Compounds and organic electroluminescent devices

Abstract

The present invention concerns particular fluorenes, the use of the compound in an electronic device, and an electronic device containing at least one of these compounds. The present invention further concerns a method for producing the compound and a formulation and composition containing one or more of the compounds.

Claims

1. An electroluminescent device comprising at least one compound of the general formula (2) ##STR00238## where the following applies to the symbols and indices used: p, q, r, s are 0 or 1, where p+q+r+s=1; Z.sup.a.sub.0, Z.sup.b.sub.0, Z.sup.c.sub.0, Z.sup.d.sub.0 are, identically or differently on each occurrence, equal to R.sup.4 Z.sup.a.sub.1, Z.sup.b.sub.1, Z.sup.c.sub.1, Z.sup.d.sub.1 are equal to ##STR00239## B is a single bond, a divalent aryl group having 6 to 30 ring atoms or a divalent heteroaryl group having 5 to 30 ring atoms, each of which is optionally substituted by one or more radicals R.sup.6, where, if B is a single bond, the nitrogen atom is bonded directly to the fluorene; Ar.sup.1 and Ar.sup.2 are selected, identically or differently on each occurrence, from the following groups of the formulae (42) to (107), (119)-(121) and (123)-(142) ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247## ##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252## ##STR00253## where the dashed line denotes the linking position to the nitrogen atom; R.sup.2, R.sup.4, and R.sup.5 are H, D, F, Cl, Br, I, C(O )R.sup.6, CN, Si(R.sup.6).sub.3, NO.sub.2, N(R.sup.6).sub.2, P(O )(R.sup.6).sub.2, S(O )R.sup.6, S(O ).sub.2R.sup.6, 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.6 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, CO, CS, CNR.sup.6, C(O)O, C(O)NR.sup.6, P(O)(R.sup.6), 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.6, or an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.6, 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.6; R.sup.1 is H, D, F, Cl, Br, I, C(O)R.sup.6, CN, Si(R.sup.6).sub.3, NO.sub.2, N(R.sup.6).sub.2, P(O)(R.sup.6).sub.2, S(O)R.sup.6, S(O).sub.2R.sup.6, a straight-chain alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkoxy or thioalkyl group having 3 to 20 C atoms or an alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.6 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, CO, CS, CNR.sup.6, C(O)O, C(O)NR.sup.6, P(O)(R.sup.6), 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.6, or an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.6, 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.6, where the radicals R.sup.1 and R.sup.2 cannot be identical and the radicals R.sup.3 to R.sup.5 may on each occurrence be identical or different, but is optionally identical to either R.sup.1or to R.sup.2; R.sup.3 is H; R.sup.6 is on each occurrence, identically or differently, H, D, F, Br, I, C(O)R.sup.7, CN, Si(R.sup.7).sub.3, NO.sub.2, P(O)(R.sup.7).sub.2, S(O)R.sup.7, S(O).sub.2R.sup.7, N(R.sup.7).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.7 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by R.sup.7CCR.sup.7, CC, Si(R.sup.7).sub.2, CO, CS, CNR.sup.7, C(O)O, C(O)NR.sup.7, P(O)(R.sup.7), 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.7, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.7, where two or more adjacent substituents R.sup.6 may form a mono- or polycyclic ring system with one another; R.sup.7 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.7 may form a mono- or polycyclic ring system with one another, and wherein the compound of formula (2) is a monoamine compound.

2. The device according to claim 1, wherein p=1 or r=1.

3. The device according to claim 1, wherein the compound has the general formula (3) ##STR00254## where the symbols and indices indicated are defined as indicated in claim 1.

4. The device according to claim 1, wherein the compound has the general formula (4) ##STR00255## where the symbols and indices indicated are defined as indicated in claim 1.

5. The device according to claim 1, wherein the compound has the general formula (5) ##STR00256## where the symbols and indices indicated are defined as indicated in claim 1.

6. The device according to claim 1, wherein the compound has the general formula (6) ##STR00257## where the symbols and indices indicated are defined as indicated in claim 1.

7. The device according to claim 1, wherein B is a single bond or a phenylene, biphenylene, terphenylene, naphthylene, pyridinylene, pyrimidinylene, pyrazin-ylene, pyridazinylene, triazinylene, dibenzofuranylene, dibenzothiophenylene fluorenylene, or carbazoylene group, which is optionally substituted by one or more radicals R.sup.6.

8. The device according to claim 1, wherein B is a single bond or a phenylene group, which is optionally substituted by one or more radicals R.sup.6.

9. The device according to claim 1, wherein the device is an organic light-emitting transistor (OLETs), an organic field-quench device (OFQDs), an organic light-emitting electrochemical cells (OLECs, LECs or LEECs), an organic laser diode (O-laser) and an organic light-emitting diode (OLEDs).

10. The device according to claim 1, wherein the at least one compound of the formula (2) ##STR00258## is employed with the following functions and in the following layers in the device: as hole-transport material in a hole-transport or hole-injection layer, as exciton-blocking material, as electron-blocking material, as matrix material in an emitting layer or as emitter in an emitting layer.

11. A compound of the general formula (2) ##STR00259## where the following applies to the symbols and indices used: p, q, r, s are 0 or 1, where p+q+r+s=1; Z.sup.a.sub.0, Z.sup.b.sub.0, Z.sup.c.sub.0, Z.sup.d.sub.0 are, identically or differently on each occurrence, equal to R.sup.4 Z.sup.a.sub.1,Z.sup.b.sub.1, Z.sup.c.sub.1, Z.sup.d.sub.1 are equal to ##STR00260## B is a single bond, a divalent aryl group having 6 to 30 ring atoms or a divalent heteroaryl group having 5 to 30 ring atoms, each of which is optionally substituted by one or more radicals R.sup.6, where, if B is a single bond, the nitrogen atom is bonded directly to the fluorene; Ar.sup.1 and Ar.sup.2 are selected, identically or differently on each occurrence, from the following groups of the formulae (42) to (107) (119)-(121) and (123)-(142) ##STR00261## ##STR00262## ##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267## ##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## where the dashed line denotes the linking position to the nitrogen atom; R.sup.2 and R.sup.4 are H, D, F, Cl, Br, I, C(O)R.sup.6, CN, Si(R.sup.6).sub.3, NO.sub.2, N(R.sup.6).sub.2, P(O)(R.sup.6).sub.2, S(O)R.sup.6, S(O).sub.2R.sup.6, 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.6 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, CO, CS, CNR.sup.6, C(O)O, C(O)NR.sup.6, P(O)(R.sup.6), 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.6, or an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.6, 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.6, and where at least one of the radicals from R.sup.1 and R.sup.2 represents 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.6; R.sup.1 is H, D, F, Cl, Br, I, C(O)R.sup.6, CN, Si(R.sup.6).sub.3, NO.sub.2, N(R.sup.6).sub.2, P(O)(R.sup.6).sub.2, S(O)R.sup.6, S(O).sub.2R.sup.6, a straight-chain alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkoxy or thioalkyl group having 3 to 20 C atoms or an alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.6 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, CO, CS, CNR.sup.6, C(O)O, C(O)NR.sup.6, P(O)(R.sup.6), O, S, SO or SO.sub.2 and where one or more H atoms in the abovementioned 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.6, or an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.6, 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.6, where the radicals R.sup.1 and R.sup.2 cannot be identical and the radicals R.sup.3 to R.sup.5 may on each occurrence be identical or different, but is optionally identical to either R.sup.1 or to R.sup.2; R.sup.3 is H; R.sup.5 is H, D, C(O)R.sup.6, CN, Si(R.sup.6).sub.3, NO.sub.2, N(R.sup.6).sub.2, P(O)(R.sup.6).sub.2, S(O)R.sup.6, S(O).sub.2R.sup.6, 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.6 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, CO, CS, CNR.sup.6, C(O)O, C(O)NR.sup.6, P(O)(R.sup.6), 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.6, or an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.6, 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.6, R.sup.6 is on each occurrence, identically or differently, H, D, F, Br, I, C(O)R.sup.7, CN, Si(R.sup.7).sub.3, NO.sub.2, P(O)(R.sup.7).sub.2, S(O)R.sup.7, S(O).sub.2R.sup.7, N(R.sup.7).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.7 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by R.sup.7CCR.sup.7, CC, Si(R.sup.7).sub.2, CO, CS, CNR.sup.7, C(O)O, C(O)NR.sup.7, P(O)(R.sup.7), 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.7, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.7, where two or more adjacent substituents R.sup.6 may form a mono- or polycyclic ring system with one another; R.sup.7 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.7 may form a monoor polycyclic ring system with one another; and wherein the compound of formula (2) is a monoamine compound.

12. A process for the preparation of the compound according to claim 11 by means of Buchwald coupling.

13. An electronic device which comprises the compound according to claim 11.

14. An electronic device comprising at least one compound according to claim 11, wherein the electronic device is selected from the group consisting of organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), and organic laser diodes O-lasers).

Description

EXAMPLES

(1) Materials

(2) ##STR00110## ##STR00111## ##STR00112## ##STR00113##

(3) Materials HIL1, HIL2 (EP 0676461), H1 (WO 2008/145239), ETM1 (WO 2005/053055), SEB1 (WO 2008/006449), LiQ and NPB are well known to the person skilled in the art from the prior art. Compound HTMV1 can be prepared analogously to the synthesis shown in Example 1, where 2-bromo-9,9-dimethyl-9H-fluorene is converted in a Buchwald reaction with bisbiphenyl-4-ylamine. Compounds (2-7), (2-4), (2-5), (1-11), (2-1) and (2-8) are according to the invention.

Example 1

Synthesis of the compound biphenyl-2-ylbiphenyl-4-yl-(9-methyl-9-p-tolyl-9H-fluoren-2-yl)amine (1-1) and compounds (1-2) to (1-11)

(4) ##STR00114##

2-Bromo-9-methyl-9-p-tolyl-9H-fluorene

(5) 40 g (154 mmol) of 2-bromo-9H-fluorenone are dissolved in 500 ml of dried THF in a flask which has been dried by heating. The solution is saturated with N.sub.2, and 15.0 g (170 mmol) of cerium(III) chloride are added. The clear solution is cooled to 10 C., and 121 ml (170 mmol) of a 1.4M methylmagnesium bromide solution are then added. The reaction mixture is slowly warmed to room temperature and then quenched using NH.sub.4Cl (500 ml). The mixture is subsequently partitioned between ethyl acetate and water, the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. 60 ml of toluene are added to the evaporated solution. The batch is heated to 50 C., and 27.2 ml of trifluoromethanesulfonic acid (308 mmol) are subsequently added dropwise. After one hour, the reaction mixture is cooled to room temperature and poured into 1 l of water. The mixture is partitioned between toluene and water, the organic phase is washed three times with water and 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) gave 32 g (60% of theory)

(6) The following brominated compounds are prepared analogously:

(7) TABLE-US-00001 Starting Starting material 1 Starting material 2 material 3 Product Yield 55% 0 62% 58% 0 60% 52% 61% MeMgBr 0 62% 50% 65%

Biphenyl-2-ylbiphenyl-4-yl-(9-methyl-9-p-tolyl-9H-fluoren-2-yl)amine (1-1)

(8) 27.6 g of biphenyl-2-ylbiphenyl-4-ylamine (85.9 mmol), 30.0 g of 2-bromofluorene (85.9 mmol) are dissolved in 500 ml of toluene: the solution is degassed and saturated with N.sub.2. 4.3 ml (4.3 mmol) of a 1 M tri-tert-butylphosphine solution and 0.48 g (2.15 mmol) of palladium(II) acetate are then added. 20.6 g of sodium tert-butoxide (214.7 mmol) are subsequently added. The reaction mixture is heated at the boil for 5 h under protective atmosphere. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and 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, purity is 99.9%. The yield is 39.5 g (78% of theory).

(9) Compounds (1.2) to (1-11) are prepared analogously:

(10) TABLE-US-00002 Starting material 1 Starting material 2 Product Yield 0 78% 92% 88% 0 85% 80% 75% 0 75% 80% 70% 75%

Example 2

Synthesis of the compound biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9-methyl-9-phenyl-9H-fluoren-4-yl)amine (2-1) and compounds (2-2) to (2-8)

(11) ##STR00180##

4-Bromo-9-methyl-9-phenyl-9H-fluorene

(12) 30 g (94 mmol) of 2,2-dibromobiphenyl are dissolved in 200 ml of dried THF in a flask which has been dried by heating. The reaction mixture is cooled to 78 C. 37.7 ml of a 2.5 M solution of n-BuLi in hexane (94 mmol) are slowly added dropwise (duration: about 1 h) at this temperature. The batch is stirred at 70 C. for a further 1 h. 11.1 ml of acetophenone (94 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. 300 ml of acetic acid are carefully added to the evaporated solution, and 50 ml of fuming HCl are subsequently added. The batch is heated to 75 C. and held there for 6 h. A white solid precipitates out during this time. The batch is then cooled to room temperature, the solid which has precipitated out is filtered off with suction and rinsed with methanol. The residue is dried at 40 C. in vacuo. Yield is 25.3 g (75 mmol) (80% of theory)

(13) The following brominated compounds are prepared analogously.

(14) TABLE-US-00003 Starting material 1 Starting material 2 Product Yield 78% 80% 87%

Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9-methyl-9-phenyl-9H-fluoren-4-yl)amine (2-1)

(15) 17.8 g of biphenyl-2-ylbiphenyl-4-ylamine (49.4 mmol), 18.2 g of 2.bromo-(9-methyl-9-phenyl-9H-fluorene (54.3 mol) are dissolved in 400 ml of toluene: the solution is degassed and saturated with N.sub.2. 2.96 ml (2.96 mmol) of tri-tert-butylphosphine and 0.33 g (1.48 mmol) of palladium(II) acetate are then added, and 9.8 g of sodium tert-butoxide (98.8 mmol) are subsequently added. The reaction mixture is heated at the boil for 3 h under protective atmosphere. The mixture is subsequently partitioned between toluene and water, 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, purity is 99.9%. The yield is 24.3 g (80% of theory).

(16) Compounds (2-2) to (2-8) are prepared analogously:

(17) TABLE-US-00004 Starting material 1 Starting material 2 Product Yield 0 78% 75% 80% 00 01 80% 02 03 04 88% 05 06 07 85% 08 09 0 78%

Example 3

Synthesis of the compound biphenyl-4-ylbiphenyl-2-yl-(7,9-diphenyl-9-p-tolyl-9H-fluoren-2-yl)amine (3-1) and compounds (3-2) to (3-4)

(18) ##STR00211##

2-Bromo-7-phenylfluoren-9-one

(19) 21.6 g (178 mmol) of phenylboronic acid, 60 g (178 mmol) of 2,7-dibromo-fluorenone are suspended in 800 ml of dimethoxyethane and 265 ml of a 2 M sodium carbonate solution (533 mmol). 6.154 g (5 mmol) of tetrakis-(triphenylphosphine)palladium are added to this suspension, and the reaction mixture is heated under reflux for 18 h. After cooling of the reaction mixture, the organic phase is separated off, filtered through silica gel, washed three times with 100 ml of water and subsequently evaporated to dryness. Filtration of the crude product through silica gel with toluene gives 38.6 g (85%) of 2-bromo-7-phenyfluoren-9-one.

(20) The following brominated compounds are prepared analogously:

(21) TABLE-US-00005 Starting material 1 Starting material 2 Product Yield 85% 90%

2-Bromo-7,9-diphenyl-9-p-tolyl-9H-fluorene

(22) 35 g (104 mmol) of 2-bromo-7-phenylfluorenone are dissolved in 600 ml of dried THE in a flask which has been dried by heating. The clear solution is cooled to 10 C., and 38.3 ml (115 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.4Cl (300 ml). The mixture is subsequently partitioned between ethyl acetate and water, the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. 100 ml of toluene are added to the evaporated solution. The batch is heated to 50 C., and 20.4 ml of trifluoromethanesulfonic acid (208 mmol) are subsequently added dropwise. After one hour, the reaction mixture is cooled to room temperature and poured into 1 l of water. The mixture is partitioned between toluene and water, the organic phase is washed three times with water and 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 41 g (61% of theory).

(23) The following brominated compounds are prepared analogously:

(24) TABLE-US-00006 Starting Starting Starting material 1 material 2 material 3 Product Yield 0 60% 55% CH3MgBr 60%

Biphenyl-4-ylbiphenyl-2-yl-(7,9-diphenyl-9-p-tolyl-9H-fluoren-2-yl)amine (3-1)

(25) 13.18 g of biphenyl-2-ylbiphenyl-4-ylamine (41 mmol), 20 g of 2-bromo-7,9-diphenyl-9-p-tolyl-9H-fluorene (41 mmol) are dissolved in 350 ml of toluene: the solution is degassed and saturated with N.sub.2. 1.6 ml (1.6 mmol) of tri-tert-butylphosphine and 184 mg (0.82 mmol) of palladium(II) acetate are then added. 9.86 g of sodium tert-butoxide (102 mmol) are subsequently added. The reaction mixture is heated at the boil for 5 h under protective atmosphere. The mixture is subsequently partitioned between toluene and water, 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 21.8 g (73% of theory).

(26) The following compounds are prepared analogously:

(27) TABLE-US-00007 Starting material 1 Starting material 2 Product Yield 0 85% 82% 80%

Example 4

(28) Characterisation of the Compounds

(29) 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 (e.g. layer-thickness variation, materials).

(30) The data of various OLEDs are presented in the following examples V1, V2 and E1 to E3 (see Tables 1 and 2). 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/hole-injection layer (HIL1)/hole-transport layer (HTL)/hole-injection layer (HIL2)/electron-blocking layer (EBL)/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 precise structure of the OLEDs is shown in Table 1. The materials required for the production of the OLEDs are indicated above.

(31) 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.

(32) 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 per cent) 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 @ 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 at a luminosity of 6000 cd/m.sup.2 has dropped to 80% of the initial intensity, i.e. to 4800 cd/m.sup.2. The data of the various OLEDs are summarised in Table 2.

(33) Use of Compounds According to the Invention as Hole-transport Materials in Fluorescent OLEDs

(34) Compounds according to the invention are particularly 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.

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

(36) Compared with reference material HTMV1 (V2), compounds (2-7), (2-4), (2-5), (1-11), (2-1) and (2-8) according to the invention (E1-E4) have a better lifetime.

(37) In green triplet components, compounds (2-7), (2-4), (2-1) according to the invention exhibit better efficiencies and better lifetimes compared with reference components V3 (NPB) and V4 (HTMV1).

(38) TABLE-US-00008 TABLE 1 Structure of the OLEDs (Layer structure: substrate/IL/HTL/IL/EBL/EML/ETL/EIL (1 nm LiQ)/cathode) HIL1 HTL HIL2 EBL EML ETL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/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 E1 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 E2 HIL1 HIL2 HIL1 (2-4) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E3 HIL1 HIL2 HIL1 (2-5) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E4 HIL1 HIL2 HIL1 (1-11) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E5 HIL1 HIL2 HIL1 (2-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E6 HIL1 HIL2 HIL1 (2-8) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm

(39) TABLE-US-00009 TABLE 2 Data of the OLEDs EQE @ LT80 @ 1000 cd/m2 6000 cd/m.sup.2 CIE Ex. % [h] x y V1 4.8 70 0.14 0.17 V2 7.0 130 0.13 0.15 E1 6.1 155 0.13 0.15 E2 7.0 161 0.14 0.15 E3 6.9 158 0.13 0,14 E4 8.5 155 0.13 0.15 E5 7.0 155 0.14 0.15 E6 6.9 160 0.14 0.15

(40) TABLE-US-00010 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 V3 HIL2 HIL1 NPB H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V4 HIL2 HIL1 HTMV1 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 m 20 nm 30 nm 40 nm E7 HIL2 HIL1 (2-7) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E8 HIL2 HIL1 (2-4) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E9 HIL2 HIL1 (2-1) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm

(41) TABLE-US-00011 TABLE 4 Data of the OLEDs Efficiency @ LT80 @ 1000 cd/m2 8000 cd/m.sup.2 CIE Ex. % [h] x Y V3 13.4 85 0.36 0.61 V4 17.0 170 0.35 0.62 E7 17.5 190 0.34 0.62 E8 18.3 215 0.35 0.62 E9 18.5 225 0.37 0.60