Compounds having fluorene structures

Abstract

The present invention describes fluorene derivatives substituted by electron-transporting groups, especially for use as triplet matrix materials in electronic devices. The invention further relates to a process for preparing the compounds of the invention and to electronic devices comprising these.

Claims

1. A compound of formulae (I) or (II) or a mixture of a compound of formula (I) and a compound of formula (II): ##STR00457## wherein X is, the same or differently in each instance, N or CR.sup.1, with the proviso that not more than two groups X in one cycle are N; Q is selected from the group consisting of structures of formulae (Q-1) and (Q-3): ##STR00458## wherein the dotted bond denotes the attachment position; and Ar.sup.1 is an aromatic or heteroaromatic ring system having 6 to 40 carbon atoms and is optionally substituted in each case by one or more radicals R.sup.2, an aryloxy group having 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or an aralkyl group having 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more radicals R.sup.2, and wherein two or more adjacent radicals R.sup.1 or R.sup.2 together optionally define a mono- or polycyclic aliphatic ring system with each other and which is optionally substituted by one or more radicals R.sup.3; L.sup.1 is a bond, C(═O), pyrimidine which is optionally substituted by one or more R.sup.1, triazine which is optionally substituted by one or more R.sup.1 radicals or a group of the Formula (L-1) to (L-70) ##STR00459## ##STR00460## ##STR00461## ##STR00462## ##STR00463## ##STR00464## ##STR00465## ##STR00466## ##STR00467## ##STR00468## ##STR00469## wherein the dotted bonds in each case mark the attachment positions, the index 1 is 0, 1 or 2, the index g is 0, 1, 2, 3, 4 or 5, j independently at each instance is 0, 1, 2 or 3; h independently at each instance is 0, 1, 2, 3 or 4; Y is O, S or NR.sup.2; R.sup.1 is, the same or differently in each instance, H, D, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more nonadjacent CH.sub.2 groups is optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO, or SO.sub.2, and wherein one or more hydrogen atoms are 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, each of which is optionally substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more radicals R.sup.2, or a combination of these systems; and wherein two or more adjacent radicals R.sup.1 together optionally define a mono- or polycyclic aliphatic or aromatic ring system with one another; R.sup.2 is, the same or differently in each instance, H, D, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more radicals R.sup.3, wherein one or more nonadjacent CH.sub.2 groups is optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO, or SO.sub.2, and wherein one or more hydrogen 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, each of which is optionally substituted by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.3 radicals, or a combination of these systems; and wherein two or more adjacent radicals R.sup.2 together optionally define a mono- or polycyclic aliphatic or aromatic ring system with one another; R.sup.3 is, the same or differently in each instance, H, D, F, or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms is optionally replaced by D or F, an aromatic and/or heteroaromatic ring system having 5 to 30 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by D or F; and wherein two or more adjacent radicals R.sup.3 together optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another.

2. The compound or mixture of compounds of claim 1, wherein the compound is a compound of formulae (III) or (IV) and the mixture is a mixture of a compound of formula (III) and a compound of formula (IV): ##STR00470##

3. The compound or mixture of compounds of claim 1, wherein the compound is a compound of formulae (Ia), (IIa), (IIIa), or (IVa) and the mixture is a mixture of at least one compound of formulae (Ia), (IIa), (IIIa), and (IVa): ##STR00471##

4. The compound or mixture of compounds of claim 3, wherein not more than two groups X in the compounds of formulae (Ia), (IIa), (IIIa), and (IVa) are N.

5. The compound or mixture of compounds of claim 1, wherein the compound is a compound of formulae (Ib), (IIb), (IIIb), or (IVb) and the mixture is a mixture of at least one compound of formulae (Ib), (IIb), (IIIb), and (IVb): ##STR00472## wherein m is 0, 1, 2, 3, or 4.

6. The compound or mixture of compounds of claim 1, wherein Q is selected from the group consisting of structures of formulae (Q-4), (Q-6), (Q-8), (Q-9), (Q-10), (Q-12), (Q-13), and (Q-15): ##STR00473## ##STR00474## wherein m is 0, 1, 2, 3 or 4.

7. The compound or mixture of compounds of claim 1, wherein Ar.sup.1 and/or a radical R.sup.2 bonded to Ar.sup.1 of formulae (Q-1) or (Q-3) comprises a structural element selected from the group consisting of structures of formulae (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), (Q-15), (Q-16), and (Q-17): ##STR00475## ##STR00476## ##STR00477## wherein m is 0, 1, 2, 3 or 4; and the dotted bond denotes the attachment position or, with regard to formulae (Q-16) and (Q-17), the attachment positions at which the structural element of formula (Q-16) or (Q-17) binds to other structural elements of the radical Ar.sup.1 or to the radical R.sup.2 or to a structure of formulae (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), or (Q-15).

8. The compound or mixture of compounds of claim 6, wherein Ar.sup.1 and/or a radical R.sup.2 bonded to Ar.sup.1 of formulae (Q-4), (Q-6), (Q-8), (Q-9), (Q-10), (Q-12), (Q-13), and (Q-15) comprises a structural element selected from the group consisting of structures of formulae (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), (Q-15), (Q-16), and (Q-17): ##STR00478## ##STR00479## wherein the dotted bond denotes the attachment position or, with regard to formulae (Q-16) and (Q-17), the attachment positions at which the structural element of formula (Q-16) or (Q-17) binds to other structural elements of the radical Ar.sup.1 or to the radical R.sup.2 or to a structure of formulae (Q-1), (Q-2), (Q-3), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), or (Q-15).

9. The compound or mixture of compounds of claim 1, wherein the compound does not or the compounds of the mixture do not comprise a carbazole and/or triarylamine group.

10. The compound or mixture of compounds of claim 1, wherein the compound does not or the compounds of the mixture do not comprise a hole-transporting group.

11. An oligomer, polymer, or dendrimer comprising the compound or mixture of compounds of claim 1, wherein one or more bonds of the compound or mixture of compounds to the polymer, oligomer, or dendrimer are present.

12. A composition comprising the compound or mixture of compounds of claim 1 and at least one further compound 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 blocker materials, and hole blocker materials.

13. A composition comprising the oligomer, polymer, or dendrimer of claim 11 and at least one further compound 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 blocker materials, and hole blocker materials.

14. A formulation comprising the compound or mixture of compounds of claim 1 and at least one solvent.

15. A formulation comprising the oligomer, polymer, or dendrimer of claim 11 and at least one solvent.

16. A formulation comprising the composition of claim 12 and at least one solvent.

17. A formulation comprising the composition of claim 13 and at least one solvent.

18. A process for preparing a compound or a compound of the mixture of compounds of claim 1 comprising reacting a compound comprising at least one electron-transporting group with a compound comprising at least one fluorene radical in a coupling reaction.

19. An electronic device comprising a compound or mixture of compounds of claim 1.

20. The electronic device of claim 19, wherein the electronic 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, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

21. An electronic device comprising the oligomer, polymer, or dendrimer of claim 11.

22. The electronic device of claim 21, wherein the electronic 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, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

23. An electronic device comprising the composition of claim 12.

24. The electronic device of claim 23, wherein the electronic 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, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

25. An electronic device comprising the composition of claim 13.

26. The electronic device of claim 25, wherein the electronic 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, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

27. A compound of formulae (I) or (II) or a mixture of a compound of formula (I) and a compound of formula (II): ##STR00480## wherein X is, the same or differently in each instance, N or CR′, with the proviso that not more than two groups X in one cycle are N; Q is selected from the group consisting of structures of formulae (Q-4), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), (Q-15), (Q-16), and (Q-17): ##STR00481## ##STR00482## ##STR00483## wherein the dotted bond denotes the attachment position or, with regard to formulae (Q-16) and (Q-17), the attachment positions at which the structural element of formula (Q-16) or (Q-17) binds to other structural elements of the radical Ar.sup.1 or to the radical R.sup.2 or to a structure of formulae (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), or (Q-15); Ar.sup.1 is an aromatic or heteroaromatic ring system having 6 to 40 carbon atoms and is optionally substituted in each case by one or more radicals R.sup.2, an aryloxy group having 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or an aralkyl group having 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more radicals R.sup.2, and wherein two or more adjacent radicals R.sup.1 or R.sup.2 together optionally define a mono- or polycyclic aliphatic ring system with each other and which is optionally substituted by one or more radicals R.sup.3; L.sup.1 is a bond, C(═O), pyrimidine which is optionally substituted by one or more R.sup.1, triazine which is optionally substituted by one or more R.sup.1 radicals or a group of the Formula (L-1) to (L-70): ##STR00484## ##STR00485## ##STR00486## ##STR00487## ##STR00488## ##STR00489## ##STR00490## ##STR00491## ##STR00492## ##STR00493## ##STR00494## wherein the dotted bonds in each case mark the attachment positions, the index 1 is 0, 1 or 2, the index g is 0, 1, 2, 3, 4 or 5, j independently at each instance is 0, 1, 2 or 3; h independently at each instance is 0, 1, 2, 3 or 4; Y is O, S or NR.sup.2; R.sup.1 is, the same or differently in each instance, H, D, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more nonadjacent CH.sub.2 groups is optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO, or SO.sub.2, and wherein one or more hydrogen atoms are 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, each of which is optionally substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more radicals R.sup.2, or a combination of these systems; and wherein two or more adjacent radicals R.sup.1 together optionally define a mono- or polycyclic aliphatic or aromatic ring system with one another; R.sup.2 is, the same or differently in each instance, H, D, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more radicals R.sup.3, wherein one or more nonadjacent CH.sub.2 groups is optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO, or SO.sub.2, and wherein one or more hydrogen 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, each of which is optionally substituted by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.3 radicals, or a combination of these systems; and wherein two or more adjacent radicals R.sup.2 together optionally define a mono- or polycyclic aliphatic or aromatic ring system with one another; R.sup.3 is, the same or differently in each instance, H, D, F, or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms is optionally replaced by D or F, an aromatic and/or heteroaromatic ring system having 5 to 30 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by D or F; and wherein two or more adjacent radicals R.sup.3 together optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another.

28. The compound or mixture of compounds of claim 3, wherein L.sup.1 is selected from the formulae (L-1) to (L-54).

29. The compound or mixture of compounds of claim 3, wherein L.sup.1 is selected from the group consisting of ortho-phenylene, meta-phenylene, para-phenylene, biphenyl, fluorene, pyridine, pyrimidine, triazine, dibenzofuran and dibenzothiophene, each of which may be substituted by one or more R.sup.2 radicals.

30. A compound of formulae (I) or (II) or a mixture of a compound of formula (I) and a compound of formula (II): ##STR00495## wherein X is, the same or differently in each instance, N or CR′, with the proviso that not more than two groups X in one cycle are N; Q is selected from the group consisting of structures of formulae (Q-1), and (Q-3): ##STR00496## wherein the dotted bond denotes the attachment position; and Ar.sup.1 is an aromatic or heteroaromatic ring system having 6 to 40 carbon atoms and is optionally substituted in each case by one or more radicals R.sup.2, an aryloxy group having 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or an aralkyl group having 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more radicals R.sup.2, and wherein two or more adjacent radicals R.sup.1 or R.sup.2 together optionally define a mono- or polycyclic aliphatic ring system with each other and which is optionally substituted by one or more radicals R.sup.3; L.sup.1 is a bond, C(═O), or an aromatic ring system having 5 to 24 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals with the proviso that L.sup.1 does not comprise an anthracene; R.sup.1 is, the same or differently in each instance, H, D, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more nonadjacent CH.sub.2 groups is optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO, or SO.sub.2, and wherein one or more hydrogen atoms are 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, each of which is optionally substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more radicals R.sup.2, or a combination of these systems; and wherein two or more adjacent radicals R.sup.1 together optionally define a mono- or polycyclic aliphatic or aromatic ring system with one another; R.sup.2 is, the same or differently in each instance, H, D, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more radicals R.sup.3, wherein one or more nonadjacent CH.sub.2 groups is optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO, or SO.sub.2, and wherein one or more hydrogen 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, each of which is optionally substituted by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.3 radicals, or a combination of these systems; and wherein two or more adjacent radicals R.sup.2 together optionally define a mono- or polycyclic aliphatic or aromatic ring system with one another; R.sup.3 is, the same or differently in each instance, H, D, F, or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms is optionally replaced by D or F, an aromatic and/or heteroaromatic ring system having 5 to 30 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by D or F; and wherein two or more adjacent radicals R.sup.3 together optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another.

31. The compound or mixture of compounds of claim 3, wherein indices l, g, h and j in the structures of the formula (L-1) to (L-70) is at most 3 in each case.

32. The compound or mixture of compounds of claim 3, wherein indices l, g, h and j in the structures of the formula (L-1) to (L-70) is at most 1 in each case.

33. A compound of formulae (I) or (II) or a mixture of a compound of formula (I) and a compound of formula (II): ##STR00497## wherein X is, the same or differently in each instance, N or CR′, with the proviso that not more than two groups X in one cycle are N; Q is selected from the group consisting of structures of formulae (Q-1), (Q-2), and (Q-3): ##STR00498## wherein the dotted bond denotes the attachment position; and Ar.sup.1 is an aromatic ring system having 6 to 40 carbon atoms and is optionally substituted in each case by one or more radicals R.sup.2, an aryloxy group having 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or an aralkyl group having 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more radicals R.sup.2, and wherein two or more adjacent radicals R.sup.1 or R.sup.2 together optionally define a mono- or polycyclic aliphatic ring system with each other and which is optionally substituted by one or more radicals R.sup.3; L.sup.1 is a bond, C(═O), or an aromatic ring system having 5 to 24 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals with the proviso that L.sup.1 does not comprise an anthracene; R.sup.1 is, the same or differently in each instance, H, D, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more nonadjacent CH.sub.2 groups is optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO, or SO.sub.2, and wherein one or more hydrogen atoms are 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, each of which is optionally substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more radicals R.sup.2, or a combination of these systems; and wherein two or more adjacent radicals R.sup.1 together optionally define a mono- or polycyclic aliphatic or aromatic ring system with one another; R.sup.2 is, the same or differently in each instance, H, D, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more radicals R.sup.3, wherein one or more nonadjacent CH.sub.2 groups is optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO, or SO.sub.2, and wherein one or more hydrogen 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, each of which is optionally substituted by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.3 radicals, or a combination of these systems; and wherein two or more adjacent radicals R.sup.2 together optionally define a mono- or polycyclic aliphatic or aromatic ring system with one another; R.sup.3 is, the same or differently in each instance, H, D, F, or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms is optionally replaced by D or F, an aromatic and/or heteroaromatic ring system having 5 to 30 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by D or F; and wherein two or more adjacent radicals R.sup.3 together optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another.

34. The compound or mixture of compounds of claim 27, wherein the compound is a compound of formulae (III) or (IV) and the mixture is a mixture of a compound of formula (III) and a compound of formula (IV): ##STR00499##

35. The compound or mixture of compounds of claim 27, wherein the compound is a compound of formula (Ia), (IIa), (IIIa), or (IVa) and the mixture is a mixture of at least one compound of formulae (Ia), (IIa), and (IVa): ##STR00500##

36. The compound or mixture of compounds of claim 35, wherein not more than two groups X in the compounds of formulae (Ia), (IIa), (IIIa) and (IVa) are N.

37. The compound or mixture of compounds of claim 27, wherein the compound does not or the compounds of the mixture do not comprise a carbazole and/or triarylamine group.

38. The compound or mixture of compounds of claim 27, wherein the compound does not or the compounds of the mixture do not a hole-transporting group.

39. An oligomer, polymer, or dendrimer comprising the compound or mixture of compounds of claim 27, wherein one or more bonds of the compound or mixture of compounds to the polymer, oligomer, or dendrimer are present.

40. A composition comprising the oligomer, polymer, or dendrimer of claim 39 and at least one further compound 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 blocker materials, and hole blocker materials.

41. A formulation comprising the oligomer, polymer, or dendrimer of claim 39 and at least one solvent.

42. A formulation comprising the composition of claim 40 and at least one solvent.

43. An electronic device comprising the oligomer, polymer, or dendrimer of claim 39.

44. The electronic device of claim 43, wherein the electronic 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, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

45. An electronic device comprising the composition of claim 40.

46. The electronic device of claim 45, wherein the electronic 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, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

47. The compound or mixture of compounds of claim 30, wherein the compound is a compound of formulae (III) or (IV) and the mixture is a mixture of a compound of formula (III) and a compound of formula (IV): ##STR00501##

48. The compound or mixture of compounds of claim 30, wherein the compound is a compound of formulae (Ia), (IIa), (IIIa), or (IVa) and the mixture is a mixture of at least one compound of formulae (Ia), (IIa), (IIIa), and (IVa): ##STR00502##

49. The compound or mixture of compounds of claim 48, wherein not more than two groups X in the compounds of formulae (Ia), (IIa), (IIIa) and (IVa) are N.

50. The compound or mixture of compounds of claim 30, wherein the compound does not or the compounds of the mixture do not comprise a carbazole and/or triarylamine group.

51. The compound or mixture of compounds of claim 30, wherein the compound does not or the compounds of the mixture do not a hole-transporting group.

52. An oligomer, polymer, or dendrimer comprising the compound or mixture of compounds of claim 30, wherein one or more bonds of the compound or mixture of compounds to the polymer, oligomer, or dendrimer are present.

53. A composition comprising the oligomer, polymer, or dendrimer of claim 52 and at least one further compound 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 blocker materials, and hole blocker materials.

54. A formulation comprising the oligomer, polymer, or dendrimer of claim 52 and at least one solvent.

55. A formulation comprising the composition of claim 53 and at least one solvent.

56. An electronic device comprising the oligomer, polymer, or dendrimer of claim 52.

57. The electronic device of claim 56, wherein the electronic 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, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

58. An electronic device comprising the composition of claim 53.

59. The electronic device of claim 58, wherein the electronic 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, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

60. The compound or mixture of compounds of claim 33, wherein the compound is a compound of formulae (III) or (IV) and the mixture is a mixture of a compound of formula (III) and a compound of formula (IV): ##STR00503##

61. The compound or mixture of compounds of claim 33, wherein the compound is a compound of formulae (Ia), (IIa), (IIIa), or (IVa) and the mixture is a mixture of at least one compound of formulae (Ia), (IIa), (IIIa), and (IVa): ##STR00504##

62. The compound or mixture of compounds of claim 61, wherein not more than two groups X in the compounds of formulae (Ia), (IIa), (IIIa), and (IVa) are N.

63. The compound or mixture of compounds of claim 33, wherein the compound does not or the compounds of the mixture do not comprise a carazole and/or triarylamine group.

64. The compound or mixture of compounds of claim 33, wherein the compound does not or the compounds of the mixture do not a hole-transporting group.

65. An oligomer, polymer, or dendrimer comprising the compound or mixture of compounds of claim 33, wherein one or more bonds of the compound or mixture of compounds to the polymer, oligomer, or dendrimer are present.

66. A composition comprising the oligomer, polymer, or dendrimer of claim 65 and at least one further compound 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 blocker materials, and hole blocker materials.

67. A formulation comprising the oligomer, polymer, or dendrimer of claim 65 and at least one solvent.

68. A formulation comprising the composition of claim 66 and at least one solvent.

69. An electronic device comprising the oligomer, polymer, or dendrimer of claim 65.

70. The electronic device of claim 69, wherein the electronic 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, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

71. An electronic device comprising the composition of claim 66.

72. The electronic device of claim 71, wherein the electronic 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, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

73. The compound of mixture of compounds of claim 27, wherein Ar.sup.1 and/or a radical R.sup.2 bonded to Ar.sup.1 of formulae (Q-1) (Q-2), or (Q-3) comprises a structural element selected from the group consisting of structures of formulae (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), (Q-15), (Q-16), and (Q-17): ##STR00505## ##STR00506## ##STR00507## wherein m is 0, 1, 2, 3 or 4; and the dotted bond denotes the attachment position or, with regard to formulae (Q-16) and (Q-17), the attachment positions at which the structural element of formula (Q-16) or (Q-17) binds to other structural elements of the radical Ar.sup.1 or to the radical R.sup.2 or to a structure of formulae (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), or (Q-15).

74. The compound or mixture of compounds of claim 30, wherein Ar.sup.1 and/or a radical R.sup.2 bonded to Ar.sup.1 of formulae (Q-1) or (Q-3) comprises a structural element selected from the group consisting of structures of formulae (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), (Q-15), (Q-16), and (Q-17): ##STR00508## ##STR00509## ##STR00510## wherein m is 0, 1, 2, 3 or 4; and the dotted bond denotes the attachment position or, with regard to formulae (Q-16) and (Q-17), the attachment positions at which the structural element of formula (Q-16) or (Q-17) binds to other structural elements of the radical Ar.sup.1 or to the radical R.sup.2 or to a structure of formulae (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12), (Q-13), (Q-14), or (Q-15).

Description

EXAMPLES

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

Synthesis Examples

(2) ##STR00139##

(3) 30 g (94 mmol) of 2,2′-dibromobiphenyl are dissolved in a baked-out flask in 200 ml of dried THF. The reaction mixture is cooled to −78° C. At this temperature, 37.7 ml of a 2.5 M solution of n-butyllithium in hexane (94 mmol) are slowly added dropwise (over about 1 h). The mixture is stirred at −70° C. for a further 1 h. Subsequently, 11.1 ml of acetophenone (94 mmol) are dissolved in 100 ml of THF and added dropwise at −70° C. After the addition has ended, the reaction mixture is warmed gradually to room temperature, quenched with NH.sub.4Cl and then concentrated on a rotary evaporator. 300 ml of acetic acid are added cautiously to the concentrated solution and then 50 ml of fuming HCl are added. The mixture is heated to 75° C. and kept there for 6 h. During this time, a white solid precipitates out.

(4) The mixture is cooled to room temperature, and the precipitated solid is filtered off with suction and washed with methanol. The residue is dried at 40° C. under reduced pressure. Yield is 25.3 g (75 mmol) (80% of theory).

(5) ##STR00140##

(6) 37 g (152 mmol) of 2,2′-dibromobiphenyl are dissolved in a baked-out flask in 300 ml of dried THF. The reaction mixture is cooled to −78° C. At this temperature, 75 ml of a 15% solution of n-butyllithium in hexane (119 mmol) are slowly added dropwise (over about 1 hour). The mixture is stirred at −70° C. for a further 1 h. Subsequently, 21.8 g of benzophenone (119 mmol) are dissolved in 100 ml of THF and added dropwise at −70° C. After the addition has ended, the reaction mixture is warmed gradually to room temperature, quenched with NH.sub.4Cl and then concentrated on a rotary evaporator. 510 ml of acetic acid are added cautiously to the concentrated solution and then 100 ml of fuming HCl are added. The mixture is heated to 75° C. and kept at this temperature for 4 h. During this time, a white solid precipitates out. The mixture is then cooled to room temperature, and the precipitated solid is filtered off with suction and washed with methanol. The residue is dried at 40° C. under reduced pressure. Yield is 33.2 g (83 mmol) (70% of theory).

(7) In an analogous manner, the following brominated compounds are prepared:

(8) TABLE-US-00001 Reactant 1 Reactant 2 Product Yield b1 78% b2 70% b3 82%

(9) ##STR00150##

(10) 2.7 g (110 mmol) of iodine-activated magnesium turnings and a mixture of 25.6 g (110 mmol) of 2-bromobiphenyl, 0.8 ml of 1,2-dichloroethane, 50 ml of 1,2-dimethoxyethane, 400 ml of THF and 200 ml of toluene are used to prepare the corresponding Grignard reagent by trace heating with an oil bath at 70° C. Once the magnesium has reacted fully, the mixture is cooled to room temperature and then a solution of 25.9 g (100 mmol) of 1-bromofluorenone [36804-63-4] in 500 ml of THF is added dropwise, and the reaction mixture is heated to 50° C. for 4 h and then stirred at room temperature for a further 12 h. 100 ml of water are added, the mixture is stirred briefly, the organic phase is removed and the solvent is removed under reduced pressure. The residue is suspended in 500 ml of glacial acetic acid heated to 40° C., 0.5 ml of conc. sulphuric acid is added to the suspension and the mixture is then stirred at 100° C. for 2 h. After cooling, the precipitated solid is filtered off with suction and washed once with 100 ml of glacial acetic acid and three times with 100 ml each time of ethanol, and finally recrystallized from dioxane. Yield: 26.9 g (68 mmol), 68%; purity: about 98% by .sup.1H NMR.

(11) The following compound is obtained in an analogous manner:

(12) TABLE-US-00002 Reactant 1 Reactant 2 Product Yield 1c 90%
d) 4-Biphenyl-4-yl-2-chloroquinazoline

(13) ##STR00154##

(14) 13 g (70 mmol) of biphenyl-4-boronic acid, 13.8 g (70 mmol) of 2,4-dichloroquinazoline and 14.7 g (139 mmol) of sodium carbonate are suspended in 200 ml of toluene, 52 ml of ethanol and 100 ml of water. 800 mg (0.69 mmol) of tetrakisphenylphosphinepalladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The residue is recrystallized from heptane/dichloromethane. The yield is 13 g (41 mmol), corresponding to 59% of theory.

(15) In an analogous manner, the following compounds are obtained:

(16) TABLE-US-00003 Reactant 1 Reactant 2 Product Yield 2d 76% 3d 0 75% 4d 73% 5d 78% 6d 76% 7d 0 77% 8d 72% 9d 73% 10d  0 72%

(17) ##STR00182##

Step 1) Synthesis of spiro-9,9′-bifluorene-1-boronic acid

(18) To a solution, cooled to −78° C., of 106 g (270 mmol) of 1-bromo-9-spirobifluorene in 1500 ml of diethyl ether are added dropwise 110 ml (276 mmol) of n-butyllithium (2.5 M in hexane). The reaction mixture is stirred at −78° C. for 30 min. The mixture is allowed to come to room temperature and cooled again to −78° C., and then a mixture of 40 ml (351 mmol) of trimethyl borate in 50 ml of diethyl ether is added rapidly. After warming to −10° C., hydrolysis is effected with 135 ml of 2 N hydrochloric acid. The organic phase is removed, washed with water, dried over sodium sulphate and concentrated to dryness. The residue is taken up in 300 ml of n-heptane, and the colourless solid is filtered off with suction, washed with n-heptane and dried under reduced pressure. Yield: 94.5 g (255 mmol), 99% of theory; purity: 99% by HPLC.

(19) In an analogous manner, the following compounds are obtained:

(20) TABLE-US-00004 Reactant 1 Product Yield 1e 83% 2e 80% 3e 83% 4e 0 75% 5e 70% 6e 72% 7e 63% 8e 74% 9e 00 70%

Step 2) 4-(9H,9′H-[9,9′]bifluorenyl-1-yl)-2-phenylquinazoline

(21) 56.8 g (110 mmol) of spiro-9,9′-bifluorene-1-boronic acid, 26 g (110.0 mmol) of 4-chloro-2-phenylquinazoline and 44.6 g (210.0 mmol) of tripotassium phosphate are suspended in 500 ml of toluene, 500 ml of dioxane and 500 ml of water. Added to this suspension are 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane/iso-propanol and finally sublimed under high vacuum (p=5×10.sup.−5 mbar, T=350° C.). The yield is 64 g (43.5 mmol), corresponding to 80% of theory.

(22) In an analogous manner, the following compounds are obtained:

(23) TABLE-US-00005 Reactant 1 Reactant 2 Product Yield 9e 01 02 03 81% 10e 04 05 06 80% 11e 07 08 09 72% 12e 0 70% 13e 82% 14e 78% 15e 0 79% 16e 70% 17e 65% 18e 0 79% 19e 63% 20e 73% 21e 72% 22e 0 77% 23e 74% 24e 81% 25e 0 80% 26e 69% 27e 73% 28f 0 68% 29e 65% 30e 68% 31e 63% 32e 0 79% 33e 81% 34e 65% 35e 0 66% 36e 71% 37e 69% 38e 0 63% 39e 65% 40e 60% 41e 61% 42e 00 01 02 69% 43e 03 04 05 64% 44e 06 07 08 66% 45e 09 0 69% 46e 70% 47e 61% 48e 0 64% 49e 73% 50e 62% 51e 75% 52e 0 68% 53e 60% 54e 61% 55e 0 59% 56e 63% 57e 65% 58e 0 62% 59e 60% 60e 64%

f) 2-(7-Bromo-9,9-dimethyl-9H-fluoren-4-yl)-4-phenylquinazoline

(24) ##STR00357##

(25) 75.6 g (190.0 mmol) of 2-(9,9-dimethyl-9H-fluoren-4-yl)-4-phenylquinazoline are suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulphuric acid (95-98%). 34 g (190 mmol) of NBS are added to this suspension and the mixture is stirred in the dark for 2 hours. Thereafter, water/ice is added and solids are removed and washed with ethanol. The residue is recrystallized in toluene. The yield is 68 g (142 mmol), corresponding to 76% of theory.

(26) The following compounds are prepared in an analogous manner:

(27) TABLE-US-00006 Reactant 1 Product Yield 1f 71%% 2f 0 74% 36 65%

g) 9,9-Dimethyl-5-(4-phenylquinazolin-2-yl)-9H-fluorene-2-boronic acid

(28) ##STR00364##

(29) To a solution, cooled to −78° C., of 128 g (270 mmol) of 4-[3-(7′-bromo-9,9′-spirobi[fluoren]-4′-yl)phenyl]-1-phenylbenzimidazole in 1500 ml of diethyl ether are added dropwise 110 ml (276 mmol) of n-butyllithium (2.5 M in hexane). The reaction mixture is stirred at −78° C. for 30 min. The mixture is allowed to come to room temperature and cooled again to −78° C., and then a mixture of 40 ml (351 mmol) of trimethyl borate in 50 ml of diethyl ether is added rapidly. After warming to −10° C., hydrolysis is effected with 135 ml of 2 N hydrochloric acid. The organic phase is removed, washed with water, dried over sodium sulphate and concentrated to dryness. The residue is taken up in 300 ml of n-heptane, and the colourless solid is filtered off with suction, washed with n-heptane and dried under reduced pressure. Yield: 126 g (241 mmol), 99% of theory; purity: 90% by HPLC.

(30) In an analogous manner, the following compounds are obtained:

(31) TABLE-US-00007 Reactant 1 Product Yield 1g 83% 2g 87% 3g 0 80%

h) 2-[7-(4,6-Diphenyl-[1,3,5]triazin-2-yl)-9,9-dimethyl-9H-fluoren-4-yl]-4-phenylquinazoline

(32) ##STR00371##

(33) 48 g (110.0 mmol) of 9,9-dimethyl-5-(4-phenylquinazolin-2-yl)-9H-fluorene-2-boronic acid, 29.5 g (110.0 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 21 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. Added to this suspension are 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane/iso-propanol and finally sublimed under high vacuum (p=5×10.sup.−5 mbar, T=350° C.). The yield is 58 g (93 mmol), corresponding to 86% of theory.

(34) The following compounds are prepared in an analogous manner:

(35) TABLE-US-00008 Reactant 1 Reactant 2 Product Yield 1h 73% 2h 82% 3h 0 73% 4h 70% 5h 72% 6h 70% 7h 0 69% 8h 68% 9h 70% 10h 00 01 71%

(36) ##STR00402##

(37) A 2 l four-neck flask under protective gas is initially charged with 50.0 g (105 mmol, 1.00 eq) of 4,4′-dibromo-9,9′-spirobifluorene, 41.7 g (105 mmol, 1.00 eq) of 1-phenyl-2-[e-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-y-yl)phenyl]-1H-benzimidazole, and 36.4 g (263 mmol, 2.50 eq) of potassium carbonate in 400 ml of toluene, 400 ml 1,4-dioxane and 200 ml of demineralized water, and the mixture is degassed. Subsequently, 1.22 g (1.05 mmol, 0.01 eq) of tetrakis(triphenylphosphine)palladium(0) are added and the mixture is heated at reflux overnight. After the reaction has ended, the mixture is cooled down, filtered through Celite and diluted with 1 l of toluene. The solution is washed 3× with 300 ml each time of semi-saturated sodium chloride solution, dried over sodium sulphate and concentrated to about 200 ml on a rotary evaporator. The precipitated solids are filtered off and dried under reduced pressure. The disubstituted by-product is removed by means of sublimation. 21.0 g (32 mmol, 31%) of the desired product are obtained.

(38) Variant B:

(39) Procedure analogous to variant A; rather than tetrakis(triphenylphosphine)palladium(0), 0.01 eq of palladium(II) acetate and 0.01 eq of dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine (SPhos) are used.

(40) In an analogous manner, the following compounds are obtained:

(41) TABLE-US-00009 No. Reactant 1 Reactant 2 Product 3 Variant Yield 1i 03 04 05 B 41% 2i 06 07 08 B 62%

(42) ##STR00409##

(43) A 1 l four-neck flask is initially charged with 22.0 g (33.1 mmol, 1.00 eq) of 2-[3-(7′-bromo-9,9′-spirobi[fluoren]-2′-yl)phenyl]-1-phenylbenzimidazole, 8.84 g (30.1 mmol, 0.91 eq) of bis(pinacolato)diboron and 26.0 g (265 mmol, 8.00 eq) of potassium acetate in 500 ml of dried 1,4-dioxane and the mixture is degassed for 30 minutes. Subsequently, 812 mg (0.995 mmol, 0.0300 eq) of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II) complex are added together with DCM and the mixture is heated to internal temperature 80° C. After stirring overnight, the mixture is cooled down and the precipitated solids are filtered off with suction. The filtrate is concentrated to about 50 ml on a rotary evaporator and the precipitated solids are likewise filtered off with suction. The solids are combined and dried. 21.0 g (29.5 mmol, 89%) of the boronic ester are obtained.

(44) In an analogous manner, the following compounds are obtained:

(45) TABLE-US-00010 No. Reactant 3 Product 4 Yield 1j 0 97% 2j 47%

(46) ##STR00414##
Variant A:

(47) In a 1 l three-neck flask, 21.0 g (29.5 mmol, 1.00 eq) of 1-phenyl-2-[3-[7′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9′-spirobi[fluoren]-2′-yl]phenyl]benzimidazole and 7.2 g (29.5 mmol, 1.00 eq) of 4-chloro-2-phenylquinazoline are initially charged together with 3.75 g (35.4 mmol, 1.20 eq) of sodium carbonate in 200 ml of toluene, 200 ml of 1,4-dioxane and 100 ml of demineralized water, and the mixture is degassed for 20 minutes. After adding 1.02 g (0.885 mmol, 0.0300 eq) of tetrakis(triphenylphosphine)palladium(0), the mixture is heated under reflux for 2 days and, after the reaction has ended, cooled down. The precipitated solids are filtered off with suction, washed with water and a little toluene, and then recrystallized repeatedly from toluene/heptane until an HPLC purity of >99.9% is attained. After sublimation, 11.5 g (14.0 mmol, 46%) of a colourless solid are obtained.

(48) Variant B:

(49) Procedure analogous to variant A; rather than tetrakis(triphenylphosphine)palladium(0), 0.01 eq of palladium(II) acetate and 0.04 eq of tri(o-tolyl)phosphine (SPhos) are used.

(50) Variant C:

(51) Procedure analogous to variant A; rather than tetrakis(triphenylphosphine)palladium(0), 0.01 eq of palladium(II) acetate and 0.01 eq of dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine (SPhos) are used.

(52) The following were prepared analogously:

(53) TABLE-US-00011 No. Reactant 4 Reactant 5 Product 6 Variant Yield 6k B 62% 7k 0 A 41% 8k A 40% 9k B 57% 10k A 61%
Production of the OLEDs

(54) In examples C1 to I14 which follow (see tables 1 and 2), the data of various OLEDs are presented.

(55) Pretreatment for Examples C1-I14:

(56) Glass plaques which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm are the substrates to which the OLEDs are applied.

(57) The OLEDs basically have the following layer structure: substrate/hole transport layer (HTL)/optional interlayer (IL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in table 1. The materials required for production of the OLEDs are shown in table 3.

(58) All materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as IC1:IC3:TEG1 (55%:35%:10%) mean here that the material 101 is present in the layer in a proportion by volume of 55%, 103 in a proportion of 35% and TEG1 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.

(59) The OLEDs are characterized in a standard manner. 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) are determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter U1000 in table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. CE1000 and PE1000 respectively refer to the current and power efficiencies which are achieved at 1000 cd/m.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2.

(60) The data for the various OLEDs are collated in table 2. Examples C1-C4 are comparative examples according to the prior art; examples I1-I14 show data of OLEDs of the invention.

(61) Some of the examples are elucidated in detail hereinafter, in order to illustrate the advantages of the OLEDs of the invention.

(62) Use of Materials of the Invention in Phosphorescent OLEDs

(63) The materials of the invention, when used as hole blocker layer (HBL) in phosphorescent OLEDs, give a significant improvement in efficiency over the prior art. By use of the inventive compounds 24e, 52e and 58e, it is possible to observe an increase in external quantum efficiency by about 10% compared to the prior art PA1, PA2 and PA3. In the case of use of the materials of the invention in the electron transport layer (ETL) as well, it is possible to achieve an improvement in external quantum efficiency over the prior art (compare Example C4 to Example I4).

(64) TABLE-US-00012 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness C1 SpA1 HATCN SpMA1 IC1:TEG1 PA1 ST2:LiQ — 70 nm 5 nm 110 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm C2 SpA1 HATCN SpMA1 IC1:IC3:TEG1 PA2 ST2:LiQ — 70 nm 5 nm 110 nm (50%:45%:5%) 10 nm (50%:50%) 30 nm 30 nm C3 SpA1 HATCN SpMA1 IC1:TEG1 PA3 ST2:LiQ — 70 nm 5 nm 110 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm C4 SpA1 HATCN SpMA1 IC1:IC3:TEG1 — ST2:PA4 LiQ 70 nm 5 nm 110 nm (50%:45%:5%) (40%:60%) 3 nm 30 nm 40 nm I1 SpA1 HATCN SpMA1 IC1:TEG1 24e ST2:LiQ — 70 nm 5 nm 110 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm I2 SpA1 HATCN SpMA1 IC1:IC3:TEG1 52e ST2:LiQ — 70 nm 5 nm 110 nm (50%:45%:5%) 10 nm (50%:50%) 30 nm 30 nm I3 SpA1 HATCN SpMA1 IC1:TEG1 58e ST2:LiQ — 70 nm 5 nm 110 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm I4 SpA1 HATCN SpMA1 IC1:IC3:TEG1 — ST2:60e LiQ 70 nm 5 nm 110 nm (50%:45%:5%) (40%:60%) 3 nm 30 nm 40 nm I5 SpMA1 — — 16e:TER4 — ST2:LiQ — 140 nm  (95%:5%) (50%:50%) 40 nm 35 nm I6 SpMA1 — — IC1:TER4 19e ST2:LiQ — 140 nm  (95%:5%) 10 nm (50%:50%) 40 nm 25 nm I7 SpMA1 — — 22e:TER4 — ST2:LiQ — 140 nm  (97%:3%) (50%:50%) 40 nm 35 nm I8 SpA1 HATCN SpMA1 IC1:TEG1 10k ST2:LiQ — 70 nm 5 nm 110 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm I9 SpMA1 — — 41e:SpMA1:TER4 — ST2:LiQ — 140 nm  (55%:22%:3%) (50%:50%) 40 nm 35 nm I10 SpMA1 — — 43e:TER4 IC1 ST2:LiQ — 140 nm  (95%:5%) 10 nm (50%:50%) 40 nm 25 nm I11 SpA1 HATCN SpMA1 IC1:TEG1 IC1 ST2:44e LiQ 70 nm 5 nm 110 nm (90%:10%) 10 nm (40%:60%) 3 nm 30 nm 40 nm I12 SpMA1 — — IC1:TER4 48e ST2:LiQ — 140 nm  (95%:5%) 10 nm (50%:50%) 40 nm 25 nm I13 SpA1 HATCN SpMA1 IC1:TEG1 — 1h:LiQ — 70 nm 5 nm 110 nm (90%:10%) (50%:50%) 30 nm 30 nm I14 SpMA1 — — 7h:TEG1:TER4 ST2:LiQ — 140 nm  (85%:10%:5%) (50%:50%) 40 nm 35 nm

(65) TABLE-US-00013 TABLE 2 Measurement results for the various OLEDs U1000 CE1000 PE1000 EQE CIE x/y at Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 C1 3.6 55 48 15.2% 0.31/0.64 C2 3.4 55 51 14.9% 0.34/0.63 C3 3.5 56 50 15.5% 0.31/0.64 C4 3.7 52 44 14.1% 0.34/0.62 I1 3.6 64 56 17.2% 0.33/0.63 I2 3.3 59 56 16.2% 0.32/0.64 I3 3.5 63 57 17.1% 0.33/0.63 I4 3.7 56 48 15.3% 0.33/0.63 I5 4.6 17 12 14.6% 0.66/0.34 I6 4.9 16 10 14.4% 0.67/0.33 I7 4.7 16 11 14.9% 0.67/0.33 I8 3.5 64 57 17.4% 0.32/0.64 I9 4.5 16 11 15.3% 0.67/0.33 I10 4.6 17 12 15.1% 0.66/0.34 I11 3.6 58 51 15.8% 0.31/0.64 I12 5.0 15 9 14.8% 0.67/0.33 I13 3.7 63 53 17.2% 0.31/0.64 I14 4.4 18 13 16.5% 0.67/0.33

(66) TABLE-US-00014 TABLE 3 Structural formulae of the materials for the OLEDs 0 HATCN SpA1 SpMA1 LiQ IC1 TEG1 ST2 TER4 IC3 PA1 0 PA2 PA3 PA4 24e 52e 58e 60e 16e 19e 22e 0 10k 41e 43e 44e 48e 1h 7h