Compounds for electronic devices

Abstract

The present invention relates to compounds of the formula (1), (17) 18) or (20) and to the use thereof in electronic devices, and to electronic devices which contain these compounds. The invention furthermore relates to the preparation of the compounds of the formula (1), (17) 18) or (20) and to formulations contains one or more compounds of the formula (1), (17) 18) or (20).

Claims

1. A compound of the formula (17) ##STR00502## where the following applies to the symbols and indices occurring: Z is on each occurrence, identically or differently, CR, or is equal to C if a substituent is bonded to the group Z; L is on each occurrence, identically or differently, a divalent group selected from the group consisting of C(R).sub.2 and NR; R is, identically or differently on each occurrence, H, D, F, Cl, Br, I, CHO, N(R.sup.1).sub.2, C(═O)R.sup.1, P(═O)(R.sup.1).sub.2, S(═O).sub.2R.sup.1, S(═O).sub.2R.sup.1, CR.sup.1═C(R.sup.1).sub.2, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, OSO.sub.2R.sup.1, OH, COOR.sup.1, CON(R.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, each of which may be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by —R.sup.1C═CR.sup.1—, —C≡C—, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C═O, C═S, C═Se, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, —O—, —S—, —COO— or —CONR.sup.1— and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic ring system having 6 to 60 aromatic ring atoms 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, or an aryloxy group having 6 to 60 aromatic ring atoms or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a combination of these systems; R.sup.1 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, CHO, N(R.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, CR.sup.2═C(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, OH, COOR.sup.2, CON(R.sup.2).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, each of which may be substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups may be replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, C═O, C═S, C═Se, C═NR.sup.2, P(═O)(R.sup.2), SO, SO.sub.2, NR.sup.2, —O—, —S—, —COO— or —CONR.sup.2— and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic ring system having 6 to 60 aromatic ring atoms 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 group having 6 to 60 aromatic ring atoms or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, or a combination of these systems; R.sup.2 is, identically or differently on each occurrence, H, D, F or an aliphatic, aromatic and/or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by D or F; n is on each occurrence, identically or differently, 0 or 1, where the sum of the values of the indices n is 1; and where the compound contains only a single carbazole group.

2. The compound according to claim 1, wherein R is on each occurrence, identically or differently, H, D, F, CN, Si(R.sup.1).sub.3, N(R.sup.1).sub.2 or a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each of which may be substituted by one or more radicals R.sup.1, where one or more adjacent or non-adjacent CH.sub.2 groups may be replaced by —C≡C—, —R.sup.1C═CR.sup.1—, Si(R.sup.1).sub.2, C═O, C═NR.sup.1, —NR.sup.1—, —O—, —S—, —COO— or —CONR.sup.1—, or an aryl group having 6 to 30 aromatic ring atoms or heteroaryl group having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1.

3. An oligomer, polymer or dendrimer comprising one or more compounds according to claim 1, whereon the bond(s) to the polymer, oligomer or dendrimer may be localised at any desired positions substituted by a radical R in formula (17).

4. A formulation comprising at least one polymer, oligomer or dendrimer according to claim 3 and at least one solvent.

5. An electronic device comprising at least one polymer, oligomer or dendrimer according to claim 3.

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

7. A process for the preparation of a compound of the formula (17) according to claim 1, comprising at least one coupling reaction for the linking of the moiety containing the carbazole group to the moiety containing the arylamino group.

8. An electronic device comprising at least one compound according to claim 1.

9. The electronic device according to claim 8, wherein the device is selected from the group consisting of 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 electroluminescent devices (OLEDs).

10. An organic electroluminescent device wherein the compound according to claim 1 is employed as hole-transport material in a hole-transport layer or hole-injection layer and/or as matrix material in an emitting layer.

11. The compound according to claim 1, wherein R.sup.3 is selected, identically or differently, from straight-chain alkyl groups having 1 to 40 C atoms and branched or cyclic alkyl groups having 3 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.1.

12. The compound according to claim 1, wherein R.sup.3 is methyl.

13. The compound according to claim 1, wherein L is C(R.sup.3).sub.2.

14. A compound of the formula (I-A) ##STR00503## where the following applies to the symbols and indices occurring: W is on each occurrence equal to Z; Z is on each occurrence, identically or differently, CR or N, or is equal to C if a substituent is bonded to the group Z; L is on each occurrence, identically or differently, a divalent group selected from the group consisting of C(R).sub.2, NR, O, S, S═O and S(═O).sub.2, where at least one group L is selected from NR, O, S, S═O and S(═O).sub.2; R is, identically or differently on each occurrence, H, D, F, Cl, Br, I, CHO, 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, CR.sup.1═C(R.sup.1).sub.2, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, OSO.sub.2R.sup.1, OH, COOR.sup.1, CON(R.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, each of which may be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by —R.sup.1C═CR.sup.1—, —C≡C—, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C═O, C═S, C═Se, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, —O—, —S—, —COO— or —CONR.sup.1— and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic ring system having 6 to 60 aromatic ring atoms 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, or an aryloxy group having 6 to 60 aromatic ring atoms or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a combination of these systems; R.sup.1 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, CHO, N(R.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, CR.sup.2═C(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, OH, COOR.sup.2, CON(R.sup.2).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, each of which may be substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups may be replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, C═O, C═S, C═Se, C═NR.sup.2, P(═O)(R.sup.2), SO, SO.sub.2, NR.sup.2, —O—, —S—, —COO— or —CONR.sup.2— and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic ring system having 6 to 60 aromatic ring atoms 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 group having 6 to 60 aromatic ring atoms or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, or a combination of these systems; R.sup.2 is, identically or differently on each occurrence, H, D, F or an aliphatic, aromatic and/or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by D or F; i is equal to 0, 1 or 2, where, for i=0, the two groups which are bonded to the group with the index i are connected directly to one another; and wherein the compound contains only a single carbazole group.

15. The compound according to claim 14, wherein one group L is C(R).sub.2.

16. The compound according to claim 14, wherein Z is equal to CR or is equal to C if a substituent is bonded to the group Z.

17. The compound according to claim 14, wherein R is on each occurrence, identically or differently, H, D, F, CN, Si(R.sup.1).sub.3, N(R.sup.1).sub.2 or a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each of which may be substituted by one or more radicals R.sup.1, where one or more adjacent or non-adjacent CH.sub.2 groups may be replaced by —C≡C—, —R.sup.1C═CR.sup.1—, Si(R.sup.1).sub.2, C═O, C═NR.sup.1, —NR.sup.1—, —O—, —S—, —COO— or —CONR.sup.1—, or an aryl or heteroaryl group having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1.

18. A formulation comprising at least one compound according to claim 14 and at least one solvent.

19. An electronic device comprising at least one compound according to claim 14.

20. The electronic device according to claim 19, wherein the device is selected from the group consisting of 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 electroluminescent devices (OLEDs).

21. An organic electroluminescent device wherein the compound according to claim 14 is employed as hole-transport material in a hole-transport layer or hole-injection layer and/or as matrix material in an emitting layer.

22. The compound according to claim 14, wherein R in a group L=C(R).sub.2 is selected, identically or differently, from straight-chain alkyl groups having 1 to 40 C atoms and branched or cyclic alkyl groups having 3 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.1.

23. The compound according to claim 14, wherein R in a group L=C(R).sub.2 is methyl.

Description

USE EXAMPLES

A) Synthesis Examples

(1) The following syntheses were carried out, unless indicated otherwise, under a protective-gas atmosphere. The starting materials were purchased from ALDRICH or ABCR.

Example 1: Synthesis of 10-biphenyl-4-yl-9,9-dimethyl-2-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine (HTM2)

(2) ##STR00396##

a) Methyl 2-[4-(9-phenyl-9H-carbazol-3-yl)phenylamino]benzoate

(3) Caesium carbonate (25.4 g, 78 mmol), palladium acetate (0.9 g, 4 mmol) and xantphos (1.5 g, 8 mmol) are added to a solution of 3-(4-bromo phenyl)-9-phenyl-9H-carbazole (CAS 1028647-93-9, 31.0 g, 78 mmol) and methyl anthranilate (10.1 ml, 78 mmol) in degassed toluene (300 ml), and the mixture is heated under reflux for 8 h. The precipitated salts are filtered off, and the mother liquor is evaporated in vacuo. The residue is extracted with chloroform in a Soxhlet extractor and subsequently recrystallised from toluene.

(4) Yield: 26.0 g (55 mmol), 71% of theory, colourless solid.

b) 9,9-Dimethyl-2-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine

(5) Methyl 2-[4-(9-phenyl-9H-carbazol-3-yl)phenylamino]benzoate (26.0 g, 55 mmol) is added in portions to a suspension of anhydrous cerium(III) chloride (15.0 g, 61 mmol) in dried tetrahydrofuran (400 ml). A 3 M solution of methylmagnesium chloride in tetrahydrofuran (56.2 ml, 169 mmol) is subsequently added dropwise at 0° C., and the mixture is stirred at room temperature for 20 h. The reaction mixture is neutralised using 25% acetic acid (about 55 ml) with ice-cooling and diluted with dist. water and ethyl acetate. The aqueous phase is extracted with ethyl acetate, dried over sodium sulfate and evaporated in vacuo.

(6) The residue is dissolved in dichloromethane (100 ml) and added dropwise over the course of 20 min to a solution of polyphosphoric acid (43.4 g, 376 mmol) and methanesulfonic acid (24.9 ml, 379 mmol) in dichloro methane (100 ml). The reaction mixture is stirred at room temperature for 1 h and subsequently evaporated in vacuo. The residue is taken up in ethyl acetate, washed with dist. water, dried over sodium sulfate and evaporated in vacuo. The crude product is dissolved in ethyl acetate/dichloromethane (15/1), filtered through basic aluminium oxide and purified by recrystallisation from ethyl acetate.

(7) Yield: 18.7 g (42 mmol), 75% of theory, colourless solid.

c) 10-Biphenyl-4-yl-9,9-dimethyl-2-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine

(8) Caesium carbonate (26.0 g, 80 mmol), palladium acetate (0.4 g, 2 mmol) and xantphos (0.8 g, 4 mmol) are added to a solution of 9,9-dimethyl-2-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine (18.0 g, 40 mmol) and 4-bromobiphenyl (9.3 g, 40 mmol) in degassed toluene (250 ml), and the mixture is heated under reflux for 8 h. The precipitated salts are filtered off, and the mother liquor is evaporated in vacuo. The residue is extracted with toluene in a Soxhlet extractor. The crude product is subsequently recrystallised four times from toluene and purified by sublimation twice in vacuo (p=5×10.sup.−5 mbar, T=290° C.).

(9) Yield: 8.6 g (14 mmol), 36% of theory, purity >99.9% according to HPLC, colourless solid.

Example 2: Synthesis of 10-biphenyl-4-yl-2-(4-carbazol-9-ylphenyl)-9,9-dimethyl-9,10-dihydroacridine (HTM3)

(10) ##STR00397##

(11) 10-Biphenyl-4-yl-2-(4-carbazol-9-ylphenyl)-9,9-dimethyl-9,10-dihydroacridine is prepared analogously to Example 1 starting from 9-(4′-bromo-[1,1′-biphenyl]-4-yl)-9H-carbazole (CAS 212385-73-4) and methyl anthranilate in three steps.

(12) Yield after sublimation: 7.2 g (12 mmol), 37% of theory, purity >99.9% according to HPLC, colourless solid.

Example 3: Synthesis of 9,9-diphenyl-10-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine (H3)

(13) ##STR00398##

(14) Caesium carbonate (30.6 g, 94 mmol), palladium acetate (0.5 g, 2 mmol) and xantphos (0.9 g, 5 mmol) are added to a solution of 9,10-dihydro-9,9-diphenylacridine (CAS 20474-15-1, 15.7 g, 47 mmol) and 3-bromo-9-phenyl-9H-carbazole (CAS 1153-85-1, 15.1 g, 47 mmol) in degassed tolu ene (300 ml), and the mixture is heated under reflux for 8 h. The precipitated salts are filtered off, and the mother liquor is evaporated in vacuo. The residue is extracted with toluene in a Soxhlet extractor. The crude product is subsequently recrystallised three times from toluene and purified by sublimation twice in vacuo (p=5×10.sup.−5 mbar, T=280° C.).

(15) Yield: 10.5 g (18 mmol), 38% of theory, purity >99.9% according to HPLC, colourless solid.

Example 4: Synthesis of 9,9-dimethyl-10-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,10-dihydroacridine (HTM4)

(16) ##STR00399##

(17) 9,9-Dimethyl-10-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,10-dihydroacridine is prepared analogously to Example 3 starting from 3-(4-bromophenyl)-9-phenyl-9H-carbazole (CAS 1028647-93-9) and 9,10-dihydro-9,9-dimethylacridine (CAS 6267-02-3).

(18) Yield after sublimation: 9.6 g (18 mmol), 36% of theory, purity >99.9% according to HPLC, colourless solid.

Example 5: Synthesis of 10-[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]-9,9-dimethyl-9,10-dihydroacridine (H4)

(19) ##STR00400##

(20) 10-[4-(3,6-Di-tert-butylcarbazol-9-yl)phenyl]-9,9-dimethyl-9,10-dihydroacridine is prepared analogously to Example 3 starting from 9-(4-bromophenyl)-3,6-bis-tert-butyl-9H-carbazole (CAS 601454-33-5) and 9,10-dihydro-9,9-dimethylacridine (CAS 6267-02-3).

(21) Yield after sublimation: 11.2 g (20 mmol), 39% of theory, purity >99.9% according to HPLC, colourless solid.

Example 6: Synthesis of 10-(4′-carbazol-9-ylbiphenyl-4-yl)-9,9-diphenyl-9,10-dihydroacridine (H5)

(22) ##STR00401##

(23) 10-(4′-Carbazol-9-ylbiphenyl-4-yl)-9,9-diphenyl-9,10-dihydroacridine is pre pared analogously to Example 3 starting from 9-(4′-bromo-[1,1′-biphenyl]-4-yl)-9H-carbazole (CAS 212385-73-4) and 9,10-dihydro-9,9-diphenyl acridine (CAS 20474-15-1).

(24) Yield after sublimation: 8.7 g (13 mmol), 34% of theory, purity >99.9% according to HPLC, colourless solid.

Example 7: Synthesis of 5,5,9,9-tetramethyl-3-(9-phenyl-9H-carbazol-3-yl)-5H,9H-13b-azanaphtho[3,2,1-de]anthracene (HTM5)

(25) ##STR00402##

a) Dimethyl 2-[(4-bromophenyl)phenylamino]isophthalate

(26) N-Bromosuccinimide (35.4 g, 199 mmol) is added in portions to a solution of dimethyl 2-diphenylaminoisophthalate (CAS 66131-47-3, 80 g, 221 mmol) in chloroform (2000 ml) at 0° C. with exclusion of light, and the mixture is stirred at this temperature for 2 h. The reaction is terminated by addition of sodium sulfite solution, and the mixture is stirred at room temperature for a further 30 min. After phase separation, the organic phase is washed with water, and the aqueous phase is extracted with dichloromethane. The combined organic phases are dried over sodium sulfate and evaporated in vacuo. The residue is dissolved in ethyl acetate and filtered through silica gel. The crude product is subsequently recrystallised from heptane.

(27) Yield: 57.2 g (129 mmol), 65% of theory, colourless solid.

b) 3-Bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene

(28) Dimethyl 2-[(4-bromophenyl)phenylamino]isophthalate (57.0 g, 129 mmol) is added in portions to a suspension of anhydrous cerium(III) chloride (35.0 g, 142 mmol) in dried tetrahydrofuran (800 ml). A 3 M solution of methylmagnesium chloride in tetrahydrofuran (129.0 ml, 387 mmol) is subsequently added dropwise at 0° C., and the mixture is stirred at room temperature for 20 h. The reaction mixture is neutralised using 25% acetic acid (about 120 ml) with ice-cooling and diluted with dist. water and ethyl acetate. The aqueous phase is extracted with ethyl acetate, dried over sodium sulfate and evaporated in vacuo.

(29) The residue is dissolved in dichloromethane (200 ml) and added dropwise over the course of 20 min to a solution of polyphosphoric acid (101.1 g, 877 mmol) and methanesulfonic acid (57.5 ml, 877 mmol) in dichloromethane (200 ml). The reaction mixture is stirred at room temperature for 1 h and subsequently evaporated in vacuo. The residue is taken up in ethyl acetate, washed with dist. water, dried over sodium sulfate and evaporated in vacuo. The residue is dissolved in ethyl acetate and filtered through basic aluminium oxide. The crude product is subsequently recrystallised from ethyl acetate.

(30) Yield: 39.6 g (98 mmol), 76% of theory, colourless solid.

c) 5,5,9,9-Tetramethyl-3-(9-phenyl-9H-carbazol-3-yl)-5H,9H-13b-azanaphtho[3,2,1-de]anthracene

(31) (9-Phenyl-9H-carbazol-3-yl)boronic acid (CAS 854952-58-2, 33.0 g, 115 mmol), 3-bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene (39.0 g, 96 mmol) and potassium phosphate monohydrate (66.3 g, 288 mmol) are initially introduced in a mixture of 300 ml of dist. water, 200 ml of toluene and 100 ml of dioxane and saturated with N.sub.2 for 30 min. Tetrakis(triphenylphosphine)palladium (3.3 g, 3 mmol) is subsequently added, and the mixture is heated under reflux for 3 h. After dilution with toluene, the organic phase is separated off, washed twice with water, dried over Na.sub.2SO.sub.4 and evaporated in vacuo. The residue is extracted with toluene in a Soxhlet extractor. The crude product is subsequently recrystallised four times from toluene and purified by sublimation twice in vacuo (p=5×10.sup.−5 mbar, T=290° C.).

(32) Yield: 17.6 g (31 mmol), 32% of theory, purity >99.9% according to HPLC, colourless solid.

Example 8: Synthesis of 3-(4-carbazol-9-ylphenyl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene (H6)

(33) ##STR00403##

(34) 3-(4-Carbazol-9-ylphenyl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene is prepared analogously to Example 7c) starting from 3-bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene and [4-(carbazol-9-yl)phenyl]boronic acid (CAS 419536-33-7).

(35) Yield after sublimation: 9.4 g (17 mmol), 37% of theory, purity >99.9% according to HPLC, colourless solid.

Example 9: Synthesis of 5,5,9,9-tetramethyl-7-(9-phenyl-9H-carbazol-3-yl)-5H,9H-13b-azanaphtho[3,2,1-de]anthracene (HTM6)

(36) ##STR00404##

a) 7-Bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene

(37) N-Bromosuccinimide (24.7 g, 139 mmol) is added in portions to a solution of 5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene (CAS 52066-62-3, 50 g, 154 mmol) in chloroform (1000 ml) at 0° C. with exclusion of light, and the mixture is stirred at this temperature for 2 h. The reaction is terminated by addition of sodium sulfite solution, and the mixture is stirred at room temperature for a further 30 min. After phase separation, the organic phase is washed with water, and the aqueous phase is extracted with dichloromethane. The combined organic phases are dried over sodium sulfate and evaporated in vacuo. The residue is dissolved in ethyl acetate and filtered through silica gel. The crude product is subsequently recrystallised from heptane.

(38) Yield: 35.6 g (88 mmol), 63% of theory, colourless solid.

b) 5,5,9,9-Tetramethyl-7-(9-phenyl-9H-carbazol-3-yl)-5H,9H-13b-azanaphtho[3,2,1-de]anthracene

(39) (9-Phenyl-9H-carbazol-3-yl)boronic acid (CAS 854952-58-2, 29.9 g, 104 mmol), 7-bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene (35.0 g, 87 mmol) and potassium phosphate monohydrate (60.1 g, 261 mmol) are initially introduced in a mixture of 300 ml of dist. water, 200 ml of toluene and 100 ml of dioxane and saturated with N.sub.2 for 30 min. Tetrakis(triphenylphosphine)palladium (3.0 g, 3 mmol) is subsequently added, and the mixture is heated under reflux for 3 h. After dilution with toluene, the organic phase is separated off, washed twice with water, dried over Na.sub.2SO.sub.4 and evaporated in vacuo. The residue is extracted with toluene in a Soxhlet extractor. The crude product is subsequently recrystallised four times from toluene and purified by sublimation twice in vacuo (p=5×10.sup.−5 mbar, T=290° C.).

(40) Yield: 17.0 g (30 mmol), 34% of theory, purity >99.9% according to HPLC, colourless solid.

Example 10: Synthesis of 7-(4-carbazol-9-ylphenyl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene (H7)

(41) ##STR00405##

(42) 7-(4-Carbazol-9-ylphenyl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene is prepared analogously to Example 9b) starting from 7-bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene and [4-(carbazol-9-yl)phenyl]boronic acid (CAS 419536-33-7).

(43) Yield after sublimation: 10.3 g (18 mmol), 34% of theory, purity >99.9% according to HPLC, colourless solid.

Example 11: Synthesis of 4,4,8,8,12,12-hexamethyl-2-(9-phenyl-9H-carbazol-3-yl)-4H,8H,12H-12c-azadibenzo[cd,mn]pyrene (HTM7)

(44) ##STR00406##

(45) (9-Phenyl-9H-carbazol-3-yl)boronic acid (CAS 854952-58-2, 31.0 g, 108 mmol), 2-bromo-4,4,8,8,12,12-hexamethyl-4H,8H,12H-12c-azadibenzo[cd,mn]pyrene (40.0 g, 90 mmol) and potassium phosphate monohydrate (62.2 g, 270 mmol) are initially introduced in a mixture of 300 ml of dist. water, 200 ml of toluene and 100 ml of dioxane and saturated with N.sub.2 for 30 min. Tetrakis(triphenylphosphine)palladium (3.1 g, 3 mmol) is subsequently added, and the mixture is heated under reflux for 3 h. After dilution with toluene, the organic phase is separated off, washed twice with water, dried over Na.sub.2SO.sub.4 and evaporated in vacuo. The residue is extracted with toluene in a Soxhlet extractor. The crude product is subsequently recrystallised three times from toluene and purified by sublimation twice in vacuo (p=5×10.sup.−5 mbar, T=295° C.).

(46) Yield: 15.8 g (26 mmol), 29% of theory, purity >99.9% according to HPLC, colourless solid.

Example 12: Synthesis of 2,6-di-tert-butyl-10-(4-carbazol-9-ylphenyl)-4,4,8,8,12,12-hexamethyl-4H,8H,12H-12c-azadibenzo[cd,mn]pyrene (HTM8)

(47) ##STR00407##

(48) 2,6-Di-tert-butyl-10-(4-carbazol-9-ylphenyl)-4,4,8,8,12,12-hexamethyl-4H,8H,12H-12c-azadibenzo[cd,mn]pyrene is prepared analogously to Example 11 starting from 2-bromo-6,10-di-tert-butyl-4,4,8,8,12,12-hexamethyl-4H,8H,12H-12c-azadibenzo[cd,mn]pyrene (CAS 1097721-82-8) and [4-(carbazol-9-yl)phenyl]boronic acid (CAS 419536-33-7).

(49) Yield after sublimation: 7.8 g (11 mmol), 27% of theory, purity >99.9% according to HPLC, colourless solid.

Example 13: Synthesis of 3-(10-biphenyl-4-yl-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluoren-7-yl)-5,5,9,9-tetramethyl-5H,9H-13b-aza naphtho[3,2,1-de]anthracene (HTM9)

(50) ##STR00408##

a) 5,5,9,9-Tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene-3-boronic acid

(51) 74.5 ml (149 mmol) of a 2 M solution of n-butyllithium in cyclohexane are slowly added to a solution of 3-bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene (Example 7b, 50.0 g, 124 mmol) in dry tetrahydrofuran (600 ml) at −75° C. The reaction mixture is stirred at −75° C. for 1 h, 27.6 ml (248 mmol) of trimethyl borate are added, and the mixture is warmed overnight at room temperature. For work-up, the mixture is diluted with ethyl acetate/dist. water/glacial acetic acid (6/2/1). The organic phase is separated off, washed with dist. water and dried over sodium sulfate. The crude product obtained after removal of the solvent in vacuo is employed in the next step without further purification.

(52) Yield: 39.9 g (108 mmol), 87% of theory, colourless solid.

b) 3-(10-Biphenyl-4-yl-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluoren-7-yl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene

(53) 5,5,9,9-Tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene-3-boronic acid (20.0 g, 54 mmol), 10-biphenyl-4-yl-7-bromo-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene (see as yet unpublished DE 102009023155.2, 23.2 g, 45 mmol) and potassium phosphate monohydrate (31.1 g, 135 mmol) are initially introduced in a mixture of 150 ml of dist. water, 100 ml of toluene and 50 ml of dioxane and saturated with N.sub.2 for 30 min. Tetrakis(triphenylphosphine)palladium (1.6 g, 1 mmol) is subsequently added, and the mixture is heated under reflux for 3 h. After dilution with toluene, the organic phase is separated off, washed twice with water, dried over Na.sub.2SO.sub.4 and evaporated in vacuo. The residue is extracted with toluene in a Soxhlet extractor. The crude product is subsequently recrystallised five times from toluene and purified by sublimation twice in vacuo (p=5××10.sup.−5 mbar, T=320° C.).

(54) Yield: 10.9 g (14 mmol), 32% of theory, purity >99.9% according to HPLC, colourless solid.

Example 14: Synthesis of 3-(11,12-diphenyl-11,12-dihydro-11,12-diazaindeno[2,1-a]fluoren-3-yl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene (HTM10)

(55) ##STR00409##

a) 3-Bromo-(11,12-diphenyl-11,12-dihydro-11,12-diazaindeno[2,1-a]fluorene

(56) N-Bromosuccinimide (15.7 g, 88 mmol) is added in portions to a solution of 11,12-diphenyl-11,12-dihydro-11,12-diazaindeno[2,1-a]fluorene (CAS 222044-88-4, 40 g, 98 mmol) in chloroform (800 ml) at 0° C. with exclusion of light, and the mixture is stirred at this temperature for 2 h. The reaction is terminated by addition of sodium sulfite solution, and the mixture is stirred at room temperature for a further 30 min. After phase separation, the organic phase is washed with water, and the aqueous phase is extracted with dichloromethane. The combined organic phases are dried over sodium sulfate and evaporated in vacuo. The residue is dissolved in ethyl acetate and filtered through silica gel. The crude product is subsequently recrystallised from heptane.

(57) Yield: 28.3 g (58 mmol), 66% of theory, colourless solid.

b) 3-(11,12-Diphenyl-11,12-dihydro-11,12-diazaindeno[2,1-a]fluoren-3-yl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene

(58) 5,5,9,9-Tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene-3-boronic acid (Example 13a, 19.0 g, 51 mmol), 3-bromo-(11,12-diphenyl-11,12-dihydro-11,12-diazaindeno[2,1-a]fluorene (21.0 g, 43 mmol) and potassium phosphate monohydrate (29.7 g, 129 mmol) are initially introduced in a mixture of 150 ml of dist. water, 100 ml of toluene and 50 ml of dioxane and saturated with N.sub.2 for 30 min. Tetrakis(triphenylphosphine)palladium (1.5 g, 1 mmol) is subsequently added, and the mixture is heated under reflux for 3 h. After dilution with toluene, the organic phase is separated off, washed twice with water, dried over Na.sub.2SO.sub.4 and evaporated in vacuo. The residue is extracted with toluene in a Soxhlet extractor. The crude product is subsequently recrystallised five times from toluene and purified by sublimation twice in vacuo (p=5×10.sup.−5 mbar, T=315° C.).

(59) Yield: 9.5 g (13 mmol), 30% of theory, purity >99.9% according to HPLC, colourless solid.

Examples 15-26: Syntheses of Compounds Containing Bridging Groups —O— and —S—

a) Synthesis of the Precursor 7-bromo-9,9-dimethyl-9H-quino[3,2,1-kl]phenothiazine

(60) ##STR00410##

(61) N-Bromosuccinimide (24.7 g, 139 mmol) is added in portions to a solution of 9,9-dimethyl-9H-quino[3,2,1-kl]phenothiazine (CAS 73183-70-7, 48.5 g, 154 mmol) in chloroform (1000 ml) at 0° C. with exclusion of light, and the mixture is stirred at this temperature for 2 h. The reaction is terminated by addition of sodium sulfite solution, and the mixture is stirred at room temperature for a further 30 min. After phase separation, the organic phase is washed with water, and the aqueous phase is extracted with dichloromethane. The combined organic phases are dried over sodium sulfate and evaporated in vacuo. The residue is dissolved in ethyl acetate and filtered through silica gel. The crude product is subsequently recrystallised from heptane.

(62) Yield: 41.9 g (104 mmol), 69% of theory, colourless solid.

b) Synthesis of the Precursor 7-bromo-9,9-dimethyl-9H-quino[3,2,1-kl]phenoxazine

(63) ##STR00411##

(64) N-Bromosuccinimide (24.7 g, 139 mmol) is added in portions to a solution of 9,9-dimethyl-9H-quino[3,2,1-kl]phenoxazine (CAS 73183-73-0, 46 g, 154 mmol) in chloroform (1000 ml) at 0° C. with exclusion of light, and the mixture is stirred at this temperature for 2 h. The reaction is terminated by addition of sodium sulfite solution, and the mixture is stirred at room temperature for a further 30 min. After phase separation, the organic phase is washed with water, and the aqueous phase is extracted with dichloromethane. The combined organic phases are dried over sodium sulfate and evaporated in vacuo. The residue is dissolved in ethyl acetate and filtered through silica gel. The crude product is subsequently recrystallised from heptane.

(65) Yield: 37 g (100 mmol), 64% of theory, colourless solid.

c) Synthesis of the Precursor 7-bromo-1,4-benzothiazino[2,3,4-kl]phenothiazine

(66) ##STR00412##

(67) N-Bromosuccinimide (24.7 g, 139 mmol) is added in portions to a solution of 1,4-benzothiazino[2,3,4-kl]phenothiazine (CAS 1050521-47, 48.5 g, 154 mmol) in chloroform (1000 ml) at 0° C. with exclusion of light, and the mixture is stirred at this temperature for 2 h. The reaction is terminated by addition of sodium sulfite solution, and the mixture is stirred at room temperature for a further 30 min. After phase separation, the organic phase is washed with water, and the aqueous phase is extracted with dichloromethane. The combined organic phases are dried over sodium sulfate and evaporated in vacuo. The residue is dissolved in ethyl acetate and filtered through silica gel. The crude product is subsequently recrystallised from heptane.

(68) Yield: 42 g (110 mmol), 64% of theory, colourless solid.

d) Synthesis of the Precursor 7-bromo 1,4-benzoxazino[2,3,4-kl]phenoxazine

(69) ##STR00413##

(70) N-Bromosuccinimide (24.7 g, 139 mmol) is added in portions to a solution of 1,4-benzoxazino[2,3,4-kl]phenoxazine (CAS 784189-24-8, 42 g, 154 mmol) in chloroform (1000 ml) at 0° C. with exclusion of light, and the mixture is stirred at this temperature for 2 h. The reaction is terminated by addition of sodium sulfite solution, and the mixture is stirred at room temperature for a further 30 min. After phase separation, the organic phase is washed with water, and the aqueous phase is extracted with dichloromethane. The combined organic phases are dried over sodium sulfate and evaporated in vacuo. The residue is dissolved in ethyl acetate and filtered through silica gel. The crude product is subsequently recrystallised from heptane.

(71) Yield: 31 g (89 mmol), 58% of theory, colourless solid.

e) Synthesis of Compound Examples 15-26

General Procedure for Compound Example 15: 9,9-Dimethyl-7-(9-phenyl-9H-carbazol-3-yl)-9H-5-thia-13b-azanaphtho[3,2,1-de]anthracene (HTM12)

(72) ##STR00414##

(73) (9-Phenyl-9H-carbazol-3-yl)boronic acid (CAS 854952-58-2, 33.0 g, 115 mmol), 7-bromo-9,9-dimethyl-9H-quino[3,2,1-kl]-phenothiazine (27 g, 96 mmol) and potassium phosphate monohydrate (66.3 g, 288 mmol) are initially introduced in a mixture of 300 ml of dist. water, 200 ml of toluene and 100 ml of dioxane and saturated with N.sub.2 for 30 min. Tetrakis(triphenylphosphine)palladium (3.3 g, 3 mmol) is subsequently added, and the mixture is heated under reflux for 3 h. After dilution with toluene, the organic phase is separated off, washed twice with water, dried over Na.sub.2SO.sub.4 and evaporated in vacuo. The residue is extracted with toluene in a Soxhlet extractor. The crude product is subsequently recrystallised four times from toluene and purified by sublimation twice in vacuo (p=5×10.sup.−5 mbar, T=290° C.).

(74) Yield: 28 g (50 mmol), 75% of theory, purity >99.9% according to HPLC, colourless solid.

(75) The following compounds are obtained analogously (Examples 16-26):

(76) TABLE-US-00005 Starting Starting Ex. material 1 material 2 Product Yield 16 (HTM15) 63% 17 (HTM17) 0 73% 18 (HTM11) 79% 19 (HTM16) 70% 20 (H8) 74% 21 (HTM14) 0 77% 22 (HTM18) 63% 23 (H9) 56% 24 (HTM13) 0 70% 25 (HTM19) 78% 26 (H10) 77%

Example 27: Synthesis of 9,9-dimethyl-10-phenyl-2,7-bis-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine

a) 2,7-Dibromo-9,9-dimethyl-9,10-dihydroacridine

(77) ##STR00448##

(78) N-Bromosuccinimide (94.5 g, 531 mmol) is added in portions to a solution of 9,9-dimethyl-9,10-dihydroacridine (CAS 6267-02-3, 45 g, 252 mmol) in chloroform (1000 ml) at 0° C. with exclusion of light, and the mixture is stirred at this temperature for 2 h. 500 ml of water are subsequently added to the mixture. After phase separation, the organic phase is washed with water, and the aqueous phase is extracted with chloroform. The combined organic phases are dried over sodium sulfate and evaporated in vacuo. The residue is dissolved in ethyl acetate and filtered through silica gel. The crude product is subsequently recrystallised from heptane.

(79) Yield: 64.7 g (176 mmol), 70% of theory, colourless solid.

b) 2,7-Dibromo-9,9-dimethyl-10-phenyl-9,10-dihydroacridine

(80) ##STR00449##

(81) A degassed solution of 16.6 ml (147 mmol) of 4-iodobenzene and 45.1 g (123 mmol) of 2,7-dibromo-9,9-dimethyl-9,10-dihydroacridine in 600 ml of toluene is saturated with N.sub.2 for 1 h. Then, firstly 2.09 ml (8.6 mmol) of P(tBu).sub.3, then 1.38 g (6.1 mmol) of palladium(II) acetate are added to the solution, and 17.7 g (185 mmol) of NaOtBu in the solid state are subsequently added. The reaction mixture is heated under reflux for 1 h. After cooling to room temperature, 500 ml of water are carefully added. The aqueous phase is washed with 3×50 ml of toluene, dried over MgSO.sub.4, and the solvent is removed in vacuo. Filtration of the crude product through silica gel with heptane/ethyl acetate (20:1) gives 44.1 g (99.6 mmol, 81%) of 2,7-dibromo-9,9-dimethyl-10-phenyl-9,10-dihydroacridine as pale-yellow crystals.

c) 9,9-Dimethyl-10-phenyl-2,7-bis-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine

(82) ##STR00450##

(83) (9-Phenyl-9H-carbazol-3-yl)boronic acid (CAS 854952-58-2, 60.6 g, 211 mmol), 2,7-dibromo-9,9-dimethyl-10-phenyl-9,10-dihydroacridine (42.5 g, 96 mmol) and potassium phosphate monohydrate (66.3 g, 288 mmol) are initially introduced in a mixture of 300 ml of dist. water, 200 ml of toluene and 100 ml of dioxane and saturated with N.sub.2 for 30 min. Tetrakis(triphenylphosphine)palladium (3.3 g, 3 mmol) is subsequently added, and the mixture is heated under reflux for 3 h. After dilution with toluene, the organic phase is separated off, washed twice with water, dried over Na.sub.2SO.sub.4 and evaporated in vacuo. The residue is extracted with toluene in a Soxhlet extractor. The crude product is subsequently recrystallised four times from toluene and purified by sublimation twice in vacuo.

(84) Yield: 21.5 g (50 mmol), 75% of theory, purity >99.9% according to HPLC, colourless solid.

B) Device Examples

(85) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 04/058911, which is adapted to the circumstances described here (layer-thickness variation, materials).

(86) The data for various OLEDs are presented in Examples C1 to I44 below (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.

(87) These coated glass plates form the substrates to which the OLEDs are applied. The OLEDs have basically the following layer structure: substrate/optional hole-injection layer (HIL)/hole-transport layer (HTL)/optional interlayer (IL)/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. The precise structure of the OLEDs is shown in Table 1. The materials employed for the production of the OLEDs are shown in Table 3.

(88) 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 materials in a certain proportion by volume by coevaporation. A specification such as ST1:CBP:TER1 (55%:35%:10%) here means that material ST1 is present in the layer in a proportion by volume of 55%, CBP is present in the layer in a proportion of 35% and TER1 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

(89) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density, calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines), and the lifetime are determined. The electroluminescence spectrum are determined at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The term U1000 in Table 2 denotes the voltage required for a luminous density of 1000 cd/m.sup.2. CE1000 and PE1000 denote the current and power efficiencies achieved at 1000 cd/m=. Finally, EQE1000 is the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2. The lifetime LT is defined as the time after which the luminous density drops from the initial luminous density L0 to a certain proportion L1 on operation at constant current. A specification of L0=4000 cd/m.sup.2 and L1=80% in Table 2 means that the lifetime indicated in column LT corresponds to the time after which the initial luminous density of the corresponding OLED drops from 4000 cd/m.sup.2 to 3200 cd/m.sup.2. The values for the lifetime can be converted into a specification 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 specification here.

(90) The data for the various OLEDs are summarised in Table 2. Example C1-C16 are comparative examples in accordance with the prior art, Examples I1-I44 show data of OLEDs in which materials according to the invention are employed.

(91) Some of the examples are explained in greater detail below in order to illustrate the advantages of the compounds according to the invention. However, it should be pointed out that this only represents a selection of the data shown in Table 2. As revealed by the table, significant improvements over the prior art are also achieved on use of the compounds according to the invention which are not discussed in detail below.

(92) In some cases, an improvement in all parameters is achieved, but in some cases only an improvement in either the efficiency or the voltage or the lifetime is observed. However, even the improvement of one of the said parameters represents a significant advance, since different applications require optimisation with respect to different parameters.

(93) Use of Compounds According to the Invention as Hole-Transport or Hole-Injection Materials

(94) OLEDs C1-C4 are comparative examples in accordance with the prior art in which fluorescent dopants D1-D3 are employed in combination with matrix materials H1 and H2, hole-transport materials HTM1, SpNPB, NPB, the carbazole-substituted planar amine PACbz and electron-transport materials Alq.sub.3, ETM1, ST1 and ST2.

(95) If material HTM1 in accordance with the prior art is replaced by compound HTM7 according to the invention (Examples I1, I2 and C2, C3), the current efficiency of the OLEDs remains approximately the same, while the operating voltage drops slightly and the lifetime increases significantly by up to about 30% (Examples I1, C3). A similar improvement in the performance data is obtained if HTM7 is employed directly as hole-injection layer (Examples I24, C5). In this case, the improvement in the lifetime is about 40%, and the power efficiency also increases significantly by about 10% due to the significantly reduced operating voltage.

(96) Significant improvements are likewise obtained on use of compounds according to the Invention if these are directly adjacent to the emission layer of a fluorescent OLED (Examples I3-I12, I25, C1-4). The use of compounds HTM2 and HTM3 according to the invention is mentioned here merely by way of example compared with NPB and PACbz (Examples I3, I6-8, C1-4, C15). On replacement of NPB by HTM3 in combination with the amine-free dopant D3, a significant increase in the power efficiency by about 15% is obtained (Examples I3, C4), and a very significant increase in the lifetime by somewhat more than 50%.

(97) Compared with PACbz, compound HTM3 in combination with dopant D1 exhibits an approximately 30% increased lifetime; compared with NPB, the increase is somewhat greater than 40% (Examples I7, C2, C15).

(98) The compounds according to the invention also exhibit advantages in OLEDs which comprise a phosphorescent emission layer if they are employed as hole-transport material. This is demonstrated with reference to OLEDs which comprise compound ST1 as matrix material and the red-phosphorescent compound TER2 or the green-emitting dopant TEG1 as dopant (Examples I13-16, C5, C8, C16).

(99) With compound HTM2 according to the invention, an approximately 20% increased power efficiency is obtained compared with EBM1, for example (Examples I13, C8); with HTM7, the lifetime can be increased very significantly by almost 40% (Examples I15, C8).

(100) The use of compounds according to the invention on the hole-transport side of OLEDs thus produces significant improvements with respect to operating voltage, efficiency and lifetime.

(101) Use of Compounds According to the Invention as Component in Mixed-Matrix Systems

(102) The use of compounds according to the invention as component in mixed-matrix systems is described below. Systems are shown here which consist of two matrix materials and one dopant. The compounds in accordance with the prior art used are the materials CBP, TCTA and FTPh (Examples C6, C7, C9-C14). The materials according to the invention used are compounds H3-H10 (Examples I17-I27, I29, I30). The compounds ST1, Ket1 and DAP1 are used as the second matrix component.

(103) If, for example, compound H3 according to the invention is used in combination with ketone matrix Ket1, an increase in the lifetime by more than 50% compared with the prior art is obtained (Examples C9 and I18). Together with ST1 as second matrix component, a very significant improvement in the power efficiency by more than 25% compared with the prior art can furthermore be achieved (Examples C7, I17). This is attributable, in particular, to the operating voltage, which is significantly improved by 0.7 V compared with the prior art. As revealed by Table 2, similar improvements can be achieved with other materials according to the invention, including in red-phosphorescent OLEDs.

(104) Significant improvements thus arise compared with mixed-matrix components in accordance with the prior art, especially with respect to voltage and lifetime. Since the materials according to the invention can be employed together with very different classes of matrix materials (ST1, Ket1, DAP1), it can be expected that significant improvements can also be achieved in combination with other classes of matrix materials, such as, for example, indolocarbazoles, dibenzothiophene derivatives, dibenzofuran derivatives or the like.

(105) TABLE-US-00006 TABLE 1 Structure of the OLEDs HIL HTL IL EBL EMU HBL ETL EIL Thick- Thick- Thick- Thick- Thick- Thick- Thick- Thick- Ex. ness ness ness ness ness ness ness ness C1 HIL1 HTM1 — NPB H1:D1 (95%:5%) — Alq.sub.3 LiF 5 nm 140 nm 20 nm 30 nm 20 nm 1 nm C2 HIL1 HTM1 — NPB H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm 20 nm 30 nm 20 nm C3 HIL1 HTM1 — NPB H2:D2 (90%:10%) — Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm C4 HIL1 SpNPB — NPB H2:D3 (98.5%:1.5%) — ST2:LiQ (50%:50%) — 5 nm 40 nm 20 nm 30 nm 20 nm C5 — HTM1 — NPB ST1:TER2 (85%:15%) — Alq.sub.3 LiF 20 nm 20 nm 30 nm 20 nm 1 nm C6 — HTM1 — NPB ST1:CBP:TER1 ST1 Alq.sub.3 LiF 20 nm 20 nm (45%:45%:10%) 10 nm 20 nm 1 nm 30 nm C7 — HTM1 HIL1 EBM1 ST1:CBP:TEG1 ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 10 nm 30 nm 30 nm C8 — HTM1 HIL1 EBM1 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm C9 HIL1 — — EBM1 Ket1:FTPh:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (30%:60%:10%) 10 nm 20 nm 1 nm 30 nm C10 HIL1 — — EBM1 Ket1:FTPh:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 10 nm 20 nm 1 nm 30 nm C11 HIL1 — — EBM1 Ket1:TCTA:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 10 nm 20 nm 1 nm 30 nm C12 HIL1 — — EBM1 Ket1:CBP:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 10 nm 20 nm 1 nm 30 nm C13 — HTM1 HIL1 EBM1 DAP1:CBP:TEG1 — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 30 nm C14 — HTM1 HIL1 EBM1 ST1:TCTA:TEG1 — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 30 nm C15 HIL1 HTM1 — PACbz H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm 20 nm 30 nm 20 nm C16 — HTM1 HIL1 PACbz ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I1 HIL1 HTM7 — NPB H2:D2 (90%:10%) — Alq3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I2 HIL1 HTM7 — NPB H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm 20 nm 30 nm 20 nm I3 HIL1 SpNPB — HTM3 H2:D3 (98.5%:1.5%) — ST2:LiQ (50%:50%) — 5 nm 40 nm 20 nm 30 nm 20 nm I4 HIL1 SpNPB — HTM4 H2:D3 (98.5%:1.5%) — ST2:LiQ (50%:50%) — 5 nm 40 nm 20 nm 30 nm 20 nm I5 HIL1 SpNPB — HTM8 H2:D3 (98.5%:1.5%) — ST2:LiQ (50%:50%) — 5 nm 40 nm 20 nm 30 nm 20 nm I6 HIL1 HTM1 — HTM2 H1:D1 (95%:5%) — Alq.sub.3 LiF 6 nm 140 nm 20 nm 30 nm 20 nm 1 nm I7 HIL1 HTM1 — HTM2 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 6 nm 140 nm 20 nm 30 nm 20 nm I8 HIL1 HTM1 — HTM2 H2:D2 (90%:10%) — Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I9 HIL1 HTM1 — HTM5 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm 20 nm 30 nm 20 nm I10 HIL1 HTM1 — HTM6 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm 20 nm 30 nm 20 nm I11 HIL1 HTM1 — HTM9 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm 20 nm 30 nm 20 nm I12 HIL1 HTM1 — HTM7 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm 20 nm 30 nm 20 nm I13 — HTM1 HIL1 HTM2 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I14 — HTM1 HIL1 HTM6 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I15 — HTM1 HIL1 HTM7 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (60%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I16 — HTM1 — HTM2 ST1:TER2 (85%:15%) — Alq.sub.3 LiF 20 nm 20 nm 30 nm 20 nm 1 nm I17 — HTM1 HIL1 EBM1 ST1:H3:TEG1 ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 10 nm 30 nm 30 nm I18 HIL1 — — EBM1 Ket1:H3:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (30%:60%:10%) 10 nm 20 nm 1 nm 30 nm I19 — HTM1 HIL1 EBM1 DAP1:H3:TEG1 — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 30 nm I20 — HTM1 HIL1 EBM1 ST1:H5:TEG1 ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 10 nm 30 nm 30 nm I21 HIL1 — — EBM1 Ket1:H7:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (30%:60%:10%) 10 nm 20 nm 1 nm 30 nm I22 — HTM1 — NPB ST1:H4:TER1 ST1 Alq.sub.3 LiF 20 nm 20 nm (45%:45%:10%) 10 nm 20 nm 1 nm 30 nm I23 — HTM1 — NPB ST1:H6:TER1 ST1 Alq.sub.3 LiF 20 nm 20 nm (45%:45%:10%) 10 nm 20 nm 1 nm 30 nm I24 — HTM7 — NPB ST1:TER2 (85%:15%) — Alq.sub.3 LiF 20 nm 20 nm 30 nm 20 nm 1 nm I25 HIL1 HTM1 — HTM9 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm 20 nm 30 nm 20 nm I26 — HTM1 — NPB ST1:H8:TER1 ST1 Alq.sub.3 LiF 20 nm 20 nm (45%:45%:10%) 10 nm 20 nm 1 nm 30 nm I27 — HTM1 HIL1 EBM1 ST1:H8:TEG1 ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 10 nm 30 nm 30 nm I28 HIL1 SpNPB — H8 H2:D3 (98.5%:1.5%) — ST2:LiQ (50%:50%) — 5 nm 40 nm 20 nm 30 nm 20 nm I29 — HTM1 — NPB ST1:H9:TER1 ST1 Alq.sub.3 LiF 20 nm 20 nm (45%:45%:10%) 10 nm 20 nm 1 nm 30 nm I30 — HTM1 — NPB ST1:H10:TER1 ST1 Alq.sub.3 LiF 20 nm 20 nm (45%:45%:10%) 10 nm 20 nm 1 nm 30 nm I31 HIL1 HTM1 — HTM11 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm 20 nm 30 nm 20 nm I32 HIL1 HTM1 — HTM11 H2:D2 (90%:10%) — Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I33 — HTM1 HIL1 HTM11 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I34 — HTM1 HIL1 HTM12 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm 135 — HTM1 HIL1 HTM13 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm 136 — HTM1 HIL1 HTM14 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I37 — HTM1 HIL1 HTM15 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I38 — HTM1 HIL1 HTM16 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I39 — HTM1 HIL1 HTM17 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I40 — HTM1 HIL1 HTM18 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I41 — HTM1 HIL1 HTM19 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I42 HIL1 HTM1 — HTM16 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm 20 nm 30 nm 20 nm I43 HIL1 HTM1 — HTM16 H2:D2 (90%:10%) — Alq.sub.3 LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I44 HIL1 SpNPB — HTM16 H2:D3 (98.5%:1.5%) — ST2:LiQ (50%:50%) — 5 nm 40 nm 20 nm 30 nm 20 nm

(106) TABLE-US-00007 TABLE 2 Data for the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at L0 L1 LT Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 (cd/m.sup.2) % (h) C1 6.4 5.1 2.5 4.2% 0.14/0.15 6000 50 150 C2 4.7 8.1 5.4 6.3% 0.14/0.15 6000 50 145 C3 5.0 17.1 10.7 5.0% 0.28/0.61 25000 50 480 C4 4.3 9.8 7.1 7.6% 0.14/0.16 6000 50 210 C5 6.5 9.0 4.3 8.3% 0.66/0.33 1000 50 18000 C6 5.2 8.1 4.9 11.4% 0.68/0.32 1000 50 15000 C7 4.4 48 34 13.3% 0.37/0.60 4000 80 450 C8 4.2 52 39 14.5% 0.36/0.60 4000 80 330 C9 4.3 45 33 12.6% 0.36/0.61 1000 50 39000 C10 4.0 46 36 12.8% 0.36/0.61 1000 50 34000 C11 3.9 42 34 11.6% 0.35/0.60 1000 50 14000 C12 4.1 44 34 12.3% 0.36/0.61 1000 50 25000 C13 4.6 47 32 13.2% 0.36/0.60 1000 50 43000 C14 4.2 43 32 12.0% 0.35/0.60 1000 50 17000 C15 4.8 8.0 5.2 6.2% 0.14/0.15 6000 50 160 C16 4.3 51 37 14.2% 0.36/0.60 4000 80 350 I1 4.8 16.7 10.9 4.9% 0.28/0.61 25000 50 615 I2 4.5 8.3 6.8 6.5% 0.14/0.15 6000 50 180 I3 4.0 10.5 8.2 8.1% 0.14/0.16 6000 50 320 I4 4.1 10.2 7.8 7.8% 0.14/0.16 6000 50 305 I5 4.3 9.3 6.8 7.2% 0.14/0.16 6000 50 270 I6 6.1 5.1 2.6 4.2% 0.14/0.15 6000 50 200 I7 4.5 7.7 5.4 6.0% 0.14/0.15 6000 50 210 I8 4.8 17.5 11.5 5.1% 0.28/0.61 25000 50 655 I9 4.6 8.0 5.5 6.3% 0.14/0.15 6000 50 185 I10 4.6 7.6 5.2 5.9% 0.14/0.15 6000 50 185 I11 4.6 7.8 5.3 6.1% 0.14/0.15 6000 50 190 I12 4.5 8.5 5.9 6.6% 0.14/0.15 6000 50 225 I13 4.2 63 47 17.5% 0.36/0.60 4000 80 400 I14 4.0 56 44 15.5% 0.36/0.60 4000 80 375 I15 4.1 61 47 17.1% 0.36/0.60 4000 80 455 I16 5.8 10.3 5.6 9.5% 0.66/0.33 1000 50 29000 I17 3.7 51 43 14.3% 0.37/0.61 4000 80 585 I18 3.6 52 45 14.5% 0.36/0.61 1000 50 60000 I19 3.7 46 39 13.0% 0.37/0.60 1000 50 56000 I20 3.8 52 43 14.5% 0.36/0.61 4000 80 610 I21 3.5 49 44 13.7% 0.36/0.61 1000 50 57000 I22 4.9 8.8 5.6 12.3% 0.68/0.32 1000 50 18000 I23 4.7 9.1 6.1 12.7% 0.68/0.32 1000 50 23000 I24 6.1 9.3 4.8 8.6% 0.66/0.33 1000 50 26000 I25 4.5 7.5 5.2 6.0% 0.14/0.15 6000 50 175 I26 4.9 8.7 5.6 12.2% 0.68/0.32 1000 50 17000 I27 4.4 47 33 12.9% 0.37/0.61 4000 80 490 I28 4.2 10.7 8.0 8.3% 0.14/0.16 6000 50 215 I29 5.0 8.4 5.3 11.8% 0.68/0.32 1000 50 17000 I30 5.1 8.5 5.2 12.0% 0.68/0.32 1000 50 21000 I31 4.7 9.5 6.4 7.4% 0.14/0.15 6000 50 190 I32 4.9 18.5 11.8 5.4% 0.28/0.61 25000 50 640 I33 4.2 57 43 15.9% 0.36/0.60 4000 80 390 I34 4.1 55 43 15.4% 0.36/0.60 4000 80 310 I35 4.1 57 43 15.8% 0.36/0.60 4000 80 350 I36 4.2 55 41 15.2% 0.36/0.60 4000 80 300 I37 4.3 56 41 15.6% 0.36/0.60 4000 80 290 I38 4.1 52 40 14.4% 0.36/0.60 4000 80 350 I39 4.2 55 41 15.3% 0.36/0.61 4000 80 300 I40 4.1 56 42 15.5% 0.36/0.59 4000 80 270 I41 4.3 58 42 16.0% 0.36/0.60 4000 80 280 I42 4.6 8.8 6.0 6.9% 0.14/0.15 6000 50 110 I43 4.8 17.8 11.5 5.2% 0.28/0.61 25000 50 410 I44 4.2 10.1 7.7 7.9% 0.14/0.16 6000 50 180

(107) TABLE-US-00008 TABLE 3 Structural formulae of the materials HIL1 HTM1 (prior art) NPB (prior art) EBM1 (prior art) Alq.sub.3 H1 H2 D1 D2 0 ETM1 ST1 ETM2 LiQ TEG1 TER1 TER2 CBP (prior art) Ket1 (prior art) TCTA (prior art) 0 ST2 DAP1 FTPh (prior art) D3 PA3Cbz (prior art) SpNPB HTM2 (according to the invention) HTM3 (according to the invention) HTM4 (according to the invention) HTM5 (according to the invention) 0 HTM6 (according to the invention) HTM7 (according to the invention) HTM8 (according to the invention) HTM9 (according to the invention) H3 (according to the invention) H4 (according to the invention) H5 (according to the invention) H6 (according to the invention) H7 (according to the invention) HTM10 (according to the invention) 0 H8 (according to the invention) H9 (according to the invention) H10 (according to the invention) HTM11 (according to the invention) HTM12 (according to the invention) HTM13 (according to the invention) HTM14 (according to the invention) HTM15 (according to the invention) HTM16 (according to the invention) HTM17 (according to the invention) 00 HTM18 (according to the invention) 01 HTM19 (according to the invention)