Compounds and organic electronic devices

Abstract

The present invention relates to certain fluorenes, to the use of the compounds in an electronic device, and to an electronic device comprising at least one of these compounds. The present invention furthermore relates to a process for the preparation of the compounds and to a formulation and composition comprising one or more of the compounds.

Claims

1. A compound of the general formula (1) ##STR00503## where the following applies to the symbols and indices used: R.sup.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, NO.sub.2, P(═O)(R.sup.4).sub.2, S(═O)R.sup.4, S(═O).sub.2R.sup.4, a straight-chain alkyl, alkoxy or thio-alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl 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.4 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.4C═CR.sup.4—, —C≡C—, Si(R.sup.4).sub.2, C═O, C═S, C═NR.sup.4, —C(═O)O—, —C(═O)NR.sup.4—, P(═O)(R.sup.4), —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, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.4, or an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.4, or an aralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.4, where the two radicals R.sup.1 is optionally linked to one another and may form a ring, so that a spiro compound forms in position 9 of the fluorene, where spirobifluorenes are excluded; R.sup.2 and R.sup.3 are on each occurrence, identically or differently, preferably identically, H, D, F, Cl, Br, I, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, NO.sub.2, P(═O)(R.sup.4).sub.2, S(═O)R.sup.4, S(═O).sub.2R.sup.4, N(R.sup.4).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl 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.4 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.4C═CR.sup.4—, —C≡C—, Si(R.sup.4).sub.2, C═O, C═S, C═NR.sup.4, —C(═O)O—, —C(═O)NR.sup.4—, P(═O)(R.sup.4), —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, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.4, or an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.4, or an aralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.4, where two or more radicals R.sup.2 or two or more radicals R.sup.3 is optionally linked to one another and may form a ring; R.sup.4 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, NO.sub.2, P(═O)(R.sup.5).sub.2, S(═O)R.sup.5, S(═O).sub.2R.sup.5, N(R.sup.5).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thio-alkyl 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.5 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═S, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, P(═O)(R.sup.5), —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, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.5, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.5; R.sup.5 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 C atoms, in which one or more H atoms is optionally replaced by D or F, where two or more adjacent substituents R.sup.5 may form a mono- or polycyclic, aliphatic ring system with one another; q is 1, and p and r are 0; Z.sup.a.sub.0, Z.sup.c.sub.0 are R.sup.3; Z.sup.b.sub.1 is ##STR00504## B′ is an aryl group having 6 to 30 ring atoms or a mono- or bicyclic heteroaryl group having 5 to 30 ring atoms, each of which is optionally substituted by one or more radicals R.sup.4; Ar.sup.1, Ar.sup.2 are on each occurrence, identically or differently, an aromatic radical having 10 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.6, which are identical to or different from one another, where the two groups Ar.sup.1 or Ar.sup.2 each contain at least two or more aromatic rings, R.sup.6 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, NO.sub.2, P(═O)(R.sup.5).sub.2, S(═O)R.sup.5, S(═O).sub.2R.sup.5, a straight-chain alkyl, alkoxy or thio-alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl 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.5 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═S, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, P(═O)(R.sup.5), —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, Cl, Br, I, CN or NO.sub.2, or an aromatic or hetero-aromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.5, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.5; with the proviso that Z.sup.a.sub.1, Z.sup.b.sub.1 and Z.sup.c.sub.1 in the compound of the formula (1) contain no fluorene or carbazole groups.

2. The compound according to claim 1, wherein Ar.sup.1 is selected from the following groups of the formulae (37) to (75), optionally substituted by one or more radicals R.sup.6 ##STR00505## ##STR00506## ##STR00507## ##STR00508## ##STR00509## ##STR00510## ##STR00511##

3. The compound according to claim 1, wherein Ar.sup.2 is selected from the following groups of the formulae (37) to (75), which may be substituted by one or more radicals R.sup.6 ##STR00512## ##STR00513## ##STR00514## ##STR00515## ##STR00516## ##STR00517## ##STR00518##

4. The compound according to claim 1, wherein the compound has the general formula (2) ##STR00519## where the definitions from claim 1 apply to the symbols used.

5. The compound according to claim 1, wherein the compound has the general formula (4) ##STR00520## where the definitions from claim 1 apply to the symbols used.

6. The compound according to claim 1, wherein the two R.sup.1 are identical.

7. The compound according to claim 1, wherein B′ is a phenylene, biphenylene, terphenylene, naphthylene, pyridinylene, pyrimidinylene, pyrazinylene, pyridazinylene, triazin-ylene, dibenzofuranylene or dibenzothiophenylene group, which is optionally substituted by one or more radicals R.sup.4.

8. The compound according to claim 1, wherein B′ is a phenylene, biphenylene, terphenylene, naphthylene, dibenzofuranylene or dibenzothiophenylene group, which is optionally substituted by one or more radicals R.sup.4.

9. The compound according to claim 1, wherein B′ is a phenylene, biphenylene or terphenylene group, which is optionally substituted by one or more radicals R.sup.4.

10. The compound according to claim 1, wherein B′ is a phenylene group, which is optionally substituted by one or more radicals R.sup.4.

11. The compound according to claim 1, wherein B′ is an unsubstituted phenylene group.

12. The compound according to claim 1, wherein B′ is a single bond.

13. The compound according to claim 1, wherein the compound is a monoamine compound.

14. A process for the preparation of the compound according to claim 1 by means of one-step Buchwald coupling by reacting a fluorene derivative which contains a leaving group with Ar.sup.2—NH—Ar.sup.1.

15. A process for the preparation of the compound according to claim 1 by means of two-step Buchwald coupling by stepwise reacting a fluorene derivative which contains a leaving group with (1) Ar.sup.2—NH.sub.2 and (2) NH.sub.2—Ar.sup.1.

16. A process for the preparation of the compound according to claim 1, wherein the compound is prepared from a benzochromen-6-one.

17. The process according to claim 16, comprising the following steps: a) adding an organometallic compound onto a benzochromen-6-one and subsequent b) acid-catalysed cyclisation to give a 4-hydroxyfluorene derivative and subsequent c) converting the hydroxyl group in position 4 of the fluorene into a leaving group and subsequent d) converting the fluorene into the desired product.

18. An oligomer, polymer or dendrimer containing one or more compounds according to claim 1, where the bond(s) to the polymer, oligomer or dendrimer is optionally localised at any position in formula (1) that are substituted by R.sup.1 to R.sup.6.

19. A composition comprising one or more compounds according to claim 1 and at least one further organically functional material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron-transport materials, electron-injection materials, hole-conductor materials, hole-injection materials, electron-blocking materials and hole-blocking materials.

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

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

22. The electronic device according to claim 21, 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).

23. An organic electroluminescent device which comprises the compound according to claim 1 is employed in one or more of the following functions: as hole-transport material in a hole-transport or hole-injection layer, as matrix material in an emitting layer, as electron-blocking material or as exciton-blocking material.

Description

EXAMPLES

(1) Materials

(2) ##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247##

(3) Materials HIL1, HIL2 (EP 0676461), H1 (WO 2008/145239), H2 (WO 2010/136109), ETM1 (WO 2005/053055), SEB1 (WO 2008/006449), LiQ, Irpy and NPB are well known to the person skilled in the art from the prior art. Compounds HTMV1 to HTMV6 are comparative compounds, which can be prepared analogously to the process described in Example 1. Compounds (1-1), (1-4), (1-7) (5-1), (4-1), (1-12), (1-13), (1-14), (1-15), (6-3), (6-2), (6-1), (6-4), (6-5), (8-1), (7-2), (7-1), (9-2), (2-7), (2-8) and (1-17) are in accordance with the invention.

Example 1

Synthesis of the compound bisbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-4-yl)amine (1-1) and compounds (1-2) to (1-12)

(4) ##STR00248##

4-Bromo-9,9-diphenyl-9H-fluorene

(5) 37 g (152 mmol) of 2,2′-dibromobiphenyl are dissolved in 300 ml of dried THF in a flask which has been dried by heating. The reaction mixture is cooled to −78° C. 75 ml of a 15% solution of n-BuLi in hexane (119 mmol) are slowly added dropwise at this temperature (duration: about 1 hour). The batch is stirred at −70° C. for a further 1 h. 21.8 g of benzophenone (119 mmol) are subsequently dissolved in 100 ml of THF and added dropwise at −70° C. When the addition is complete, the reaction mixture is slowly warmed to room temperature, quenched using NH.sub.4Cl and subsequently evaporated in a rotary evaporator. 510 ml of acetic acid are carefully added to the evaporated solution, and 100 ml of fuming HCl are subsequently added. The batch is heated to 75° C. and kept at this temperature for 4 h. A white solid precipitates out during this time. The batch is then cooled to room temperature, the precipitated solid is filtered off with suction and rinsed with methanol. The residue is dried at 40° C. in vacuo. The yield is 33.2 g (83 mmol) (70% of theory).

(6) The following brominated compounds are prepared analogously:

(7) TABLE-US-00002 Starting Starting material 1 material 2 Product Yield 0 78% 70% 82% 0 85% 80% 85% 77%

Bisbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-4-yl)amine (1-1)

(8) 17 g of bisbiphenyl-4-ylamine (53 mmol) and 23.1 g of 4-bromo-9,9-diphenyl-9H-fluorene (58 mmol) are dissolved in 500 ml of toluene: the solution is degassed and saturated with N.sub.2. 5.3 ml (5.3 mmol) of a 1 M tri-tert-butylphosphine solution and 0.6 g (2.65 mmol) of palladium(II) acetate are then added. 12.7 g of sodium tert-butoxide (132.23 mmol) are subsequently added. The reaction mixture is heated at the boil for 3 h under a protective atmosphere. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum.

(9) The purity is 99.9%. The yield is 29 g (87% of theory).

(10) The following compounds (1-2) to (1-17) are prepared analogously

(11) TABLE-US-00003 Starting Starting material 1 material 2 Product Yield 0 78% (1-2) 83% (1-3) 92% (1-4) 0 88% (1-5) 77% (1-6) 75% (1-7) 0 80% (1-8) 77% (1-9) 71% (1-10) 70% (1-11) 00 01 02 75% 2 equiv. (1-12) 03 04 05 77% 2 equiv. (1-13) 06 07 08 75% (1-14) 09 0 85% (1-15) 79% (1-16) 72% (1-17)

Example 2

Synthesis of the compound biphenyl-3-ylbiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-3-yl)amine (2-1) and compounds (2-2) to (2-10)

(12) ##STR00318##

3-Bromo-9,9-dimethyl-9H-fluorene

(13) 29.5 g (120 mmol) of 3-bromo-9H-fluorene (Tetrahedron Letters, 51, 37, 4894-4897; 2010) are dissolved in 220 ml of dried DMSO in a flask which has been dried by heating. 34.7 g (361 mmol) of NaO.sup.tBu are added at room temperature. The suspension is brought to an internal temperature of 65° C. A solution of 22.5 ml (361 mmol) of iodomethane in DMSO (50 ml) is added dropwise at this temperature at such a rate that the internal temperature does not exceed 65° C. (duration: about 30 min). The batch is kept at an internal temperature of 65° C. for a further 30 min., and subsequently poured into 400 ml of an ice-cold aqueous NH.sub.4OH solution (1/1, v/v) and stirred for about 20 min. The precipitated solid is filtered off with suction and washed successively with about 200 ml of H.sub.2O and methanol. Yield: 31 g (114 mmol) (95% of theory).

(14) The following brominated compounds are prepared analogously:

(15) TABLE-US-00004 Starting Starting material 1 material 2 Product Yield H.sub.3C—I 0 78% 85%

Biphenyl-3-ylbiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-3-yl)amine (2-1)

(16) 30 g of biphenyl-3-ylbiphenyl-4-ylamine (93.4 mmol) and 25.5 g of 3-bromo-9,9-dimethyl-9H-fluorene (93.4 mmol) are dissolved in 600 ml of toluene: the solution is degassed and saturated with N.sub.2. 3.2 g (3.73 mmol) of tri-tert-butylphosphine and 0.42 g (1.87 mmol) of palladium(II) acetate are then added. 13.9 g of sodium tert-butoxide (140 mmol) are subsequently added. The reaction mixture is heated at the boil for 5 h under a protective atmosphere. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9%. The yield is 37.8 g (79% of theory).

(17) The following compounds (2-2) to (2-10) are prepared analogously:

(18) TABLE-US-00005 Starting Starting material 1 material 2 Product Yield 78% (2-2) 82% (2-3) 0 80% (2-4) 92% (2-5) 75% (2-6) 0 67% (2-7) 73% (2-8) 70% (2-9) 0 66% (2-10)

Example 3

Synthesis of the compound biphenyl-2-ylbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (3-1) and compounds (3-2) to (3-5)

(19) ##STR00351##

3-Bromo-9,9-diphenyl-9H-fluorene

(20) 50 g (193 mmol) of 3-bromo-9H-fluorenone (Tetrahedron, 51, 7, 2039-54; 1995) are dissolved in 500 ml of dried THF in a flask which has been dried by heating. The clear solution is cooled to −10° C., and 70.7 ml (212 mmol) of a 3 M phenylmagnesium bromide solution are then added. The reaction mixture is slowly warmed to room temperature and then quenched using NH.sub.4C (500 ml). The mixture is subsequently partitioned between ethyl acetate and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The crude product is recrystallised from heptane/toluene. 400 ml of benzene are added to the residue. The batch is heated to 50° C., and 18.6 ml of trifluoromethanesulfonic acid are subsequently added dropwise. After 30 min., the reaction mixture is cooled to room temperature and poured into 1 l of water. The mixture is partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. Filtration of the crude product through silica gel with heptane/ethyl acetate 1:1 gives 55.6 g (135 mmol) (70% of theory).

(21) The following brominated compounds are prepared analogously:

(22) TABLE-US-00006 Starting Starting Starting material 1 material 2 material 3 Product Yield 75% 65%

Biphenyl-2-ylbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (3-1)

(23) 12 g of biphenyl-2-ylbiphenyl-4-ylamine (37 mmol), 16.3 g of 3-bromo-9,9-diphenyl-9H-fluorene (41 mmol) are dissolved in 360 ml of toluene: the solution is degassed and saturated with N.sub.2. 3.7 ml (3.7 mmol) of a 1 M solution of tri-tert-butylphosphine and 0.42 g (1.87 mmol) of palladium(II) acetate are then added. 9.0 g of sodium tert-butoxide (93.3 mmol) are subsequently added. The reaction mixture is heated at the boil for 3 h under a protective atmosphere. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9%. The yield is 20 g (85% of theory).

(24) The following compounds (3-2) to (3-5) are prepared analogously:

(25) TABLE-US-00007 Starting Starting material 1 material 2 Product Yield 0 78% (3-2) 80% (3-3) 85% (3-4) 0 80% (3-5)

Example 4

Synthesis of the compound bisbiphenyl-4-yl-[4-(9,9-diphenyl-9H-fluoren-4-yl)phenyl]amine (4-1) and compounds (4-2) to (4-7)

(26) ##STR00372##

4-(4-Chlorophenyl)-9,9-diphenyl-9H-fluorene

(27) 7.9 g (50 mmol) of 4-chlorobenzeneboronic acid, 20 g (50 mmol) of 4-bromo-9,9-diphenyl-9H-fluorene and 55 ml of an aqueous 2 M NaHCO.sub.3 solution (111 mmol) are suspended in 400 ml of dimethoxyethane. 1.45 g (1.26 mmol) of tetrakis(triphenylphosphine)palladium(0) are added to this suspension. 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 300 ml of water and subsequently evaporated to dryness. Filtration of the crude product through silica gel with heptane/ethyl acetate (20:1) gives 18.4 g (85%) of 4-(4-chlorophenyl)-9,9-diphenyl-9H-fluorene.

(28) The following chlorinated compounds are prepared analogously:

(29) TABLE-US-00008 Starting Starting material 1 material 2 Product Yield 79% 70% 0 72%

Bisbiphenyl-4-yl-[4-(9,9-diphenyl-9H-fluoren-4-yl)phenyl]amine (4-1)

(30) 13.60 g of bisbiphenyl-4-ylamine (43 mmol) and 18.2 g of 4-chloro-9,9-diphenyl-9H-fluorene (43 mmol) are dissolved in 400 ml of toluene: the solution is degassed and saturated with N.sub.2. 1.04 g (2.55 mmol) of S-Phos and 1.94 g (2.1307 mmol) of palladium(II) dba are then added. 10 g of sodium tert-butoxide (106 mmol) are subsequently added. The reaction mixture is heated at the boil for 3 h under a protective atmosphere. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator.

(31) After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9%. The yield is 23 g (77% of theory).

(32) The following compounds are prepared analogously:

(33) TABLE-US-00009 Starting Starting material 1 material 2 Product Yield 78% 70% 0 75% 88% 73% 73%

Example 5

Synthesis of the compound bisbiphenyl-4-yl-[9,9-dimethyl-1-(9-phenyl-9H-carbazol-3-yl)-9H-fluoren-4-yl]amine (5-1) and compounds (5-2) to (5-5)

(34) ##STR00400##

Bisbiphenyl-4-yl-(1-bromo-9,9-dimethyl-9H-fluoren-4-yl)amine

(35) 15.0 g (29 mmol) of bisbiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl)amine are dissolved in 150 ml of acetonitrile, and 5.2 g (29 mmol) of N-bromo-succinimide are added in portions at room temperature. When the reaction is complete, water and ethyl acetate are added, and the organic phase is separated off, dried and evaporated. The crude product is subsequently washed by stirring a number of times with hot MeOH/heptane (1:1). Yield: 13.5 g (80%) of the product.

(36) The following brominated compounds are prepared analogously:

(37) TABLE-US-00010 Starting material 1 Product Yield 01 02 85% 03 04 81%

Bisbiphenyl-4-yl-[9,9-dimethyl-1-(9-phenyl-9H-carbazol-3-yl)-9H-fluoren-4-yl]amine (5-1)

(38) 6.3 g (22 mmol) of N-phenylcarbazol-3-ylboronic acid and 13 g (22 mmol) of bisbiphenyl-4-yl-(1-bromo-9,9-dimethyl-9H-fluoren-4-yl)amine are suspended in 200 ml of dimethoxyethane and 30 ml of 2 M Na.sub.2CO.sub.3 solution. 0.6 g (2.0 mmol) of tetrakis(triphenylphosphine)palladium is added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the reaction mixture is diluted with ethyl acetate, and the organic phase is separated off, washed three times with 100 ml of water and subsequently evaporated to dryness. Filtration of the crude product through silica gel with heptane/ethyl acetate (20:1) gives 15 g (90%) of bisbiphenyl-4-yl-[9,9-dimethyl-1-(9-phenyl-9H-carbazol-3-yl)-9H-fluoren-4-yl]amine (5-1).

(39) Compounds (5-2) to (5-5) are prepared analogously:

(40) TABLE-US-00011 Starting Starting material 1 material 2 Product Yield 05 06 07 85% 08 09 0 81% 88% 85%

Example 6

Synthesis of the compound biphenyl-4-yl-(4-dibenzofuran-4-yl-phenyl)-[4-(9,9-diphenyl-9H-fluoren-4-yl)phenyl]amine (6-1) and compounds (6-2) to (6-5)

(41) ##STR00417##

Biphenyl-4-yl-(4-chlorophenyl)-(4-dibenzofuran-4-ylphenyl)amine

(42) 30.0 g of biphenyl-4-yl-(4-dibenzofuran-4-ylphenyl)amine (CAS: 955959-89-4) (73 mmol) and 17.4 g of 1-chloro-2-iodobenzene (73 mmol) are dissolved in 460 ml of toluene: the solution is degassed and saturated with N.sub.2. 2.9 ml (2.9 mmol) of a 1 M tri-tert-butylphosphine solution and 0.33 g (1.46 mmol) of palladium(II) acetate are then added. 10.5 g of sodium tert-butoxide (109 mmol) are subsequently added. The reaction mixture is heated at the boil for 3 h under a protective atmosphere. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9%. The yield is 30 g (80% of theory).

(43) The following compounds are prepared analogously:

(44) TABLE-US-00012 Starting Starting material 1 material 2 Product Yield 0 83% 80% 79%

Biphenyl-4-yl-(4-dibenzofuran-4-ylphenyl)-[4-(9,9-diphenyl-9H-fluoren-4-yl)phenyl]amine (6-1)

(45) 20.0 g (45 mmol) of pinacolyl (9,9-diphenyl-9H-fluoren-4-yl)boronate, 23.5 g (45 mmol) of biphenyl-4-yl-(4-chlorophenyl)-(4-dibenzofuran-4-yl-phenyl)-amine are suspended in 400 ml of dioxane and 13.7 g of caesium fluoride (90 mmol). 4.0 g (5.4 mmol) of bis(tricyclohexylphosphine)palladium dichloride are added to this suspension, and the reaction mixture is heated under reflux for 18 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 80 ml of water and subsequently evaporated to dryness. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9%. The yield is 25 g (80% of theory).

(46) The following compounds (6-2) to (6-5) are prepared analogously:

(47) TABLE-US-00013 Starting Starting material 1 material 2 Product Yield 65% 0 69% 75% 65%

Example 7

Synthesis of the compound bisbiphenyl-4-yl-(7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-yl)amine (7-1) and compounds (7-2) to (7-5)

(48) ##STR00439##

8-Dibenzofuran-4-ylbenzo[c]chromen-6-one

(49) 30.0 g (142 mmol) of dibenzofuran-4-boronic acid, 32 g (142 mmol) of 8-chlorobenzo[c]chromen-6-one (CAS: 742058-81-7) and 43 g of caesium fluoride (283 mmol) are suspended in 800 ml of dioxane. 12.5 g (17 mmol) of bis(tricyclohexylphosphine)palladium dichloride are added to this suspension, and the reaction mixture is heated under reflux for 18 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 100 ml of water and subsequently evaporated to dryness. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene. The yield is 45 g (88% of theory).

(50) The following compounds are prepared analogously:

(51) TABLE-US-00014 Starting Starting material 1 material 2 Product Yield 0 84% 90% 85% 0 76%

7-Dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-ol

(52) 25.4 g (70 mmol) of 8-dibenzofuran-4-ylbenzo[c]chromen-6-one are dissolved in 340 ml of dried THF in a flask which has been dried by heating. The solution is saturated with N.sub.2. The clear solution is cooled to −10° C., and 70 ml (210 mmol) of a 3 M phenylmagnesium bromide solution are then added. The reaction mixture is slowly warmed to room temperature and then quenched using acetic anhydride (70 mmol). The mixture is subsequently partitioned between ethyl acetate and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. 310 ml of acetic acid are carefully added to the evaporated solution, and 70 ml of fuming HCl are subsequently added. The batch is heated to 75° C. and kept at this temperature for 4 h. A white solid precipitates out during this time. The batch is then cooled to room temperature, and the precipitated solid is filtered off with suction and rinsed with methanol. The residue is dried at 40° C. in vacuo. Filtration of the crude product through silica gel with heptane/ethyl acetate 1:1 gives 26 g (75% of theory).

(53) The following brominated compounds are prepared analogously:

(54) TABLE-US-00015 Starting Starting material 1 material 2 Product Yield 72% 80% 0 77% CH.sub.3MgBr 72%

Bisbiphenyl-4-yl-(7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-yl)amine (7-1)

(55) 25 g (50 mmol) of 7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-ol are dissolved in 300 ml of dried THF in a flask which has been dried by heating. The solution is saturated with N.sub.2. The clear solution is cooled to 5° C., and 20 ml (150 mmol) of triethylamine, 122 mg of 4-dimethylaminopyridine and 8.65 ml of trifluoromethanesulfonic anhydride are then added. The reaction mixture is slowly warmed to room temperature. The reaction mixture is subsequently diluted with heptane, evaporated in a rotary evaporator and partitioned with water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. Filtration of the crude product through silica gel with heptane/ethyl acetate 1:1 gives 30 g (98% of theory).

(56) 18.9 g of the triflate (30 mmol) and 8.16 g of bis-4-biphenylamine (25 mmol) are dissolved in 240 ml of toluene: the solution is degassed and saturated with N.sub.2. 0.74 g (1.79 mmol) of S-Phos and 1.36 g of palladium dba (1.49 mmol) are then added. 5.7 g of sodium tert-butoxide (59.7 mmol) are subsequently added. The reaction mixture is heated at 85° C. for 3 h under a protective atmosphere. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene. The purity is 99.9%. The yield is 15 g (65% of theory).

(57) The following compounds are prepared analogously:

(58) TABLE-US-00016 Starting Starting material 1 material 2 Product Yield 73% 80% 0 69% 75%

Example 8

Synthesis of the compound N*2*,N*5*,N*5*-trisbiphenyl-4-yl-N*2*-biphenyl-2-yl-9,9-diphenyl-9H-fluorene-2,5-diamine (8-1)

(59) ##STR00475##

8-(Biphenyl-4-ylbiphenyl-2-ylamino)benzo[c]chromen-6-one

(60) 19.0 g of biphenyl-2-ylbiphenyl-4-ylamine (59 mmol) and 16.3 g of 8-bromobenzo[c]chromen-6-one (59 mmol) are dissolved in 400 ml of toluene: the solution is degassed and saturated with N.sub.2. 2.36 ml (2.36 mmol) of a 1 M tri-tert-butylphosphine solution and 0.27 g (1.18 mmol) of palladium(II) acetate are then added. 11.6 g of sodium tert-butoxide (109 mmol) are subsequently added. The reaction mixture is heated at the boil for 3 h under a protective atmosphere. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene. The yield is 27 g (90% of theory).

(61) The following compounds are prepared analogously:

(62) TABLE-US-00017 Starting Starting material 1 material 2 Product Yield 85% 0 75%

7-(Biphenyl-4-ylbiphenyl-2-ylamino)-9,9-diphenyl-9H-fluoren-4-ol

(63) The following compounds are prepared analogously to 7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-ol:

(64) TABLE-US-00018 Starting Starting material 1 material 2 Product Yield 88% 73% CH.sub.3MgBr 76%

N*2*,N*5*,N*5*-Trisbiphenyl-4-yl-N*2*-biphenyl-2-yl-9,9-diphenyl-9H-fluorene-2,5-diamine (8-1)

(65) Compound (8-1) is prepared analogously to bisbiphenyl-4-yl-(7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-yl)amine (compound (7-1)):

(66) TABLE-US-00019 Starting Starting material 1 material 2 Product Yield 0 74%

Example 9

Synthesis of the compound bisbiphenyl-4-yl-(4-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-1-yl)amine (9-1) and compounds (9-2) and (9-3)

(67) ##STR00493##

(68) 24.4 g (37 mmol) of 1-(bisbiphenyl-4-ylamino)-9,9-diphenyl-9H-fluoren-4-ol are dissolved in 210 ml of dried THF in a flask which has been dried by heating. The solution is saturated with N.sub.2. The clear solution is cooled to 5° C., and 15.5 ml (112 mmol) of triethylamine, 100 mg of 4-dimethylaminopyridine and 6.45 ml of trifluoromethanesulfonic anhydride are then added. The reaction mixture is slowly warmed to room temperature. The reaction mixture is subsequently diluted with heptane, evaporated in a rotary evaporator and partitioned with water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. Filtration of the crude product through silica gel with heptane/ethyl acetate 1:1 gives 26.7 g (91% of theory).

(69) 17.2 g (22 mmol) of 1-(bisbiphenyl-4-ylamino)-9,9-diphenyl-9H-fluoren-4-ol, 6.9 g (33 mmol) of 4-bibenzofuranboronic acid, 9.0 g of sodium metaborate octahydrate (32.9 mmol) and 0.03 ml of hydrazinium hydroxide (0.657 mmol) are suspended in 200 ml of THF. 0.3 g (0.44 mmol) of bis(triphenyl-phosphine)palladium dichloride is added to this suspension, and the reaction mixture is heated at 70° C. for 18 h. After cooling, the mixture is partitioned between ethyl acetate and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and subsequently evaporated to dryness. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and subsequently sublimed. The yield is 12 g (70% of theory).

(70) The following compounds are prepared analogously:

(71) TABLE-US-00020 Starting Starting material 1 material 2 Product Yield 74% 73% 00 01 02 76%

Example 10

(72) Characterisation of the Compounds

(73) 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).

(74) The data for various OLEDs are shown in the following examples V1 to V13 and E1 to E43 (see Tables 1, 3 and 2, 4). The substrates used are glass plates which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs basically have the following layer structure: substrate/optional hole-injection layer (HIL1)/hole-transport layer (HTL)/hole-injection layer (HIL2)/electron-blocking layer (EBL)/emission layer (EML)/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 Tables 1 and 3. The materials required for the production of the OLEDs are disclosed above.

(75) All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter) with which the matrix material or matrix materials is (are) admixed 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 may also consist of a mixture of two materials.

(76) 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) assuming Lambert emission characteristics, and the lifetime are determined. The electroluminescence spectra are determined at aluminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The expression EQE @ 1000 cd/m.sup.2 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2. LT80 @ 6000 cd/m.sup.2 is the lifetime by which the OLED has dropped from a luminance of 6000 cd/m.sup.2 to 80% of the initial intensity, i.e. to 4800 cd/m.sup.2. The data for the various OLEDs are summarised in Tables 2 and 4.

(77) Use of Compounds According to the Invention as Hole-Transport Materials in OLEDs

(78) In particular, compounds according to the invention are suitable as HIL, HTL or EBL in OLEDs. They are suitable as a single layer, but also as mixed component as HIL, HTL, EBL or within the EML.

(79) Compared with NPB reference components (V1, V8), the samples comprising the compounds according to the invention exhibit both higher efficiencies and also significantly improved lifetimes, both in singlet blue and also in triplet green.

(80) Compared with reference material HTMV1 (V2, V9), compound (1-1) according to the invention (E1, E7) has significantly better lifetimes in blue and green.

(81) Compared with reference materials HTMV2-HTMV6 (V3-V7 and V9-V13), materials (1-1), (1-4), (1-7), (5-1), (4-1), (1-12), (1-13), (1-14), (1-15), (1-3), (6-3), (6-2), (6-1), (6-4), (6-5), (8-1), (7-1), (7-2), (9-2), (2-7), (2-8), (2-9), (2-10) and (1-17) according to the invention exhibit better lifetimes in blue and/or green.

(82) Use of Compounds According to the Invention as Hole-Transport Materials in Fluorescent and Phosphorescent OLEDs

(83) In particular, compounds according to the invention are suitable as HIL, HTL or EBL in OLEDs. They are suitable as a single layer, but also as mixed component as HIL, HTL, EBL or within the EML.

(84) Compared with NPB reference components (V1), all samples comprising the compounds according to the invention exhibit both higher efficiencies and also significantly improved lifetimes in singlet blue and triplet green.

(85) TABLE-US-00021 TABLE 1 Structure of the OLEDs (layer structure: substrate/HIL1/HTL/HIL2/EBL/EML/ETL/EIL(1 nm LiQ)/cathode) HIL1 HTL HIL2 EBL EML ETL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm nm V1 HIL1 HIL2 HIL1 NPB H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V2 HIL1 HIL2 HIL1 HTMV1 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V3 HIL1 HIL2 HIL1 HTMV2 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V4 HIL1 HIL2 HIL1 HTMV3 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V5 HIL1 HIL2 HIL1 HTMV4 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V6 HIL1 HIL2 HIL1 HTMV5 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V7 HIL1 HIL2 HIL1 HTMV6 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E1 HIL1 HIL2 HIL1 (1-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E2 HIL1 HIL2 HIL1 (1-4) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E3 HIL1 HIL2 HIL1 (1-7) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E4 HIL1 HIL2 HIL1 (5-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E5 HIL1 HIL2 HIL1 (4-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E6 HIL1 HIL2 HIL1  (1-12) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E7 HIL1 HIL2 HIL1  (1-13) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E8 HIL1 HIL2 HIL1  (1-14) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E9 HIL1 HIL2 HIL1  (1-15) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E10 HIL1 HIL2 HIL1 (6-3) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E11 HIL1 HIL2 HIL1 (6-2) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E12 HIL1 HIL2 HIL1 (6-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E13 HIL1 HIL2 HIL1 (6-4) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E14 HIL1 HIL2 HIL1 (6-5) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E15 HIL1 HIL2 HIL1 (8-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E16 HIL1 HIL2 HIL1 (7-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E17 HIL1 HIL2 HIL1 (7-2) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E18 HIL1 HIL2 HIL1 (9-2) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E19 HIL1 HIL2 HIL1 (2-7) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E20 HIL1 HIL2 HIL1 (2-8) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E21 HIL1 HIL2 HIL1  (2-10) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E22 HIL1 HIL2 HIL1 (2-9) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E23 HIL1 HIL2 HIL1  (1-17) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm

(86) TABLE-US-00022 TABLE 2 Data for the OLEDs EQE @ LT80 @ 1000 cd/m.sup.2 6000 cd/m.sup.2 CIE Ex. % [h] X y V1 4.8 70 0.14 0.17 V2 6.8 160 0.14 0.14 V3 6.9 115 0.14 0.14 V4 6.8 115 0.14 0.14 V5 6.5 130 0.14 0.15 V6 6.6 100 0.14 0.14 V7 6.9 135 0.13 0.14 E1 7.0 180 0.14 0.15 E2 6.9 175 0.13 0.15 E3 7.0 165 0.13 0.15 E4 6.7 150 0.14 0.15 E5 6.9 170 0.14 0.13 E6 7.0 145 0.14 0.14 E7 7.0 155 0.14 0.14 E8 7.8 120 0.14 0.14 E9 6.9 135 0.13 0.14 E10 6.9 150 0.14 0.14 E11 7.0 135 0.14 0.13 E12 7.0 180 0.14 0.15 E13 7.0 150 0.14 0.14 E14 7.2 170 0.14 0.14 E15 7.0 150 0.14 0.14 E16 6.9 160 0.14 0.14 E17 6.9 155 0.14 0.15 E18 6.9 170 0.14 0.14 E19 6.9 135 0.14 0.14 E20 7.0 115 0.14 0.14 E21 7.0 150 0.14 0.14 E22 7.0 135 0.14 0.14 E23 7.0 140 0.14 0.14

(87) TABLE-US-00023 TABLE 3 Structure of the OLEDs (layer structure:substrate/HTL/HIL2/EBL/EML/ETL/cathode) HTL HIL2 EBL EML ETL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm V8 HIL2 HIL1 NPB H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V9 HIL2 HIL1 HTMV1 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V10 HIL2 HIL1 HTMV2 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V11 HIL2 HIL1 HTMV3 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V12 HIL2 HIL1 HTMV5 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V13 HIL2 HIL1 HTMV6 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E24 HIL2 HIL1 (1-1) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E25 HIL2 HIL1 (1-4) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E26 HIL2 HIL1 (1-7) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E27 HIL2 HIL1 (5-1) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E28 HIL2 HIL1 (4-1) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E29 HIL2 HIL1 (1-12) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E30 HIL2 HIL1 (1-13) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E31 HIL2 HIL1 (1-14) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E32 HIL2 HIL1 (1-3) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E33 HIL2 HIL1 (1-15) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E34 HIL2 HIL1 (6-2) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E35 HIL2 HIL1 (6-1) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E36 HIL2 HIL1 (6-4) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E37 HIL2 HIL1 (7-2) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E38 HIL2 HIL1 (9-2) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E39 HIL2 HIL1 (2-7) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E40 HIL2 HIL1 (2-8) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E41 HIL2 HIL1 (2-10) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E42 HIL2 HIL1 (2-9) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E43 HIL2 HIL1 (1-17) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm

(88) TABLE-US-00024 TABLE 4 Data for the OLEDs Efficiency @ LT80 @ 1000 cd/m.sup.2 8000 cd/m.sup.2 CIE Ex. % [h] x Y V8 13.4 85 0.36 0.61 V9 16.3 140 0.35 0.62 V10 16.0 130 0.36 0.61 V11 16.7 155 0.36 0.61 V12 16.4 150 0.37 0.60 V13 17.0 170 0.35 0.62 E24 17.2 210 0.35 0.61 E25 17.2 200 0.36 0.61 E26 17.5 190 0.36 0.61 E27 16.7 190 0.37 0.60 E28 17.4 200 0.35 0.61 E29 17.0 180 0.37 0.61 E30 17.0 180 0.37 0.61 E31 17.5 220 0.37 0.61 E32 17.3 170 0.37 0.61 E33 17.2 200 0.37 0.61 E34 17.3 210 0.37 0.61 E35 17.2 220 0.37 0.61 E36 17.2 190 0.37 0.61 E37 17.2 200 0.37 0.61 E38 16.9 220 0.37 0.61 E39 16.9 160 0.37 0.61 E40 170 170 0.37 0.61 E41 17.0 195 0.37 0.61 E42 17.0 180 0.37 0.61 E43 17.1 190 0.37 0.61