Materials for organic electroluminescent devices

Abstract

The present invention relates to compounds of formula (1). The compounds are suitable for use in electronic devices, in particular organic electroluminescent devices, comprising these compounds. In some embodiments, the compounds are used as matrix materials for phosphorescent or fluorescent emitters as well as a hole-blocking or electron-transport.

Claims

1. A compound of the formula (1), ##STR00607## where: X is N or CR.sup.X, with the proviso that exactly two non-adjacent groups X are equal to N; Ar.sup.S is on each occurrence, identically or differently, an aromatic ring system having 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R; Ar.sup.1 is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; R.sup.P is N(Ar).sub.2; R.sup.X is on each occurrence, identically or differently, D, F, Cl, Br, I, CHO, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, (R)C═C(R)Ar, CN, NO.sub.2, Si(R).sub.3, B(OR).sub.2, B(R).sub.2, B(N(R).sub.2).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where one or more, non-adjacent CH.sub.2 groups may be replaced by (R)C═C(R), C═C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, N(R), O, S or CON(R) and where one or more H atoms may be 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 be substituted by one or more radicals R, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, (R)C═C(R)Ar, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, B(R.sup.1).sub.2, B(N(R.sup.1).sub.2).sub.2, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 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.1)C═C(R.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, P(═O)(R.sup.1), SO, SO.sub.2, N(R.sup.1), O, S or CON(R.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 or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, where optionally two or more adjacent substituents R can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; Ar is an aromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1; R.sup.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, 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, (R.sup.2)C═C(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, B(R.sup.2).sub.2, B(N(R.sup.2).sub.2).sub.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 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.2)C═C(R.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, P(═O)(R.sup.2), SO, SO.sub.2, N(R.sup.2), O, S or CON(R.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 or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, where optionally two or more adjacent substituents R.sup.1 can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; R.sup.2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, CN, NO.sub.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms; where optionally two or more adjacent substituents R.sup.2 can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; n, m, q are, identically or differently, 0, 1, 2 or 3; p is 1.

2. The compound according to claim 1, wherein the compound is a compound of formulae (2), (3) and (4), ##STR00608## where the symbols and indices used have the same meanings as given in claim 1.

3. The compound according to claim 1, wherein the compound is a compound of formulae (2-2) to (4-6), ##STR00609## ##STR00610## ##STR00611## where the symbols and indices used have the same meanings as given in claim 1.

4. The compound according to claim 1, wherein the compound is a compound of formulae (2-2a) to (4-6a), ##STR00612## ##STR00613## ##STR00614## where the symbols and indices used have the same meanings as given in claim 1.

5. The compound according to claim 1, wherein Ar.sup.1 stands for benzene, naphthalene, anthracene, biphenyl, terphenyl, fluorene, furan, benzofuran, dibenzofuran, thiophene, benzo-thiophene, dibenzothiophene, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, azacarbazole, benzocarboline, phenanthroline, 1,3,5-triazine, 1,2,4-triazine or 1,2,3-triazine, each of which may be substituted by one or more radicals R.

6. The compound according to claim 1, wherein R.sup.X is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more radicals R.

7. The compound according to claim 1, wherein R.sup.X stands on each occurrence, identically or differently, for benzene, naphthalene, anthracene, biphenyl, terphenyl, fluorene, spirobifluorene, cis- or trans-indenofluorene, furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, azacarbazole, benzocarboline, phenanthroline, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, each of which may be substituted by one or more radicals R.

8. The compound according to claim 1, wherein at least one group Ar.sup.1 or R.sup.X is selected from triazine, pyrimidine, pyrazine, pyridazine, pyridine, imidazole, pyrazole, oxazole, oxadiazole, triazole, thiazole, thiadiazole, benzimidazole, quinolone, isoquinoline and quinoxaline, which may be substituted by one or more radicals R.

9. The compound according to claim 1, wherein at least one group Ar.sup.1 or R.sup.X is selected from pyrrole, furan, thiophene, benzothiophene, benzofuran, indole, carbazole, dibenzothiophene, dibenzofuran and azacarbazole, which may be substituted by one or more radicals R.

10. A process for the preparation of the compound according to claim 1, starting from a diarylpyrimidoindole derivative, in which an aromatic or heteroaromatic ring system is connected to the nitrogen atom of a 5-membered ring of the indole ring by a C—N coupling reaction and/or at least one aromatic or heteroaromatic ring system is connected to the diarylpyrimidoindole derivative via a C—C coupling reaction.

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

12. An electronic device comprising at least one compound according to claim 1, wherein the device is selected from the group consisting of organic electroluminescent device, organic integrated circuit, organic field-effect transistor, organic thin-film transistor, organic light-emitting transistor, organic solar cell, dye-sensitised organic solar cell, organic optical detector, organic photoreceptor, organic field-quench device, light-emitting electrochemical cell, organic laser diode and organic plasmon emitting device.

13. An organic electroluminescent device which comprises the compound according to claim 1, wherein the compound is employed as one or more of a matrix material for phosphorescent or fluorescent emitters, an electron-blocking or exciton-blocking material, a hole-blocking material, or an electron-transport material.

14. The compound according to claim 1, wherein the compound is a compound of formula (I-1) or (I-2): ##STR00615##

15. The compound according to claim 1, wherein R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, (R)C═C(R)Ar, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, B(R.sup.1).sub.2, B(N(R.sup.1).sub.2).sub.2, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.1, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, where optionally two or more adjacent substituents R can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; R.sup.X is on each occurrence, identically or differently, D, F, Cl, Br, I, CHO, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, (R)C═C(R)Ar, CN, NO.sub.2, Si(R).sub.3, B(OR).sub.2, B(R).sub.2, B(N(R).sub.2).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; R.sup.1 is on each occurrence, identically or differently, 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, (R.sup.2)C═C(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, B(R.sup.2).sub.2, B(N(R.sup.2).sub.2).sub.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, where optionally two or more adjacent substituents R.sup.1 can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.

16. The compound according to claim 1, wherein R.sup.X is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40, which may be substituted by one or more radicals R.

17. The compound according to claim 1, wherein R.sup.X stands on each occurrence, identically or differently, for benzene, naphthalene, biphenyl or carbazole, each of which may be substituted by one or more radicals R.

Description

SYNTHESES EXAMPLES

(1) The following syntheses are carried out, unless indicated otherwise, under a protective-gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The corresponding CAS numbers are also indicated in each case from the compounds known from the literature.

a) 5-bromo-1-phenyl-1H-indole-2,3-dione

(2) ##STR00127##

(3) 24.5 g (120.0 mmol) of iodobenzene, 4 g (12 mmol) of lanthanum oxide are dissolved in 200 mL of DMSO and suspended with 22.6 g (100 mmol) of 5-bromo-1H-indole-2,3-dione. Subsequently, 2.1 g (24 mmol) DMEDA and 2 equiv. KOH are added to the reaction mixture under a protective gas atmosphere and the reaction mixture is heated for 12 h at 110° C. After cooling, ethyl acetate and water are added to the mixture. Subsequently, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and evaporated to dryness. The residue is recrystallised from toluene and dichloromethane/Heptane. The yield is 20.7 g (68 mmol), corresponding to 69% of theory.

(4) The following compounds are prepared analogously:

(5) TABLE-US-00001 Reactant 1 Reactant 2 Product Yield 1a   [502161-03-7] 0 68% 2a   [83819-97-0] 56% 3a 69%

b) 8-bromo-2,3,5-triphenyl-5H-pyrazino[2,3-b]indole

(6) ##STR00137##

(7) 11.8 g (35 mmol) of 5-bromo-1-phenyl-1H-indole-2,3-dione, 7.5 g (35 mmol) of 1,2-diphenyl-1,2-ethanediamine are dissolved in 200 ml of ethanol under a protective gas atmosphere and under reflux for 6 hours. After cooling, the solution is concentrated and the residue is recrystallized from ethanol. The yield is 7.8 g (16 mmol), corresponding to 42% of theory.

(8) The following compounds are prepared analogously:

(9) TABLE-US-00002 Reactant 1 Reactant 2 Product Yield 1b   [951-87-1] 0 64% 2b   [951-87-1] 59% 3b   [951-87-1] 62% 4b   [723-89-7] 41%

c) 2,4-diphenyl-9H-pyrimido[4,5-b]indole

(10) 13.5 g (120.0 mmol) of phenylboronic acid, 14.2 g (60 mmol) of 2,4-dichloro-benzo [4,5] furo [3,2-d] pyrimidine and 21 g (210.0 mmol) of sodium carbonate are suspended in 500 mL water and 500 mL ethylene glycol diethyl ether. Subsequently, 914 mg (3.0 mmol) of tri-o-tolylphosphine and 113 mg (0.5 mmol) of palladium (II) acetate are added to the mixture, which is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 mL water and then evaporated to dryness. The residue is recrystallized from toluene and dichloromethane/heptane. Yield: 15.8 g (49 mmol), 82% of theory.

(11) The following compounds are prepared analogously:

(12) TABLE-US-00003 Reactant 1 Reactant 2 Product Yield  1c 0   74894-26-1   [317810-27-8] 75%  2c   74894-26-1   [1251825-65-6] 80%  3c   854952-58-2 70%  4c   74894-26-1 0   [1629973-75-6] 81%  5c   [1034194-21-2] 77%  6c   854952-58-2 76%  7c 0 83%  8c   [1034194-00-7] 84%  9c 82% 10c   854952-58-2 42% 11c 0 44% 12c   [1034194-21-2]   [57102-42-8] 54% 13c   74894-26-1 52% 14c 0 57% 15c   [57102-42-8] 66% 16c   [1034194-21-2] 54% 17c   [881911-81-5] 00 62%

d) 6-bromo-2,4-diphenyl-9H-pyrimido[4,5-b]indole

(13) ##STR00201##

(14) 61 g (190.0 mmol) of 2,4-diphenyl-5H-pyrimido[5,4-b]indole are suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulfuric acid (95-98%). Subsequently, 34 g (190 mmol) of NBS is slowly added to the mixture, which is then stirred for 2 hours in darkness. The mixture is then mixed with water/ice and the crude product is separated off and washed with ethanol. Afterwards, the residue is recrystallized from toluene. The yield is 65 g (163 mmol), corresponding to 86% of theory.

(15) The following compounds are prepared analogously:

(16) TABLE-US-00004 Reactant Product Yield 1d 02   74894-26-1 03 59% 2d 04 05 67% 3d 06 07 64% 4d 08 09 46% 5d 0 69%

e) 6-bromo-2,4-diphenyl-9H-pyrimido[4,5-b]indole

(17) ##STR00212##

(18) A mixture consisting of 21.2 g (100 mmol) of 5-bromo-1,3-dihydro-2H-indol-2-one, 31 g (300 mmol) of benzonitrile and 2 ml of a saturated NaOH solution is heated in the microwave for 4 min at 180° C. (Synlett, 2008 from 2.177 to 180). After cooling, the organic phase is purified by column chromatography on silica gel with ethyl acetate/heptane (1:4) and recrystallized in ethanol. The yield is 30 g (76 mmol), corresponding to 77% of theory.

(19) The following compounds are prepared analogously:

(20) TABLE-US-00005 Reactant 1 Reactant 2 1e   [1132943-23-7] 2e   [126747-14-6] 3e   [578026-69-4] 4e 0   [57103-17-0] 5e   [1443045-28-0] 6e   [141104-58-7] Product Yield 1e 67% 2e 74% 3e 72% 4e 65% 5e 53% 6e 0 68%

f) 2,4-diphenyl-6-(9-phenyl-9H-carbazol-3-yl)-9H-pyrimido[4,5-b]indole

(21) ##STR00231##

(22) 74.3 g (156 mmol) of 6-bromo-2,4-diphenyl-9H-pyrimido [4,5-b] indole, 50 g (172 mmol) of N-phenyl-carbazol-3-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 mL ethylene glycol diethyl ether and 280 mL water. Subsequently, 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)-palladium(0) are added to the reaction mixture, which is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel and then evaporated to dryness. The product is then purified by chromatography on silica gel with toluene/heptane (1:2). The yield is 65 g (102 mmol), corresponding to 66% of theory.

(23) The following compounds are prepared analogously:

(24) TABLE-US-00006 Reactant 1 Reactant 2  1f   [1379585-25-7]  2f   [402936-15-6]  3f   [162607-19-4]  4f   [108847-20-7]  5f 0   [1642121-58-1]  6f   [1266389-16-5]  7f   [1642121-53-6]  8f   [1398394-64-3]  9f   [1420067-45-3] 10f 0   [1572537-61-1] 11f 12f   [1547492-13-6] 13f   [1391729-63-7] 14f   [1547397-15-8] 15f 0   [1391729-63-7] 16f   [1373359-67-1] 17f   [1314019-74-3] 18f   [1246022-50-3] 19f   [854952-60-6] 20f 0   [1556069-50-1] 21f   [796071-96-0] 22f   [13922-41-3] 23f   [1251825-65-6] 24f   [1394815-87-2] 25f 0   [1266389-18-7] 26f   [854952-58-2] 27f   [796071-96-0] 28f   [854952-58-2] 29f   [854952-58-2] 30f 0   [854952-58-2] 31f   [854952-58-2] 32f   g37   [854952-58-2] 33f   g40   [854952-58-2] 34f   [1084334-86-0] 35f 00 01   [333432-28-3] 36f 02 03   [1001911-63-2] 37f 04 05   [854952-58-2] 38f 06 07   [100124-06-9] 39f 08 09   [100124-06-9] 40f 0   [100124-06-9] Product Yield  1f 60%  2f 73%  3f 56%  4f 72%  5f 73%  6f 67%  7f 65%  8f 77%  9f 0 67% 10f 61% 11f 70% 12f 57% 13f 60% 14f 71% 15f 69% 16f 65% 17f 52% 18f 62% 19f 0 63% 20f 72% 21f 70% 22f 78% 23f 69% 24f 64% 25f 66% 26f 46% 27f 63% 28f 68% 29f 0 69% 30f 64% 31f 69% 32f 62% 33f 69% 34f 72% 35f 75% 36f 71% 37f 73% 38f 70% 39f 0 77% 40f 73%

(25) The products 13f-16f and 27f-30f are purified by chromatography on silica gel with toluene/heptane (1:2) and finally sublimed in a high vacuum (p=5×10.sup.−7 mbar) (99.9% purity).

g) 2,4,9-triphenyl-6-(9-phenyl-9H-carbazol-3-yl)-9H-pyrimido[4,5-b]indole

(26) ##STR00352##

(27) A degassed solution of 25 g (155 mmol) bromobenzene and 84 g (150 mmol) of 2,4-diphenyl-6-(9-phenyl-9H-carbazol-3-yl)-9H-pyrimido [4,5-b]indole 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 MgSO4 and the solvent removed under vacuum. Thereafter, the crude product is purified by chromatography on silica gel with heptane/acetic ester (20/1). The residue is recrystallized from toluene, and finally sublimed in a high vacuum (p=5×10.sup.−6 mbar).

(28) The yield is 76 g (120 mmol), corresponding to 80% of theory.

(29) The following compounds are prepared analogously:

(30) TABLE-US-00007 Reactant 1 Reactant 2 Product Yield  1g 69%  2g 71%  3g 0 85%  4g 75%  5g 81%  6g 0 67%  7g 72%  8g 67%  9g 74% 10g 0 52% 11g 80% 12g 83% 13g 0 87% 14g 80% 15g 79% 16g 00 77% 17g 01 02 03 81% 18g 04 05 06 63% 19g 07 08 09 62% 20g 0 78% 21g 74% 22g 76% 23g 0 88% 24g 79% 25g 77% 26g 0 76% 27g 79% 28g 83% 29g 81% 30g 0 85% 31g 63% 32g 61% 33g 0 58% 34g 87% 35g 57% 36g 0 52% 37g 56% 38g 63% 39g 67% 40g 0 52% 41g 67% 42g 65% 43g 0 77% 44g 76% 45g 75% 46g 0 77% 47g 76% 48g 80% 49g 80%

h) 6-bromo-2,4,9-triphenyl-9H-pyrimido[4,5-b]indole

(31) ##STR00500##

(32) 20 g (50 mmol) of 6-bromo-2,4-diphenyl-9H-pyrimido [4,5-b]indole, 560 mg (25 mmol) of Pd(OAc).sub.2, 19.3 g (118 mmol) CuI and 20.8 (100 mmol) of iodobenzene are suspended in 300 ml of degassed DMF under a protective gas atmosphere. The reaction mixture is then heated 24 h under reflux at 140° C. After cooling, the solvent is removed in vacuum, the residue is dissolved in dichloromethane and water is added. Thereafter, the organic phase is separated off and filtered through silica gel. The product is purified by column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed in a high vacuum (p=5×10.sup.−7 mbar) (99.9% purity). The yield is 15.23 g (32 mmol), corresponding to 64% of theory.

(33) The following compounds are prepared analogously:

(34) TABLE-US-00008 Reactant 1 Reactant 2 Product Yield  1h 01 02 03 61%  2h 04 05 06 57%  3h 07 08 09 74%  4h 0 52%  5h 55%  6h 53%  7h 0 60%  8h 66%  9h 81% 10h 0 85% 11h 69% 12h 71% 13h 75% 14h 0 70%

i) 6-(3-carbazol-9-yl-phenyl)-2,4,9-triphenyl-9H-pyrimido[4,5-b]indole

(35) ##STR00543##

(36) 74.2 g (156 mmol) of 6-bromo-2,4-diphenyl-9H-pyrimido [4,5-b]indole, 49.3 g (172 mmol) of 3-(9H-carbazol-9-yl-phenyl]-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 mL ethylene glycol diethyl ether and 280 mL of water. Afterwards, 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)-palladium(0) is added to the reaction mixture, which is heated for 16 hours under reflux After cooling, the organic phase is separated off, filtered through silica gel and then evaporated to dryness. The product is purified by column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed in high vacuum (p=5×10.sup.−7 mbar) (purity 99.9%). The yield is 84 g (132 mmol), corresponding to 85% of theory.

(37) The following compounds are prepared analogously:

(38) TABLE-US-00009 Reactant 1 Reactant 2 Product Yield  1i 73%  2i 75%  3i 0 70%  4i 77%  5i 69%  6i 0 64%  7i 71%  8i 70%  9i 0 79% 10i 78% 11i 75%

Device Examples

(39) Fabrication of OLEDs

(40) The following examples V1 to E16 (see Table 1 and 2) show data of various OLEDs.

(41) Pre-Treatment for Examples V1-E16:

(42) Glass plates coated with structured ITO (50 nm, indium tin oxide) form the substrates on which the OLEDs are processed. Before evaporation of the OLED materials, the substrates are pre-baked for 15 minutes at 250° C., followed by an O.sub.2 and subsequent Argon plasma treatment.

(43) The OLEDs have in principle the following layer structure: substrate/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 exact layer structure is denoted in Table 1. The materials used for the OLED fabrication are presented in Table 3.

(44) 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 IC1:M1:TEG1 (55%:35%:10%) here means that material IC1 is present in the layer in a proportion by volume of 55%, M1 is present in the layer in a proportion of 35% and TEG1 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

(45) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (CE1000, measured in cd/A at 1000 cd/m.sup.2), the luminous efficacy (LE1000, measured in Im/W at 1000 cd/m.sup.2), the external quantum efficiency (EQE1000, measured in % at 1000 cd/m.sup.2) and the voltage (U1000, measured at 1000 cd/m.sup.2 in V) are determined from current/voltage/luminance characteristic lines (IUL characteristic lines) assuming a Lambertian emission profile. The electroluminescence (EL) spectra are recorded at a luminous density of 1000 cd/m.sup.2 and the CIE 1931 x and y coordinates are then calculated from the EL spectrum.

(46) The device data of various OLEDs is summarized in Table 2. The examples V1-V4 are comparison examples according to the state-of-the-art. The examples E1-E16 show data of inventive OLEDs.

(47) In the following section several examples are described in more detail to show the advantages of the inventive OLEDs.

(48) Use of Inventive Compounds as Host Material in Phosphorescent OLEDs

(49) The use of the inventive compounds as host material results in significantly improved OLED device data compared to state-of-the-art materials, especially with respect to EQE and luminous efficacy.

(50) The use of the inventive materials I2, I3 and I4 as host material in phosphorescent green OLEDs results in 9-15% improved EQE compared to a device with the material C1 (comparison of example V1 with E2, E3 and E4 in Table 2). The data of E1 were not measured as 11 is more suitable as a matrix material for red or yellow emitters rather than for green emitters like TEG2.

(51) The use of the inventive materials I5, I6 and I7 as host material in phosphorescent green OLEDs results in 9-15% improved luminous efficacy compared to a device with the material C2 (comparison of example V2 with E5, E6 and E7).

(52) The use of the inventive materials I8, I9 and I10 as host material in phosphorescent green OLEDs results in 20-25% improved EQE compared to a device with the material C3 (comparison of example V3 with E8, E9 and E10).

(53) The use of the inventive material I11 as host material in phosphorescent green OLEDs results in 5% improved EQE compared to a device with the material C4 (comparison of example V4 with E11).

(54) TABLE-US-00010 TABLE 1 OLED layer structure HIL HTL EBL EML HBL ETL Ex. Thickness Thickness Thickness Thickness Thickness Thickness V1 HATCN SpMA1 SpMA3 IC5:C1:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm V2 HATCN SpMA1 SpMA3 IC5:C2:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm V3 HATCN SpMA1 SpMA3 IC5:C3:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm V4 HATCN SpMA1 SpMA3 IC5:C4:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E1 HATCN SpMA1 SpMA3 IC5:I1:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E2 HATCN SpMA1 SpMA3 IC5:I2:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E3 HATCN SpMA1 SpMA3 IC5:I3:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E4 HATCN SpMA1 SpMA3 IC5:I4:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E5 HATCN SpMA1 SpMA3 IC5:I5:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E6 HATCN SpMA1 SpMA3 IC5:I6:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E7 HATCN SpMA1 SpMA3 IC5:I7:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E8 HATCN SpMA1 SpMA3 IC5:I8:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E9 HATCN SpMA1 SpMA3 IC5:I9:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E10 HATCN SpMA1 SpMA3 IC5:I10:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E11 HATCN SpMA1 SpMA3 IC5:I11:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 30 nm 30 nm E12 HATCN SpMA1 SpMA3 1g:IC3:TEG2 ST2 ST2:LiQ 5 nm 230 nm 20 nm (50%:40%:10%) 10 nm (50%:50%) 30 nm 30 nm E13 HATCN SpMA1 SpMA3 45g:TER5 ST2:LiQ 5 nm 125 nm 10 nm (97%:3%) 40 nm (50%:50%) 35 nm E14 HATCN SpMA1 SpMA3 8g:TER5 ST2:LiQ 5 nm 125 nm 10 nm (97%:3%) 40 nm (50%:50%) 35 nm E15 HATCN SpMA1 SpMA3 IC5:IC3:TEG2 ST2 9g:LiQ 5 nm 230 nm 20 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm E16 HATCN SpMA1 SpMA3 IC5:IC3:TEG2 ST2 3g:LiQ 5 nm 230 nm 20 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm

(55) TABLE-US-00011 TABLE 2 OLED device data U1000 CE1000 LE1000 CIE x/y at Ex. (V) (cd/A) (lm/W) EQE1000 1000 cd/m.sup.2 V1 3.4 71 66 19.4% 0.31/0.64 V2 3.5 74 66 20.1% 0.32/0.63 V3 3.3 63 60 17.2% 0.31/0.64 V4 3.3 75 71 20.2% 0.32/0.64 E2 3.3 81 77 22.1% 0.31/0.64 E3 3.5 79 71 21.3% 0.32/0.64 E4 3.4 78 72 21.1% 0.33/0.63 E5 3.4 79 73 21.4% 0.32/0.64 E6 3.3 80 76 21.6% 0.32/0.63 E7 3.4 78 72 21.3% 0.32/0.64 E8 3.4 76 70 20.7% 0.32/0.64 E9 3.4 80 74 21.5% 0.33/0.63 E10 3.3 78 74 21.0% 0.34/0.63 E11 3.4 79 73 21.3% 0.33/0.63 E12 3.2 75 74 20.2% 0.32/0.64 E13 3.4 27 25 22.7% 0.67/0.33 E14 3.6 25 22 22.4% 0.67/0.33 E15 3.4 69 64 18.9% 0.32/0.64 E16 3.3 67 64 18.4% 0.32/0.63

(56) TABLE-US-00012 TABLE 3 Chemical structures of the OLED materials HATCN SpMA1 SpMA3 0 IC5 ST2 TEG2 LiQ IC3 TER5 C1 I1 I2 I3 0 I4 C2 I5 I6 I7 C3 I8 I9 I10 C4 00 I11 01  1g 02 45g 03  8g 04  9g 05  3g 06  4i