Electronic device

Abstract

The invention relates to an electronic device containing at least one compound of formula (I) or (II) in an organic layer. The invention further relates to a method for producing the electronic device and the use of a compound of formula (I) or (II) in an electronic device.

Claims

1. An electronic device comprising anode, cathode and at least one organic layer, which comprises at least one compound of the formula (I) or (II) ##STR00510## where a group selected from the groups of the formulae ##STR00511## is bonded at the positions denoted by *, where: E is selected on each occurrence, identically or differently, from a single bond, C(R.sup.1).sub.2, Si(R.sup.1).sub.2, C═O, O, S, S═O, SO.sub.2 and NR.sup.1; Z is on each occurrence, identically or differently, CR.sup.1 or N; W is selected on each occurrence, identically or differently, from C═O, O, S, S═O, SO.sub.2 and NR.sup.1; Ar.sup.1 is selected on each occurrence, identically or differently, from aryl or heteroaryl groups having 6 to 13 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1; Ar.sup.2 is selected on each occurrence, identically or differently, from aryl or heteroaryl groups having 6 to 13 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1; X is selected on each occurrence, identically or differently, from C(R.sup.1).sub.2, Si(R.sup.1).sub.2, C═O, O, S, S═O, SO.sub.2 and NR.sup.1; Y is a single bond; R.sup.1 is on each occurrence, identically or differently, H, D, F, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, P(═O)(R.sup.2).sub.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, 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 or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.2 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO or SO.sub.2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, where two or more radicals R.sup.1 is optionally linked to one another and may form a ring; R.sup.2 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by D or F; two or more substituents R.sup.2 here is optionally linked to one another and may form a ring; n is on each occurrence, identically or differently, 0, 1, 2, 3 or 4; i is on each occurrence, identically or differently, 0 or 1; k is on each occurrence, identically or differently, 0 or 1, where at least one index k per group of the formula (C-1) must be equal to 1; and where a group selected from groups of the formulae (A-1) and (A-2) must be bonded at at least one of the positions denoted by *, and where furthermore no condensed aryl or heteroaryl group having 14 or more aromatic ring atoms is present in the compound.

2. The electronic device according to claim 1, wherein the group E is selected on each occurrence, identically or differently, from a single bond, C(R.sup.1).sub.2, C═O, O, S and NR.sup.1.

3. The electronic device according to claim 1, wherein the group Ar.sup.1 is selected on each occurrence, identically or differently, from aryl or heteroaryl groups having 6 to 10 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1.

4. The electronic device according to claim 1, wherein the group Ar.sup.2 is selected on each occurrence, identically or differently, from aryl or heteroaryl groups having 6 to 10 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1.

5. The electronic device according to claim 1, wherein R.sup.1 is on each occurrence, identically or differently, H, D, F, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, 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, where the above-mentioned groups may each be substituted by one or more radicals R.sup.2 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —C≡C—, —R.sup.2C═CR.sup.2—, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, —NR.sup.2—, —O—, —S—, —C(═O)O— or —C(═O)NR.sup.2—, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, where two or more radicals R.sup.1 is optionally linked to one another and may form a ring.

6. The electronic device according to claim 1, wherein the index n is on each occurrence, identically or differently, 0 or 1.

7. The electronic device according to claim 1, wherein the index i is equal to 0.

8. The electronic device according to claim 1, wherein in compounds of the formulae (I) and (II), a group selected from groups of the formula (A-1) and (A-2) according to claim 1 is bonded at the positions denoted by *.

9. The electronic device according to claim 1, wherein the compounds of the formulae (I) and (II) contain no further arylamino groups in addition to the groups (A-1), (A-2), (C-1) and (C-2) according to claim 1.

10. The electronic device according to claim 1, wherein the compounds of the formulae (I) and (II) contain no further carbazole groups in addition to the groups (A-1), (A-2), (C-1) and (C-2) according to claim 1.

11. The electronic device according to claim 1, wherein the compounds of the formula (I) are compounds of the following formulae (I-1) to (I-4): ##STR00512## where E.sup.1 is selected from C(R.sup.1).sub.2, Si(R.sup.1).sub.2, C═O, O, S, S═O, SO.sub.2 and NR.sup.1, where a group selected from the groups of the formulae (A-1), (A-2), (C-1) and (C-2) according to claim 1 is bonded at the positions denoted by *, and where a group selected from groups of the formulae (A-1) and (A-2) according to claim 1 is bonded at at least one of the positions denoted by *, and where all other groups are defined as in claim 1.

12. The electronic device according to claim 1, wherein the device is an organic integrated circuit (OIC), an organic field-effect transistor (OFET), an organic thin-film transistor (OTFT), an organic light-emitting transistor (OLET), an organic solar cell (OSC), an organic optical detector, an organic photoreceptor, an organic field-quench device (OFQD), an organic light-emitting electrochemical cell (OLEC), an organic laser diode (O-laser) or an organic electroluminescent device (OLED).

13. The electronic device according to claim 12, wherein the device is an organic electro-luminescent device comprising an organic layer which comprises the compound of the formula (I) or (II) is a layer having a hole-transporting function or an emitting layer.

14. A display and/or as light source in lighting applications and/or as light source in medical or cosmetic applications which comprises the electronic device according to claim 1.

15. An electronic device in a hole-transporting or in an emitting layer which comprises the compound of the formula (I) or (II) ##STR00513## where a group selected from the groups of the formulae ##STR00514## is bonded at the positions denoted by *, where: E is selected on each occurrence, identically or differently, from a single bond, C(R.sup.1).sub.2, Si(R.sup.1).sub.2, C═O, O, S, S═O, SO.sub.2 and NR.sup.1; Z is on each occurrence, identically or differently, CR.sup.1 or N; W is selected on each occurrence, identically or differently, from C═O, O, S, S═O, SO.sub.2 and NR.sup.1; Ar.sup.1 is selected on each occurrence, identically or differently, from aryl or heteroaryl groups having 6 to 13 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1; Ar.sup.2 is selected on each occurrence, identically or differently, from aryl or heteroaryl groups having 6 to 13 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1; X is selected on each occurrence, identically or differently, from C(R.sup.1).sub.2, Si(R.sup.1).sub.2, C═O, O, S, S═O, SO.sub.2 and NR.sup.1; Y is a single bond; R.sup.1 is on each occurrence, identically or differently, H, D, F, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, P(═O)(R.sup.2).sub.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, 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 or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.2 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO or SO.sub.2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, where two or more radicals R.sup.1 is optionally linked to one another and may form a ring; R.sup.2 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by D or F; two or more substituents R.sup.2 here is optionally linked to one another and may form a ring; n is on each occurrence, identically or differently, 0, 1, 2, 3 or 4; i is on each occurrence, identically or differently, 0 or 1; k is on each occurrence, identically or differently, 0 or 1, where at least one index k per group of the formula (C-1) must be equal to 1; and where a group selected from groups of the formulae (A-1) and (A-2) must be bonded at at least one of the positions denoted by *, and where furthermore no condensed aryl or heteroaryl group having 14 or more aromatic ring atoms is present in the compound.

Description

WORKING 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 numbers in square brackets for chemical compounds known from the literature relate to the CAS numbers.

Synthesis of Precursors

Example Int-1: 3-Dibenzofuran-4-yl-9-phenyl-9H-carbazole

(2) ##STR00185##

(3) 4335 g (204.1 mmol) of dibenzofuran-4-boronic acid, 60 g (186.2 mmol) of 3-bromo-9-phenyl-9H-carbazole, 118.4 ml (237 mmol) of Na.sub.2CO.sub.3 (2M solution) are suspended in 180 ml of toluene, 180 ml of ethanol and 150 ml of water. 3.9 g (3.3 mmol) of Pd(PPh.sub.3).sub.4 are added to this suspension, and the reaction mixture 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 of water and subsequently evaporated to dryness. The residue is recrystallised from toluene. The yield is 75.7 g (181 mmol), corresponding to 96% of theory.

(4) The following compounds can be obtained analogously:

(5) TABLE-US-00003 Starting Starting material 1 material 2 Product Yield Int-1a 90% Int-1b 0 92% Int-1c 89% Int-1d 92% Int-1e 00 86% Int-1f 01 02 03 96% Int-1g 04 05 06 90%

Example Int-2: Bisbiphenyl-4-yldibenzofuran-4-ylamine

(6) ##STR00207##

(7) A degassed solution of 43.92 g (176 mmol) of 4-bromodibenzofuran and 47.41 g (148 mmol) of bisbiphenyl-4-ylamine in 700 ml of toluene is saturated with N.sub.2 for 30 min. Then, firstly 2.51 ml (10.3 mmol) of 1M solution in toluene of P(tBu).sub.3, then 1.66 g (7.3 mmol) of palladium(II) acetate are added to the mixture, and 21.24 g (222 mmol) of NaOtBu in the solid state are subsequently added. The reaction mixture is heated under reflux for 6 h. After cooling to room temperature, 500 ml of water are carefully added. The aqueous phase is washed with 3×70 ml of toluene, dried over MgSO.sub.4, and the solvent is removed in vacuo. The crude product is then purified by chromatography on silica gel with heptane/ethyl acetate (20:1). The yield is 70.91 g (142.8 mmol), corresponding to 94% of theory.

(8) The following compounds can be obtained analogously:

(9) TABLE-US-00004 Starting Starting material 1 material 2 Product Yield Int-2a 08 09 0 90% Int-2b 87% Int-2c 83% Int-2d 57% Int-2e 0 86% Int-2f 85%

Example Int-3: 9-Phenyl-3-(6-trimethylsilanyldibenzofuran-4-yl)-9H-carbazole

(10) ##STR00226##

(11) 127 ml (225.4 mmol) of n-butyllithium (2.5 M in hexane) are added dropwise to a solution, cooled to 15° C., of 49 g (121 mmol) of 3-dibenzofuran-4-yl-9-phenyl-9H-carbazole and 28 g (242 mmol) of TMEDA in 1000 ml of THF. The reaction mixture is stirred at room temperature for 3 h, then cooled to 0° C., and 26 g (242 mmol) of chlorotrimethylsilane are added dropwise over the course of 30 min., and the mixture is stirred at room temperature for 16 h. The solvent is subsequently removed in vacuo, and the residue is purified by chromatography on silica gel with toluene:dichloromethane 2:1. Yield: 34 g (72 mmol), 60% of theory.

(12) The following compounds can be obtained analogously:

(13) TABLE-US-00005 Starting material 1 Product Yield Int-3a 81% Int-3b 0 88% Int-3c 84% Int-3d 88% Int-3e 70% Int-3f 86% Int-3g 0 79% Int-3h 75% Int-3i 72% Int-3j 81% Int-3k 83% Int-3l 0 88% Int-3m 84%

Example Int-4: B-[6-(Phenyl-9H-carbazol-3-yl)-4-dibenzofuranyl]boronic acid

(14) ##STR00253##

(15) Under protective gas, 21 g (86 mmol) of bromine tribromide are added dropwise to a solution of 34 g (72 mmol) of B-[6-(phenyl-9H-carbazol-3-yl)-4-dibenzofuranyl]boronic acid in 500 ml of dichloromethane, and the mixture is stirred at room temperature for 10 h. A little water is then slowly added to the mixture, and the precipitated residue is filtered off and washed with heptane. The yield is 28 g (62 mmol), corresponding to 86% of theory.

(16) The following compounds can be obtained analogously:

(17) TABLE-US-00006 Starting material 1 Product Yield Int-4a 82% Int-4b 81% Int-4c 87% Int-4d 0 86% Int-4e 79% Int-4f 78% Int-4g 83% Int-4h 85% Int-4i 0 78% Int-4j 84% Int-4k 87% Int-4l 80% Int-4m 86%

Example Int-5: B-[6-(Phenyl-9H-carbazol-3-yl)-4-dibenzofuranyl]boronic acid

(18) ##STR00280##

(19) 9 g (32 mmol) of B,B′-4,6-dibenzofurandiylbisboronic acid, 15 g (31.6 mmol) of 3-bromo-9-phenyl-9H-carbazole, 31 ml (63 mmol) of Na.sub.2CO.sub.3 (2M solution) are suspended in 120 ml of toluene and 120 ml of ethanol. 0.73 g (0.63 mmol) of Pd(PPh.sub.3).sub.4 are added to this suspension, and the reaction mixture 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 of water and subsequently evaporated to dryness. The residue is recrystallised from toluene. The yield is 11.1 g (24 mmol), corresponding to 70% of theory.

(20) The following compounds can be obtained analogously:

(21) TABLE-US-00007 Starting material 1 Starting material 2 Int-5b Int-5c Product Yield Int-5b 69% Int-5c 74%

Synthesis of Compounds According to the Invention

Example 6: Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-{4-[6-(9-phenyl-9H-carbazol-3-yl)dibenzofuran-4-yl]phenyl}amine

(22) ##STR00287##

(23) 32.1 g (70 mmol) of B-[6-(phenyl-9H-carbazol-3-yl)-4-dibenzofuranyl]boronic acid, 36.12 g (70 mmol) of biphenyl-4-yl-(4-bromophenyl)-(9,9-dimethyl-9H-fluoren-2-yl)amine, and 78.9 ml (158 mmol) of Na.sub.2CO.sub.3(2M solution) are suspended in 120 ml of ethanol and 100 ml of water. 1.3 g (1.1 mmol) of Pd(PPh.sub.3).sub.4 are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, dichloromethane is added to the mixture, the organic phase is separated off and filtered through silica gel. The yield is 40 g (47 mmol), corresponding to 67.8% of theory. The residue is recrystallised from toluene and finally sublimed in a high vacuum (p=5×10.sup.−6 mbar). The purity is 99.9%.

(24) The following compounds can be obtained analogously:

(25) TABLE-US-00008 Starting material 1 Starting material 2 6a 6b 0 6c 6d 6e 6f 6g 00 01 6h 02 03 6i 04 05 6j 06 07 6k 08 09 6l 0 6n 6o 6p 6r 6s 0 6t Product 6a 6b 6c 6d 6e 6f 6g 0 6h 6i 6j 6k 6l 6n 6o 6p 6r 6s 0 6t

(26) TABLE-US-00009 Yield 6a 60% 6b 77% 6c 82% 6d 78% 6e 84% 6f 63% 6g 52% 6h 71% 6i 69% 6j 73% 6k 52% 6l 48% 6n 56% 6o 67% 6p 69% 6r 45% 6s 64% 6t 60%

Synthesis of Precursors

Example Int-7: 3-(6-Bromodibenzofuran-4-yl)-9-phenyl-9H-carbazole

(27) ##STR00342##

(28) 10.43 g (32 mmol) of B-(9-phenyl-9H-carbazol-3-yl)boronic acid, 8.9 g (31.6 mmol) of 4,6-dibromodibenzofuran and 31 ml (63 mmol) of Na.sub.2CO.sub.3 (2M solution) are suspended in 120 ml of toluene and 120 ml of ethanol. 0.73 g (0.63 mmol) of Pd(PPh.sub.3).sub.4 are added to this suspension, and the reaction mixture 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 of water and subsequently evaporated to dryness. The residue is recrystallised from toluene. The yield is 11.4 g (23 mmol), corresponding to 73% of theory.

(29) The following compounds can be obtained analogously:

(30) TABLE-US-00010 Starting material 1 Starting material 2 Int-7a Int-7b Int-7c Int-7d 0 Int-7e Int-7f Int-7g Int-7h Int-7i 0 Int-7j Int-7k Product Yield Int-7a 51% Int-7b 65% Int-7c 69% Int-7d 67% Int-7e 62% Int-7f 0 62% Int-7g 61% Int-7h 64% Int-7i 66% Int-7j 62% Int-7k 65%

(31) Synthesis of Compounds According to the Invention:

(32) The following compounds can be obtained analogously by double addition reaction with corresponding boronic acids:

(33) TABLE-US-00011 Starting material 1 Starting material 2 7l 7m 7n 0 7o 7p 7q 7r 7s 0 7t 7u 7v Product 7l 7m 7n 00 7o 01 7p 02 7q 03 7r 04 7s 05 7t 06 7u 07 7v 08

(34) TABLE-US-00012 Yield 7l 52% 7m 67% 7n 80% 7o 79% 7p 58% 7q 78% 7r 87% 7s 87% 7t 83% 7u 80% 7v 87%

Example 8: Bisbiphenyl-4-yl-(4-{1-[3-eth-(Z)-ylidene-7-(9-phenyl-9H-carbazol-3-yl)-3H-benzofuran-(2Z)-ylidene]ethyl}phenyl)amine

(35) ##STR00409##

(36) 87 g (180.1 mmol) of 3-(6-bromodibenzofuran-4-yl)-9-phenyl-9H-carbazole, 79 g (180.7 mmol) of B-[4-[bis([1,1′-biphenyl]-4-yl]amino]phenylboronic acid and 38.3 g (180.7 mmol) of potassium phosphate are suspended in 500 ml of toluene, 250 ml of 1,4-dioxane and 120 ml of water. 1.3 g (4.1 mmol) of tri(o-tolyl)phosphine and then 461 mg (2 mmol) of palladium(II) acetate are added to the mixture, and the reaction mixture is heated under reflux for 48 h. After cooling, the organic phase is separated off, washed three times with 100 ml of water each time and evaporated. After purification by column chromatography (SiO.sub.2, n-heptane/dichloromethane 3/1), the foam obtained is dissolved in dichloromethane and precipitated using ethanol. The residue is recrystallised from toluene and from dichloromethane and finally sublimed in a high vacuum (p=5×10.sup.−5 mbar). Yield: 129 g (160 mmol), 90%. Purity about 99% according to HPLC.

(37) The following compounds can be obtained analogously:

(38) TABLE-US-00013 Starting material 1 Starting material 2 8a 0 8b 8c 8d 8e 8f 0 8g 8h 8i 8j 8k 0 8l 8m Product 8a 8b 8c 8d 8e 0 8f 8g 8h 8i 8j 8k 8l 8m

(39) TABLE-US-00014 Yield 8a 68% 8b 73% 8c 86% 8d 65% 8e 63% 8f 79% 8g 62% 8h 64% 8i 65% 8j 64% 8k 66% 8l 62% 8m 65%

Example 9: Bisbiphenyl-4-yl-[4-(9,9′-diphenyl-9H,9′H-[1,2′]bicarbazolyl-8-yl)phenyl]amine

(40) ##STR00449##

(41) 40 g (49.75 mmol) of bisbiphenyl-4-yl-[4-(9′-phenyl-9H,9′H-[1,2+]bicarbazolyl-8-yl)phenyl]amine and 16.7 g (74.62 mmol) of bromobenzene are dissolved in toluene and degassed by passing in a protective gas. 4.9 ml (4.9 mmol, 1 M solution in toluene) of tri-tert-butylphosphine, 633.7 mg (2.82 mmol) of Pd(OAc).sub.2 and 10.2 g (105.87 mmol) of t-BuONa are subsequently added. The solids are degassed in advance, the reaction mixture is degassed afterwards and subsequently stirred under reflux for 12 h. The warm reaction solution is filtered through aluminium oxide B (activity grade 1), washed with water, dried and evaporated. The yield is 29.9 g (33.98 mmol), corresponding to 68% of theory. The residue is recrystallised from toluene and finally sublimed in a high vacuum (p=5×10.sup.−5 mbar). The purity is 99.9%.

(42) The following compounds can be obtained analogously:

(43) TABLE-US-00015 Starting material 1 Starting material 2 9a 0 9b 9c 9d 9e Product 9a 0 9b 9c 9d 9e

(44) TABLE-US-00016 Yieid 9a 79% 9b 90% 9c 79% 9d 90% 9e 79%

Synthesis of Precursors

Example Int-10: Bisbiphenyl-4-yl-(6-bromodibenzofuran-4-yl)amine

(45) ##STR00465##

(46) A mixture of 16.3 g (50 mmol) of 4,6-dibromodibenzofuran, 19.2 g (60 mmol) of bisbiphenyl-4-ylamine, 7.7 g (80 mmol) of sodium tert-butoxide, 1.4 g (5 mmol) of tricyclohexylamine, 561 mg (2.5 mmol) of palladium(II) acetate and 300 ml of mesitylene is heated under reflux for 24 h. After cooling, 200 ml of water are added, the mixture is stirred for a further 30 min., the org. phase is separated off, filtered through a short Celite bed, and the solvent is then removed in vacuo. The residue is recrystallised five times from DMF and finally subjected to fractional sublimation twice (p about 10.sup.−6 mbar). Yield: 22.9 g (40 mmol), 81%; purity: 99.9% according to HPLC.

(47) The following compounds are obtained analogously:

(48) TABLE-US-00017 Ex. Starting material Product Yield Int-10a 65% Int-10b 0 69% Int-10c 76% Int-10d 75% Int-10e 0 71%

(49) Synthesis of Compounds According to the Invention:

(50) The following compounds can be obtained analogously by second addition reaction with corresponding boro acids:

(51) TABLE-US-00018 Ex. Starting material Product 10f 10g 10h 10i 10j 0 10f 10g 10h 10i 10j

(52) TABLE-US-00019 Ex. Yield 10f 65% 10g 66% 10h 76% 10i 75% 10j 77%

B) Device Examples: Production of the OLEDs

(53) 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).

(54) The data for various OLEDs are presented in the following Examples E1 to E5 according to the invention and in Reference Examples V1 to V3. The substrates used are glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs have in principle the following layer structure: substrate/p-doped hole-transport layer (HTL1)/hole-transport layer (HTL2)/p-doped hole-transport layer (HTL3)/hole-transport layer (HTL4)/emission layer (EML)/electron-transport layer (ETL)/electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The materials required for the production of the OLEDs are shown in Table 1, the various component structures are shown in Table 2.

(55) 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 H1:SEB1 (95%:5%) here means that material H1 is present in the layer in a proportion by volume of 95% and SEB1 is present in the layer in a proportion of 5%. Analogously, the electron-transport layer or hole-injection layer may also consist of a mixture of two materials.

(56) 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 Im/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) assuming Lambert emission characteristics, and the lifetime are determined. The electroluminescence spectra 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 expression EQE @ 10 mA/cm.sup.2 denotes the external quantum efficiency at a current density of 10 mA/cm.sup.2. LT80 @ 50 mA/cm.sup.2 (lifetime) is the time by which the luminance of the OLED has dropped to 80% of the initial intensity at an initial luminance at constant current of 50 mA/cm.sup.2.

(57) TABLE-US-00020 TABLE 1 Structures of the materials used   F4TCNQ   HIM1   H1   SEB1 00   H2 01   TEG 02   ETM 03   LiQ 04   HTM1 05   HTMV1 06   HTMV2 07   HTM2 08   HTM3 09   HTM4

(58) TABLE-US-00021 TABLE 2 Structure of the devices HTL1 HTL2 HTL3 HTL4 EML ETL EIL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm nm nm V1 HIM1: HIM1 HTMV1: HTMV1 H1:SEB1 (5%) ETM (50%): LiQ F4TCNQ 155 nm F4TCNQ 20 nm 20 nm LiQ (50%) 1 nm (3%) (3%) 30 nm 20 nm 20 nm E1 HIM1: HIM1 HTM1: HTM1 H1:SEB1 (5%) ETM (50%): LiQ F4TCNQ 155 nm F4TCNQ 20 nm 20 nm LiQ (50%) 1 nm (3%) (3%) 30 nm 20 nm 20 nm V2 HIM1: HIM1 HTMV1: HTMV1 H2:TEG (10%) ETM (50%): LiQ F4TCNQ 160 nm F4TCNQ 70 nm 30 nm LiQ (50%) 1 nm (3%) (3%) 40 nm 20 nm 20 nm E2 HIM1: HIM1 HTM1: HTM1 H2:TEG (10%) ETM (50%): LiQ F4TCNQ 160 nm F4TCNQ 70 nm 30 nm LiQ (50%) 1 nm (3%) (3%) 40 nm 20 nm 20 nm V3 HIM1: HIM1 HTMV2: HTMV2 H1:SEB1 (5%) ETM (50%): LiQ F4TCNQ 155 nm F4TCNQ 20 nm 20 nm LiQ (50%) 1 nm (3%) (3%) 30 nm 20 nm 20 nm E3 HIM1: HIM1 HTM2: HTM2 H1:SEB1 (5%) ETM (50%): LiQ F4TCNQ 155 nm F4TCNQ 20 nm 20 nm LiQ (50%) 1 nm (3%) (3%) 30 nm 20 nm 20 nm E4 HIM1: HIM1 HTM3: HTM3 H1:SEB1 (5%) ETM (50%): LiQ F4TCNQ 155 nm F4TCNQ 20 nm 20 nm LiQ (50%) 1 nm (3%) (3%) 30 nm 20 nm 20 nm E5 HIM1: HIM1 HTM4: HTM4 H1:SEB1 (5%) ETM (50%): LiQ F4TCNQ 155 nm F4TCNQ 20 nm 20 nm LiQ (50%) 1 nm (3%) (3%) 30 nm 20 nm 20 nm

(59) Results:

(60) The examples show the use of compound HTM1 according to the invention as hole-transport material in a hole-transport layer.

(61) A comparative device V1 is produced and compared with device E1 according to the invention. Device V1 has a compound in accordance with the prior art HTMV1 in the hole-transport layer HTL3, device E1 according to the invention has a compound HTM1 in accordance with the present invention as hole-transport material in the hole-transport layer HTL3. Both devices E1 and V1 have a fluorescent compound (SEB1) in the emitting layer.

(62) Reference device V1 has an external quantum efficiency of 7.8% and a lifetime (LT80 @ 50 mA/cm.sup.2) of 290 h at a current density of 10 mA/cm.sup.2. By comparison, both the external quantum efficiency at a current density of 10 mA/cm.sup.2 of 8.4% is higher and also the measured lifetime (LT80 @ 50 mA/cm.sup.2) of 320 h is longer in the case of device E1 according to the invention.

(63) A comparative device V2 is produced and compared with device E2 according to the invention. Device V2 has a compound in accordance with the prior art HTMV1 in the hole-transport layer HTL3, device E2 according to the invention has a compound HTM1 in accordance with the present invention as hole-transport material in the hole-transport layer HTL3. Both devices E1 and V1 have a phosphorescent compound (TEG) in the emitting layer.

(64) Compared with a reference device V2, the corresponding device E2 according to the invention exhibits both a higher quantum efficiency (@ 2 mA/cm.sup.2) of 20.4% compared with reference device V2 of 19.4% and also a longer lifetime (LT80 @ 20 mA/cm.sup.2) of 180 h compared with reference device E2 of 120 h.

(65) Compared with reference material HTMV2 (6.2%, 135 h)), the materials according to the invention HTM2 (7.4%, 270 h), HTM3 (8.2%, 300 h) and HTM4 (7.2%, 210 h) exhibit better external quantum efficiencies at 10 mA/cm.sup.2 and a better lifetime (LT80 at 50 mA/cm.sup.2) on use as hole-transport material in a blue-fluorescent OLED.

(66) The examples show the surprising advantages on use of compounds HTM1 to HTM4 according to the invention containing two arylamino groups or one arylamino group and one carbazole group bonded “face to face” to a central linker group, compared with the use of a compound containing a single arylamino group HTMV1 or the use of the diamino compound HTMV2.

(67) The examples show advantages on use of the materials as hole-transport material in combination with fluorescent and phosphorescent emitting layers. However, the invention is not restricted to this use. For example, the compounds can also be employed with comparably advantageous effect as matrix materials in the emitting layer.

C) Measurement of the Glass Transition Temperature

(68) T.sub.G measurements are carried out by standard methods (carried out on a TA-Instruments Q2000 series instrument for DSC measurement). The following results are obtained (Table 3).

(69) TABLE-US-00022 TABLE 3 T.sub.G measurements Compound Glass transition temperature T.sub.G HTMV1 111° C. HTM1 155° C. HTM2 148° C. HTM3 113° C. HTM4 142° C.

(70) It was found that material HTM1 according to the invention has a high glass transition temperature of 155° C., which is very advantageous for use in OLEDs. Compounds HTM2 and HTM4 according to the invention also have high glass transition temperatures. By contrast, the glass transition temperature T.sub.G of comparative compound HTMV1 is significantly lower.