-24-1] and 10.6 g (50 mmol) of tripotassium phosphate in a mixture of 200 ml of toluene, 50 ml of dioxane and 200 ml of water, and the mixture is heated under reflux for 30 h. After cooling, the precipitated solid is filtered off with suction, washed three times with 50 ml of a mixture of water and ethanol (1:1, v:v) each time and then three times with 50 ml of ethanol each time and dried in vacuo. The solid is subjected to hot-vapour extraction with toluene over aluminium oxide (basic, activity grade 1) four times and then subjected to fractional sublimation in vacuo twice (p about 10.sup.−6 mbar, T about 310° C.). Yield 5.0 g (8.4 mmol), 42%. Purity: 99.9% according to HPLC.

(19) The following compounds are accessible analogously by reaction with the corresponding boronic acids:

(20) TABLE-US-00005 Ex. Bromide Product Yield 47 13% 48 0 18%

Example 15: 4,4-Bis[1,1′,3′,1″]terphenyl-5′-yl-4H-cyclopenta[def]-triphenylene

(21) ##STR00181##

(22) A solution of 48.7 g (100 mmol) of bis[1,1′,3′,1″]terphenyl-5′-ylmethanone [1205748-29-3] in 500 ml of THF is added dropwise to a solution of 47.2 g (100 mmol) of 1,12-dilithiotriphenylene*2 TMEDA in 1500 ml of THF, and the mixture is then heated under reflux for 2 h. After quenching of the reaction mixture using 50 ml of ethanol and removal of the solvent in vacuo, the residue is taken up in 500 ml of glacial acetic acid, 20 ml of conc. hydrochloric acid and 20 ml of acetic anhydride are added to the suspension, and the mixture is heated under reflux for 3 h. After cooling, the precipitated solid is filtered off with suction, washed three times with 100 ml of ethanol each time and dried in vacuo. The solid is recrystallised five times from DMF and subsequently subjected to fractional sublimation in vacuo twice (p about 10.sup.−6 mbar, T about 350° C.). Yield: 38.3 g (55 mmol), 55%. Purity: 99.9% according to HPLC.

Example 49: 4,8,9,10-Pentaphenyl-4H-4-azacyclopenta[def]-triphenylene

(23) ##STR00182##

A: 8,9-Diiodo-1,2,3,4-tetraphenyltriphenylene

(24) 7.6 ml (50 mmol) of N,N-tetramethylethylenediamine are added dropwise to 31.3 ml (50 mmol) of n-butyllithium (1.6 M in n-hexane), and the mixture is stirred at room temperature for 1 h. A solution of 10.6 g (20 mmol) of 1,2,3,4-tetraphenyltriphenylene [36262-81-4] in 50 ml of n-hexane is added dropwise to the mixture, which is subsequently heated under reflux for 5 h. After about 75 ml of n-hexane have been distilled off, the reaction mixture is allowed to cool, is cooled to −100° C., 50 ml of THF are added, and a solution of 7.0 g (55 mmol) of iodine in 50 ml of THF is then slowly added dropwise. When the addition is complete, the mixture is allowed to warm slowly to room temperature. The reaction mixture is diluted with 200 ml of ethyl acetate, then washed once with 100 ml of saturated sodium sulfite solution, twice with 100 ml of water each time and once with 100 ml of sat. sodium chloride solution. After drying over magnesium sulfate and removal of the solvent in vacuo, the mixture is chromatographed on silica gel with heptane/ethyl acetate (4:1, v/v). Yield 7.1 g (9 mmol), 45%. Purity: 95% according to HPLC.

B

(25) A mixture of 7.8 g (10 mmol) of 8,9-diiodo-1,2,3,4-tetraphenyltriphenylene, 1.0 ml (11 mmol) of aniline, 2.4 g (25 mmol) of sodium tert-butoxide, 809 mg (4 mmol) of tri-tert-butylphosphine, 500 mg (2 mmol) of palladium-(II) acetate and 100 ml of toluene is heated under reflux for 16 h. After cooling, 100 ml of toluene are added to the reaction mixture, the mixture is washed twice with 100 ml of water each time, dried over magnesium sulfate, and the solvent is then removed in vacuo. The solid obtained in this way is subjected to hot-vapour extraction with toluene over aluminium oxide (basic, activity grade 1) four times and then subjected to fractional sublimation in vacuo twice (p about 10.sup.−6 mbar, T about 370° C.). Yield 2.9 g (4.6 mmol), 46%. Purity: 99.9% according to HPLC.

(26) The following compounds are accessible analogously by reaction with the corresponding amines:

(27) TABLE-US-00006 Ex. Amine Product Yield 50 38% 51 30%

B) Device Examples

Example 16: Production of OLEDs

(28) 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).

(29) The results for various OLEDs are presented in the following examples (see Tables 1, 2, 3, 4). 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 in principle the following layer structure: substrate/hole-injection layer (HIL, with HIL1, 20 nm)/hole-transport layer (HTL, with HTM1 (reference) or the HTMs according to the invention, 20 nm)/electron-blocking layer, optional (EBL, 10 nm)/emission layer (EML with the individual matrices according to the invention or mixed matrices M, 40 nm)/electron-transport layer (ETL, with ETL1, 20 nm)/electron-injection layer (EIL, with LiF, 1 nm) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The precise structure of the OLEDs, in particular the structure of the hole-conductor or emitter layer, and the results obtained with these OLEDs on use of the compounds according to the invention as hole-conductor material, matrix materials for phosphorescent emitters, as matrix materials for fluorescent emitters and as fluorescent dopants is shown in Table 1, 2, 3 and 4.

(30) The % data here relate to % by vol. The results for the use of compounds according to the invention both as matrix materials for phosphorescent emitters and also as hole-transport materials are shown in Table 1, 2, 3 and 4. Results for the use of compounds according to the invention both as matrix materials for fluorescent emitters, as blue-fluorescent emitters and also as hole-transport materials are shown in Table 5.

(31) The materials used for the production of the OLEDs are shown in Table 6.

(32) 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 admixed in a certain proportion by volume by co-evaporation.

(33) The as yet unoptimised OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A) and the voltage are determined. The efficiencies and voltages indicated in the tables relate to the corresponding values at an operating luminance of 1000 cd/m.sup.2.

(34) TABLE-US-00007 TABLE 1 Green-emitting OLEDs Efficiency Ex. EML [cd/A] Voltage [V] CIE, x/y 17 Ex. 1: 40.0 4.7 0.34/0.62 TEG1 (15%) 18 Ex. 2: 43.9 4.8 0.33/0.62 TEG1 (15%) 19 Ex. 5: 51.0 4.6 0.33/0.62 TEG1 (10%) 20 Ex. 5: 54.7 4.5 0.32/0.61 TEG2 (15%) 21 Ex. 5 (60%): 55.4 4.2 0.32/0.61 EBL (25%): TEG2 (15%) 22 Ex. 8: 28.0 4.1 0.33/0.61 TEG2 (15%) 23 Ex. 14: 45.2 4.2 0.32/0.61 TEG2 (15%)

(35) TABLE-US-00008 TABLE 2 Green-emitting OLEDs without EBL Efficiency Ex. HTM/EML [cd/A] Voltage [V] CIE, x/y 17 Ex. 28/ 46.0 4.0 0.34/0.61 TMM1: TEG2 (10%) 52 Ex. 29/ 57.9 3.8 0.35/0.61 TMM1: TEG2 (10%) 53 Ex. 37/ 67.0 3.9 0.35/0.61 TMM1: TEG2 (10%) 54 Ex. 29/ 64.5 3.7 0.35/0.61 TMM1 (60%) Ex. 29 (33%) TEG2 (7%) 55 Ex. 29/ 66.1 3.8 0.35/0.61 TMM1 (60%) Ex. 37 (33%) TEG2 (7%) 56 Ex. 29/ 56.0 4.2 0.34/0.61 Ex. 30 (60%) Ex. 29 (33%) TEG2 (7%) 57 Ex. 29/ 45.8 4.3 0.35/0.61 Ex. 31 (60%) Ex. 29 (33%) TEG2 (7%) 58 Ex. 29/ 61.8 3.9 0.33/0.62 Ex. 32 (70%) Ex. 29 (25%) TEG1 (5%) 59 Ex. 29/ 43.8 4.4 0.34/0.61 Ex. 33 (70%) Ex. 29 (25%) TEG2 (5%) 60 Ex. 29/ 48.9 4.2 0.35/0.61 Ex. 34 (60%) Ex. 29 (33%) TEG2 (7%) 61 Ex. 29/ 58.5 3.8 0.35/0.61 Ex. 35 (60%) Ex. 29 (30%) TEG2 (10%) 62 Ex. 29/ 61.6 3.8 0.35/0.61 Ex. 36 (65%) Ex. 29 (30%) TEG2 (5%) 63 Ex. 29/ 57.7 4.0 0.34/0.62 Ex. 38 (65%) Ex. 29 (30%) TEG2 (5%) 64 Ex. 37/ 45.2 4.1 0.35/0.61 Ex. 49 (50%) Ex. 29 (45%) TEG2 (5%) 65 Ex. 29/ 50.7 4.0 0.35/0.61 Ex. 50 (60%) Ex. 29 (33%) TEG2 (7%) 66 Ex. 29/ 49.3 4.2 0.35/0.61 Ex. 51 (70%) Ex. 29 (33%) TEG2 (7%)

(36) TABLE-US-00009 TABLE 3 Red-emitting OLEDs Efficiency Ex. EML [cd/A] Voltage [V] CIE, x/y 24 Ex. 13: 12.4 4.8 0.67/0.33 TER1 (15%) 25 Ex. 11: (20%) 13.6 4.6 0.67/0.33 Ex. 15: (70%) TER2 (10%)

(37) TABLE-US-00010 TABLE 4 Red-emitting OLEDs, without EBL Efficiency Ex. HTM/EML [cd/A] Voltage [V] CIE, x/y 26 Ex. 12/ 15.2 4.4 0.67/0.33 Ex. 8: TER1 (15%) 27 Ex. 13/ 14.3 4.1 0.67/0.33 Ex. 13: TER2 (10%)

(38) TABLE-US-00011 TABLE 5 Blue-emitting OLEDs Efficiency Ex. EML [cd/A] Voltage [V] CIE, x/y 67 Ex. 40: 5.3 6.5 0.14/0.15 SEB1 (5%) 68 Ex. 41: 5.2 6.4 0.14/0.15 SEB1 (5%) 69 Ex. 42: 4.9 8.0 0.14/0.16 SEB2 (1%) 70 Ex. 43: 5.5 5.2 0.14/0.16 SEB2 (1%) 71 Ex. 44: 5.0 7.8 0.14/0.16 SEB2 (1%) 72 Ex. 42: 4.0 6.0 0.15/0.18 Ex. 45 (5%) 73 Ex. 42: 6.2 5.8 0.15/0.16 Ex. 46 (5%)

(39) TABLE-US-00012 TABLE 6 Structural formulae of the materials used 0

(40) As is clearly evident from the examples given above, the materials according to the invention are particularly suitable for use as matrix materials for phosphorescent emitters and as hole conductors, where they result in high efficiencies and low operating voltages.