Materials for organic electroluminescent devices

Abstract

The present invention relates to compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices which comprise these compounds.

Claims

1. A compound of the formula (1), ##STR00294## where the following applies to the symbols and indices used: Ar.sup.N is a group of the formula (2-2) ##STR00295## V is, identically or differently, equal to CR.sup.6 or N; X is a divalent bridge selected from the group consisting of B(R.sup.0), C(R.sup.0).sub.2, Si(R.sup.0).sub.2, C═O, C═NR.sup.0, C═C(R.sup.0).sub.2, O, S, S═O, SO.sub.2, P(R.sup.0) and P(═O)R.sup.0; or X is a group of the following formula (3), ##STR00296## where the dashed bonds indicate the bonding to the 5-membered ring of formula (2-2); R.sup.0 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2, S(═O)Ar.sup.1, S(═O).sub.2Ar.sup.1, NO.sub.2, Si(R.sup.8).sub.3, B(OR.sup.8), OSO.sub.2R.sup.8, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.8, where in each case one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.8C═CR.sup.8, C═C, Si(R.sup.8).sub.2, Ge(R.sup.8).sub.2, Sn(R.sup.8).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.8), SO, SO.sub.2, O, S or CONR.sup.8 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals Rs, an aryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.8, where two substituents R.sup.0 attached to the same C or Si atom may optionally form a mono- or polycyclic aliphatic ring system, which is optionally substituted by one or more radicals R.sup.8; with the proviso that when two R.sup.0 are attached to the same C atom, then at least one R.sup.0 is selected from the group consisting of H, D, F, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.8; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.6 or R.sup.7 are selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2, S(═O)Ar.sup.1, S(═O).sub.2Ar.sup.1, NO.sub.2, Si(R.sup.8).sub.3, B(OR.sup.8), OSO.sub.2R.sup.8, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals Rs, where in each case one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.8C═CR.sup.8, C═C, Si(R.sup.8), Ge(R.sup.8).sub.2, Sn(R.sup.8).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.8), SO, SO.sub.2, O, S or CONR.sup.8 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.8, an aryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.8, where two or more adjacent substituents R.sup.1, two or more adjacent substituents R.sup.2, two or more adjacent substituents R.sup.3, two or more adjacent substituents R.sup.4, two or more adjacent substituents R.sup.6 or two or more adjacent substituents R.sup.7 may optionally form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which is optionally substituted by one or more radicals R.sup.8; R.sup.5 is selected identically or differently on each occurrence, from the group consisting of H and D; R.sup.8 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, where in each case one or more non-adjacent CH.sub.2 groups is optionally replaced by SO, SO.sub.2, O, S and where one or more H atoms is optionally replaced by D, F, Cl, Br or I, an aromatic or heteroaromatic ring system having 6 to 60 C atoms, where two or more adjacent substituents R.sup.8 may optionally form a mono- or polycyclic, aliphatic ring system; Ar.sup.1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.sup.8; Ar.sup.S is an aromatic ring system having 6 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.sup.8; t, u are, identically or differently, 0 or 1; m, n, q, r are, identically or differently, 0, 1, 2, 3 or 4, where t+m≤4 and u+n≤4; p is 0, 1 or 2; i is 0, 1 or 2, wherein i=0 means that the group AR.sup.S is absent and replaced by a single bond; j is 1, 2 or 3; s is 0, 1, 2, 3, 4 or 5.

2. The compound according to claim 1, wherein t+u=0 or 1.

3. The compound according to claim 1, wherein the index i is 0.

4. The compound according to claim 1, wherein the compound is selected from the compounds of the formulae (1-1) to (1-9), ##STR00297## ##STR00298## ##STR00299## where the symbols and indices used have the meanings given in claim 1.

5. The compound according to claim 1, wherein the compound is selected from the compounds of the formulae (1-1a) to (1-9a) ##STR00300## ##STR00301## ##STR00302## where the symbols and indices used have the meanings given in claim 1.

6. The compound according to claim 1, wherein the compound is selected from the compounds of the formulae (1-1b) to (1-9b) ##STR00303## ##STR00304##

7. The compound according to claim 1, wherein R.sup.1 to R.sup.4 are selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.8, where one or more non-adjacent CH.sub.2 groups is optionally replaced by O and where one or more H atoms is optionally replaced by F, an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.8.

8. The compound according to claim 1, wherein R.sup.6 and R.sup.7 are selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.8, where one or more non-adjacent CH.sub.2 groups is optionally replaced by O and where one or more H atoms is optionally replaced by F, an aryl or heteroaryl ring system having 5 to 14 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.8.

9. The compound according to claim 1, wherein R.sup.0 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.8, where in each case one or more non-adjacent CH.sub.2 groups is optionally replaced by O and where one or more H atoms is optionally replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 14 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.8, where two substituents R.sup.0 may optionally form a monocyclic aliphatic ring system, which is optionally substituted by one or more radicals Rs; with the proviso that when two R.sup.0 are attached to the same C atom, then at least one R.sup.0 is selected from the group consisting of H, D, F, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.8.

10. The compound according to claim 1, wherein R.sup.0 is selected on each occurrence, identically or differently, from the group consisting of H, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.8.

11. A process for the preparation of the compound according to claim 1, which comprises introducing a diarylamino group by a C—N coupling reaction between a diarylamine compound and a halogenated spirobifluorene compound.

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

13. An electronic device comprising the compound according to claim 1.

14. An organic electroluminescent device comprising the compound according to claim 1.

15. The electronic device according to claim 13, wherein the device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

16. An organic electroluminescent device comprising the compound according to claim 1 is employed as hole-transport material in a hole-transport or hole-injection or exciton-blocking or electron-blocking layer or as matrix material for fluorescent or phosphorescent emitters.

17. The compound according to claim 1, wherein the group Ar.sup.N is selected from the groups of formulae (60) to (67) and (70) to (84): ##STR00305## ##STR00306## ##STR00307## ##STR00308## where the dashed bond indicates the bond to a nitrogen atom depicted in formula (1), where R.sup.0 has the same meaning as in claim 1 and where the groups of formulae (60) to (67) and (70) to (84) is optionally substituted by one or more radicals R.sup.8.

18. The compound according to claim 1, wherein u is 1 and t is 0.

19. The compound according to claim 1, wherein s is 0.

20. A compound of the formula (1), ##STR00309## where the following applies to the symbols and indices used: Ar.sup.N is a group of the formula (2-2) ##STR00310## V is, identically or differently, equal to CR.sup.6 or N; X is a divalent bridge selected from the group consisting of B(R.sup.0), C(R.sup.0).sub.2, Si(R.sup.0).sub.2, C═O, C═NR.sup.0, C═C(R.sup.0).sub.2, O, S, S═O, SO.sub.2, P(R.sup.0) and P(═O)R.sup.0; or X is a group of the following formula (3), ##STR00311## where the dashed bonds indicate the bonding to the 5-membered ring of formula (2-2); R.sup.0 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2, S(═O)Ar.sup.1, S(═O).sub.2Ar.sup.1, NO.sub.2, Si(R.sup.8).sub.3, B(OR.sup.8), OSO.sub.2R.sup.8, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.8, where in each case one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.8C═CR.sup.8, C═C, Si(R.sup.8).sub.2, Ge(R.sup.8).sub.2, Sn(R.sup.8).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.8), SO, SO.sub.2, O, S or CONR.sup.8 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals Rs, an aryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.8, where two substituents R.sup.0 attached to the same C or Si atom may optionally form a mono- or polycyclic aliphatic ring system, which is optionally substituted by one or more radicals R.sup.8; with the proviso that when two R.sup.0 are attached to the same C atom, then at least one R.sup.0 is selected from the group consisting of H, D, F, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.8; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.6 or R.sup.7 are selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2, S(═O)Ar.sup.1, S(═O).sub.2Ar.sup.1, NO.sub.2, Si(R.sup.8).sub.3, B(OR.sup.8), OSO.sub.2R.sup.8, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals Rs, where in each case one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.8C═CR.sup.8, C═C, Si(R.sup.8), Ge(R.sup.8).sub.2, Sn(R.sup.8).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.8), SO, SO.sub.2, O, S or CONR.sup.8 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.8, an aryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.8, where two or more adjacent substituents R.sup.1, two or more adjacent substituents R.sup.2, two or more adjacent substituents R.sup.3, two or more adjacent substituents R.sup.4, two or more adjacent substituents R.sup.6 or two or more adjacent substituents R.sup.7 may optionally form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which is optionally substituted by one or more radicals R.sup.8; R.sup.5 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy or thioalkyl group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.8, where one or more non-adjacent CH.sub.2 groups is optionally replaced by 0, and where one or more H atoms is optionally replaced by F; R.sup.8 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, where in each case one or more non-adjacent CH.sub.2 groups is optionally replaced by SO, SO.sub.2, O, S and where one or more H atoms is optionally replaced by D, F, Cl, Br or I, an aromatic or heteroaromatic ring system having 6 to 60 C atoms, where two or more adjacent substituents R.sup.8 may optionally form a mono- or polycyclic, aliphatic ring system; Ar.sup.1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.sup.8; Ar.sup.S is an aromatic ring system having 6 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.sup.8; t, u are, identically or differently, 0 or 1; m, n, q, r are, identically or differently, 0, 1, 2, 3 or 4, where t+m≤4 and u+n≤4; p is 0, 1 or 2; i is 2; j is 1, 2 or 3; s is 0, 1, 2, 3, 4 or 5.

21. The compound according to claim 20, wherein t+u=0 or 1.

22. The compound according to claim 20, wherein the compound is selected from the compounds of the formulae (1-1) to (1-9), ##STR00312## ##STR00313## ##STR00314## where the symbols and indices used have the meanings given in claim 1.

23. The compound according to claim 20, wherein the compound is selected from the compounds of the formulae (1-1a) to (1-9a) ##STR00315## ##STR00316## ##STR00317## where the symbols and indices used have the meanings given in claim 1.

24. The compound according to claim 20, wherein the compound is selected from the compounds of the formulae (1-1b) to (1-9b) ##STR00318## ##STR00319## ##STR00320##

25. The compound according to claim 20, wherein R.sup.1 to R.sup.4 are selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.8, where one or more non-adjacent CH.sub.2 groups is optionally replaced by O and where one or more H atoms is optionally replaced by F, an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.8.

26. The compound according to claim 20, wherein R.sup.6 and R.sup.7 are selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.8, where one or more non-adjacent CH.sub.2 groups is optionally replaced by O and where one or more H atoms is optionally replaced by F, an aryl or heteroaryl ring system having 5 to 14 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.8.

27. The compound according to claim 20, wherein R.sup.0 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.8, where in each case one or more non-adjacent CH.sub.2 groups is optionally replaced by O and where one or more H atoms is optionally replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 14 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.8, where two substituents R.sup.0 may optionally form a monocyclic aliphatic ring system, which is optionally substituted by one or more radicals Rs; with the proviso that when two R.sup.0 are attached to the same C atom, then at least one R.sup.0 is selected from the group consisting of H, D, F, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.8.

28. The compound according to claim 20, wherein R.sup.0 is selected on each occurrence, identically or differently, from the group consisting of H, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.8.

29. A process for the preparation of the compound according to claim 20, which comprises introducing a diarylamino group by a C—N coupling reaction between a diarylamine compound and a halogenated spirobifluorene compound.

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

31. An electronic device comprising the compound according to claim 20.

32. An organic electroluminescent device comprising the compound according to claim 20.

33. The electronic device according to claim 31, wherein the device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

34. An organic electroluminescent device comprising the compound according to claim 20 is employed as hole-transport material in a hole-transport or hole-injection or exciton-blocking or electron-blocking layer or as matrix material for fluorescent or phosphorescent emitters.

35. The compound according to claim 20, wherein the group Ar.sup.N is selected from the groups of formulae (60) to (67) and (70) to (84): ##STR00321## ##STR00322## ##STR00323## where the dashed bond indicates the bond to a nitrogen atom depicted in formula (1), where R.sup.0 has the same meaning as in claim 1 and where the groups of formulae (60) to (67) and (70) to (84) is optionally substituted by one or more radicals R.sup.8.

36. The compound according to claim 20, wherein u is 1 and t is 0.

37. The compound according to claim 20, wherein s is 0.

38. The compound according to claim 20, wherein R.sup.5 is selected, identically or differently on each occurrence, from the group consisting of H and D.

39. The compound according to claim 1, wherein AR.sup.S is selected from the group consisting of ##STR00324## ##STR00325##

Description

EXAMPLES

A) Synthesis Examples

(1) The following syntheses are carried out under a protective-gas atmosphere, unless indicated otherwise. The starting materials can be purchased from ALDRICH or ABCR. The numbers in square brackets in the case of the starting materials known from the literature are the corresponding CAS numbers.

Synthesis of phenyl-(9,9′-dimethylfluorenyl)-1-spiro-9,9′-bifluorenylamine

(2) ##STR00137##

(3) A solution of 2-Bromo-biphenyl (17 g, 70 mmol) in THF (90 ml) is treated with 35 mL of n-BuLi (2.1 M in hexane, 70 mmol) under argon at −78° C. The mixture is stirred for 30 minutes. A solution of phenyl-(9,9′-dimethylfluoren-2-yl)amine-9H-Fluoren-9-one (38 g, 82 mmol) in 90 mL THF is added dropwise. The reaction proceeds at −78° C. for 30 minutes and then is stirred at room temperature overnight. The reaction is quenched with water and extracted with ethyl acetate. The intermediate alcohol is obtained after the solvent is removed (31 g, 64%). Without further purification, a mixture of the alcohol, acetic acid (700 mL) and concentrated HCl (62 mL) is refluxed for 2 hours. After cooling, the mixture is filtered and washed with water. The residue is crystallised from toluene. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo. The product is isolated in the form of a pale-yellow solid (13 g, 27% of theory, purity >99.99% according to HPLC).

(4) Similar to this phenyl-(9,9′-dimethylfluorenyl)-1-(4-phenyl)-spiro-9,9′-bifluorenylamine was synthesized:

(5) ##STR00138##

Example 3a: Synthesis of phenyl-2-(9,9′-dimethylfluorenyl)-1-spiro-9,9′-bifluorenylamine

(6) ##STR00139##

(7) Tri-tert-butylphosphine (2.7 ml of a 1.0 M solution in toluene, 2.7 mmol), palladium acetate (307 mg, 1.4 mmol) and sodium tert-butoxide (9.8 g, 102 mmol) are added to a solution of phenyl-(9,9-dimethyl-9H-fluoren-2-yl)amine (20.5 g, 71 mmol) and 4-bromo-9,9′-spirobifluorene (27 g, 68 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 2 h. The reaction mixture is cooled to room temperature, extended with toluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from ethyl acetate/heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice (p=3×10.sup.−4 mbar, T=298° C.). The product is isolated in the form of a pale-yellow solid (8 g, 20% of theory, purity >99.99% according to HPLC).

(8) The following compounds are obtained analogously:

(9) TABLE-US-00002 Ex. Br-spiro Amine Product Yield 3b 0 43% 3c 56% 3d 61% 3e 0 72% 3k 64% 3l 56% 3m 0 66% 3n 46% 3o 34% 3s 70% 3v 0 43% 3w 76% 3x 41% 3y 0 50% 3z 59% 3aa 71% 3af 0 48% 3ag 46% 3ah 41% 3ai 50% 3aj 00 01 02 43% 3ak 03 04 05 53% 3al 06 07 08 33% 3am 09 0 46% 3an 41%

Example 4a: Synthesis of biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9,9′-spirobifluoren-4-yl)amine

(10) ##STR00215##

a) Synthesis of phenyl-(9,9-dimethyl-9H-fluoren-2-yl)amine

(11) 1,1′-Bis(diphenylphosphino)ferrocene (1.5 g, 2.7 mmol), palladium acetate (616 mg, 2.7 mmol) and sodium tert-butoxide (22.9 g, 238 mmol) are added to a solution of phenyl-amine (17.0 g, 183 mmol) and 2-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol) in degassed toluene (400 ml), and the mixture is heated under reflux for 20 h. The reaction mixture is cooled to room temperature, extended with toluene and filtered through Celite. The filtrate is extended with water, re-extracted with toluene, and the combined organic phases are dried and evaporated in vacuo. The residue is filtered through silica gel (heptane/dichloromethane) and crystallised from isopropanol. Phenyl-(9,9-dimethyl-9H-fluoren-2-yl)amine is obtained in the form of a pale-yellow solid (49.0 g, 95% of theory).

b) Synthesis of phenyl-(9,9-dimethyl-9H-fluoren-2-yl)-(9,9′-spirobifluoren-4-yl)amine

(12) Tri-tert-butylphosphine (4.4 ml of a 1.0 M solution in toluene, 4.4 mmol), palladium acetate (248 mg, 1.1 mmol) and sodium tert-butoxide (16.0 g, 166 mmol) are added to a solution of phenyl-(9,9-dimethyl-9H-fluoren-2-yl)amine (40.0 g, 140 mmol) and 4-bromo-9,9′-spirobifluorene (56.9 g, 144 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 2 h. The reaction mixture is cooled to room temperature, extended with toluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from ethyl acetate/heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice (p=3×10.sup.−4 mbar, T=298° C.). The product is isolated in the form of a pale-yellow solid (20.4 g, 24% of theory, purity >99.99% according to HPLC).

(13) The following compounds are obtained analogously:

(14) TABLE-US-00003 Starting Starting Starting Ex. material 1 material 2 material 3 Product Yield 4b 78% 4c 0 73% 4d 75% 4e 0 79% 4f 78%

Example 5a: Synthesis of Synthesis of Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(9,9′-spiro-bifluoren-4-yl)-phenyl]-amine

a) Synthesis of Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl (4,4,5,5tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amine

(15) ##STR00236##

(16) 102 g (231 mmol) of phenyl-(4-bromo-phenyl)-(9,9-dimethyl-9H-fluoren-2-yl)-amine, 4.8 g (5.9 mmol) of Pd(dppf)Cl.sub.2, 61.6 g (238 mmol) of bis(pinacolato)diboron and 58.3 g (594 mmol) of potassium acetate are dissolved in 1300 mL of 1,4-dioxane. The reaction mixture is refluxed and agitated under an argon atmosphere for 12 hours and after cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from heptane. The product is isolated in the form of a pale-yellow solid (87 g, 78% of theory).

b) Synthesis of phenyl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(9,9′-spiro-bifluoren-4-yl)-phenyl]-amine

(17) ##STR00237##

(18) 24 g (49.4 mmol) of phenyl-(9,9-dimethyl-9H-fluoren-2-yl (4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amine, 20 g (49.4 mmol) of 4-bromspirobifluorene, 1.8 g (2.5 mmol) of PdCl.sub.2(Cy).sub.3, 15 g (99 mmol) of cesium fluoride are dissolved in 500 mL of toluene. The reaction mixture is refluxed and agitated under an argon atmosphere for 12 hours and after cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from heptane.

(19) The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice. The product is isolated in the form of a pale-yellow solid (9 g, 57% of theory, purity >99.99% according to HPLC).

(20) The following compounds are synthesized analogously:

(21) TABLE-US-00004 Ex. Br-Spiro Amine Product Yield 5b 0 43% 5c 55% 5d 60% 5e 63% 5f 0 70% 5g 75% 5h 55% 5i 0 64% 5j 60% 5k 67% 5l 0 58%

Example 6a: 9-Spiro-4-yl-3,6-diphenyl-9H-carbazol

(22) ##STR00271##

(23) 19.2 g (47 mmol) 4-Brom-9-spirobifluorene, 15 g (62 mmol) 3-phenyl-9-H-carbazole and 29.2 g Rb.sub.2CO.sub.3 are suspended in 250 mL p-Xylol. To the suspension are given 0.95 g (4.2 mmol) Pd(OAc).sub.2 and 12.6 ml of a 1M solution of Tri-tert-butylphosphine. The mixture is stirred 24 h under reflux. After cooling the organic phase is separated, washed three times with 150 mL water and is subsequently concentrated to dryness in vacuo. The residue is hot extracted with toluene, recrystallized three times from toluene and subsequently sublimated at high vacuum. Yield is 19.6 g (35 mmol) corresponding to 75% of theory. Purity is according to HPLC 99.9%.

(24) The following compounds are obtained analogously:

(25) TABLE-US-00005 starting material 1 starting material 2 product yield 6b 76% 6c 65% 6d 0 77%

B) Devices Examples

(26) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 2004/058911, which is adapted to the circumstances described here (layer-thickness variation, materials).

(27) The data for various OLEDs are presented in Examples E1, E2 and E3 below (see Tables 1 to 4). The substrates used are glass plates 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 (HIL)/hole-transport layer (HTL)/hole-injection layer (HIL)/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 and 3. The materials required for the production of the OLEDs are shown in Table 5.

(28) 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:SEB(5%) here means that material H1 is present in the layer in a proportion by volume of 95% and SEB is present in the layer in a proportion of 5%. Analogously, the electron-transport layer may also consist of a mixture of two materials. The OLEDs are characterised by standard methods. For this purpose, 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 (UIL characteristic lines) assuming Lambertian emission characteristics, and the lifetime are determined. The expression EQE @ 10 mA/cm.sup.2 denotes the external quantum efficiency at an operating current density of 10 mA/cm.sup.2. LT80@5000 cd/m.sup.2 is the lifetime until the OLED has dropped from a luminance of 5000 cd/m.sup.2 to 80% of the initial intensity, i.e. to 4000 cd/m.sup.2. The data for the various OLEDs are summarised in Tables 2 and 4.

(29) Use of Compounds According to the Invention as Hole-Transport Materials in Fluorescent and phosphorescentOLEDs

(30) 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. Compared with components which comprise reference materials (HTMV1, HTMV2, HTMV3), the samples comprising the compounds according to the invention exhibit both higher efficiencies and also significantly improved lifetimes. They were tested both in singlet blue and also in triplet green OLED devices.

(31) TABLE-US-00006 TABLE 1 Structure of the OLEDs HIL HTL EBL EML ETL EIL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm nm E1 HIL:F4TCNQ(5%) HIL HTM1 H1:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 170 nm 20 nm 20 nm 30 nm 1 nm E2 HIL:F4TCNQ(5%) HIL HTM2 H1:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 170 nm 20 nm 20 nm 30 nm 1 nm V1 HIL:F4TCNQ(5%) HIL HTMV1 H1:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 170 nm 20 nm 20 nm 30 nm 1 nm V2 HIL:F4TCNQ(5%) HIL HTMV2 H1:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 170 nm 20 nm 20 nm 30 nm 1 nm V3 HIL:F4TCNQ(5%) HIL HTMV3 H1:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 170 nm 20 nm 20 nm 30 nm 1 nm

(32) TABLE-US-00007 TABLE 2 Data for the OLEDs EQE LT80 @ 10 mA/cm.sup.2 @ 5000 cd/m.sup.2 Ex. % [h] E1 9.1 240 E2 9.0 180 V1 8.8 110 V2 9.0 150 V3 8.4 180

(33) TABLE-US-00008 TABLE 3 Structure of the OLEDs HIL HTL HIL EBL EML ETL EIL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm nm nm E3 HIL:F4TCNQ HIL HTM1:F4TCNQ HTM1 H2:TEG(10%) ETM1(50%):LiQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm V4 HIL:F4TCNQ HIL HTMV1:F4TCNQ HTMV1 H2:TEG(10%) ETM1(50%):LiQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm V5 HIL: F4TCNQ HIL HTMV2:F4TCNQ HTMV2 H2:TEG(10%) ETM1(50%):LiQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm

(34) TABLE-US-00009 TABLE 4 Data for the OLEDs EQE LT80 @ 2 mA/cm.sup.2 @ 10000 cd/m.sup.2 Ex. % [h] E3 21.6 240 V4 19.7 240 V5 19.9 230

(35) TABLE-US-00010 TABLE 5 Structures of the materials used F4TCNQ HIM H1 SEB H2 TEG ETM LiQ HTM1 0 HTMV1 HTMV2 HTM2 HTMV3