MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to an organic electroluminescent device comprising a benzothiazine derivative and it also relates to specific benzothiazine derivatives.

Claims

1.-15. (canceled)

16. An organic electroluminescent device comprising an anode, a cathode and at least one organic layer between the cathode and the anode, wherein the at least one organic layer comprises a compound of the formula (1), ##STR00655## where the following applies to the symbols used: Y stands for CR.sup.Y or N; with the proviso that at least two adjacent groups Y form a condensed aromatic or heteroaromatic ring system with the benzothiazine ring of formula (1); R.sup.S, R.sup.Y stand on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, N(R).sub.2, N(Ar).sub.2, NO.sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; where the radical R.sup.S may form an aliphatic, aromatic or heteroaromatic ring system ring with a radical R.sup.Y or with the adjacent ring formed by two groups Y, which may be substituted by one or more radicals R; and where two adjacent radicals R.sup.Y may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R; R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, N(R′).sub.2, N(Ar).sub.2, NO.sub.2, Si(R′).sub.3, B(OR′).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by R′C═CR′, C♭C, Si(R′).sub.2, Ge(R′).sub.2, Sn(R′).sub.2, C═O, C═S, C═Se, P(═O)(R′), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R′, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R′; where two adjacent substituents R may form an aliphatic or aromatic ring system together, which may be substituted by one or more radicals R′; Ar is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R′; R′ stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, 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, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by SO, SO.sub.2, O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.

17. An organic electroluminescent device according to claim 16, wherein the compound of formula (1) is selected from the compounds of formulae (2), (3) or (4); ##STR00656## where the rings Ar.sup.1 and Ar.sup.2 are aromatic or heteroaromatic ring systems condensed with the benzothiazine ring, which have 5 to 30 aromatic ring atoms and which may be substituted by at least one radical R; and where the symbols Y and R.sup.S have the same meaning as in 16.

18. An organic electroluminescent device according to claim 17, wherein the rings Ar.sup.1 and Ar.sup.2 are selected from the rings of the formulae (Ar-1) and (Ar-2), ##STR00657## where the dashed bonds between the signs “*” correspond to the common bond of the group of formula (Ar-1) or (Ar-2) with the benzothiazine ring, and where: V stands for C(R.sup.0).sub.2, NR.sup.N, O or S; X stands, identically or differently on each occurrence, for CR.sup.X or N; or two adjacent groups X stand for a group of the formula (Ar-3) or (Ar-4), ##STR00658##  where the dashed bonds between the signs “*” correspond to the common bond of the group of formula (Ar-3) or (Ar-4) with a group of formula (Ar-1) or (Ar-2), and furthermore: E stands for C(R.sup.0).sub.2, C═O, NR.sup.N, O or S; and T stands, identically or differently on each occurrence, for CR.sup.T or N; R.sup.T, R.sup.X stand on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, N(R).sub.2, N(Ar).sub.2, NO.sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; where two adjacent substituents R.sup.T may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R, and where two adjacent substituents R.sup.X may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R; R.sup.0 stands on each occurrence, identically or differently, for 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 a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where two adjacent substituents R.sup.0 may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R; and R.sup.N stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, Si(R).sub.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.

19. An organic electroluminescent device according to claim 16, wherein the compound of formula (1) is selected from the compounds of formulae (2-1) to (4-5) as depicted below: ##STR00659## where X, R.sup.S, R.sup.Y have the same meaning as in claim 16 and V stands for C(R.sup.0).sub.2, NR.sup.N, O or S.

20. An organic electroluminescent device according to claim 16, wherein the compound of formula (1) is selected from the compounds of formulae (2-1-1) to (4-5-3) as depicted below: ##STR00660## ##STR00661## ##STR00662## where the symbols R.sup.Y and R.sup.S have the same meaning as in claim 16 and the symbols R.sup.X, R.sup.T and V stands for C(R.sup.0).sub.2, NR.sup.N, O or S.

21. An organic electroluminescent device according to claim 16, wherein the compound of formula (1) comprises at least one radical selected from the groups of formula (R-1), ##STR00663## where Ar.sup.S stands for a single bond or for an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R; and Ar.sup.2 stands for phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, anthracene, phenanthrene, triphenylene, fluoranthene, indole, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, carbazole, indenocarbazole, indolocarbazole, phenanthroline, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinolone, benzopyridine, benzopyridazine, benzopyrimidine, quinazoline, benzimidazole, or a combination of two or three of these groups, each of which may be substituted by one or more radicals R.

22. An electroluminescent device according to claim 16, wherein the compound of formula (1) comprises at least one radical selected from the groups of formula (R-2), ##STR00664## where the dashed bond indicates the bond to the structure of formula (1), Ar.sup.S stands for a single bond or for an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R; and where: A stands, identically or differently on each occurrence, for CR.sup.A or N; or two adjacent groups A stand for a group of the formula (Ar-5) or (Ar-6), ##STR00665##  where the dashed bonds between the signs “*” correspond to the common bond of the group of formula (Ar-5) or (Ar-6) with the group of formula (R-2), and where: E.sup.1, E.sup.2 stands for C(R.sup.0).sub.2, C═O, NR.sup.N, O or S, where R.sup.0 stands on each occurrence, identically or differently, for 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 a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where two adjacent substituents R.sup.0 may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R; R.sup.N stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, Si(R).sub.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.A1 stands, identically or differently on each occurrence, for CR.sup.A1 or N; and R.sup.A, R.sup.A1 are on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, N(R).sub.2, N(Ar).sub.2, NO.sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; where two adjacent substituents R.sup.A may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R, and where two adjacent substituents R.sup.A1 may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R.

23. An organic electroluminescent device according to claim 16, wherein the compound of the formula (1) is employed as matrix material for fluorescent or phosphorescent emitters, and/or in a hole-blocking layer and/or in an electron-transport layer and/or in an electron-blocking or exciton-blocking layer and/or in a hole-transport layer.

24. An organic electroluminescent device according to claim 16, wherein the compound of the formula (1) is employed as matrix material for phosphorescent emitters.

25. A compound of formula (1′), ##STR00666## where the following applies to the symbols and indices used: Y stands for CR.sup.Y or N; with the proviso that at least two adjacent groups Y stand for a condensed aromatic or heteroaromatic ring system with the benzothiazine ring of formula (1′); R.sup.S, R.sup.Y stand on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, N(R).sub.2, N(Ar).sub.2, NO.sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; where the radical R.sup.S may form an aliphatic, aromatic or heteroaromatic ring system ring with a radical R.sup.Y or with the adjacent ring formed by two groups Y, which may be substituted by one or more radicals R; and where two adjacent radicals R.sup.Y may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R; R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, N(R′).sub.2, N(Ar).sub.2, NO.sub.2, Si(R′).sub.3, B(OR′).sub.2, OSO.sub.2R′, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by R′C═CR′, Si(R′).sub.2, Ge(R′).sub.2, Sn(R′).sub.2, C═O, C═S, C═Se, P(═O)(R′), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R′, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R′; where two adjacent substituents R may form an aliphatic or aromatic ring system together, which may be substituted by one or more radicals R′; Ar is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R′; and R′ stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or abranched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by SO, SO.sub.2, O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms; wherein the compounds of formula (1′) comprises at least one radical, which stands for a group of formula (R-2), ##STR00667## where the dashed bond indicates the bond to the structure, and where: Ar.sup.S stands for a single bond or for an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R; A stands, identically or differently on each occurrence, for CR.sup.A or N; or two adjacent groups A stand for a group of the formula (Ar-5) or (Ar-6), ##STR00668## °where the dashed bonds between the signs “*” correspond to the common bond of the group of formula (Ar-5) or (Ar-6) with the group of formula (R-2), and where: E.sup.1, E.sup.2 stands for C(R.sup.0).sub.2, C═O, NR.sup.N, O or S; A.sup.1 stands, identically or differently on each occurrence, for CR.sup.A1 or N; R.sup.0, R.sup.N are on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, Si(R).sub.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where two adjacent substituents R.sup.0 may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R; R.sup.A, R.sup.A1 are on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, N(R).sub.2, N(Ar).sub.2, NO.sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; where two adjacent substituents R.sup.A may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R; and where two adjacent substituents R.sup.A1 may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R; and n is an integer equal to 1, 2, 3 or 4.

26. The compound according to claim 25, wherein the compound is selected from compounds of formulae (2-1′) to (4-5′) as depicted below: ##STR00669## where the symbols R.sup.S, R.sup.Y have the same meaning as in claim 25, and where: V stands for C(R.sup.0).sub.2, NR.sup.N, O or S; X stands, identically or differently on each occurrence, for CR.sup.X or N; or two adjacent groups X stand for a group of the formula (Ar-3) or (Ar-4), ##STR00670##  where the dashed bonds between the signs “*” correspond to the common bond of the group of formula (Ar-3) or (Ar-4) with the rest of the structure, and furthermore: E stands for C(R.sup.0).sub.2, C═O, NR.sup.N, O or S; where R.sup.N and R.sup.0 have the same meaning as in claim 25; T stands, identically or differently on each occurrence, for CR.sup.T or N; R.sup.T, R.sup.X stand on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, N(R).sub.2, N(Ar).sub.2, NO.sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; where two adjacent substituents R.sup.T may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R, and where two adjacent substituents R.sup.X may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R; wherein the compounds of formulae (2-1′) to (4-5′) comprise at least one radical R.sup.S, R.sup.X, R.sup.Y, R.sup.T or R, which stands for a group of formula (R-2) as defined in claim 25.

27. A formulation comprising at least one compound according to claim 25 and at least one solvent.

28. An electronic device comprising at least one compound according to claim 25.

29. The electronic device according to claim 28, 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.

30. The electronic device according to claim 28, wherein the device is an organic electroluminescent device, and wherein the compound is employed as a matrix material for emitters, a hole-transport-material or an electron-transport material.

Description

A) SYNTHESES EXAMPLES

[0154] Unless otherwise stated, the following syntheses are carried out in a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained from Sigma-ALDRICH or ABCR. The CAS numbers of the compounds known from the literature are also indicated below. The compounds according to the invention can be synthesised by means of synthesis methods known to the skilled person.

[0155] a) Suzuki-Reaction

##STR00412##

[0156] 52.12 g (160 mmol) of the dibenzothiazine derivative, 50 g (172 mmol) of N-phenyl-carbazole-3-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 mL of ethylene glycol dimethyl ether and 280 mL of water. Afterwards, 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)-palladium(0) is added to the reaction mixture, which is then mixed for 16 h under reflux. After cooling, the organic phase is separated, filtered over silica gel, washed three times with 200 mL water and then concentrated to dryness. The yield is 51 g (96 mmol), corresponding to 60% of the theory.

[0157] The following compounds can be prepared analogously:

TABLE-US-00005 Educt 1 Educt 2 Product Yield  1a [00413] [00414] [00415] 66%  2a [00416] [00417] [00418] 61%  3a [00419] [00420] [00421] 67%  4a [00422] [00423] [00424] 58%  5a [00425] [00426] [00427] 75%  6a [00428] [00429] [00430] 54%  7a [00431] [00432] [00433] 66%  8a [00434] [00435] [00436] 71%  9a [00437] [00438] [00439] 70% 10a [00440] [00441] [00442] 60% 11a [00443] [00444] [00445] 65% 12a [00446] [00447] [00448] 72% 13a [00449] [00450] [00451] 49% 14a [00452] [00453] [00454] 67% 15a [00455] [00456] [00457] 74% 16a [00458] [00459] [00460] 78% 17a [00461] [00462] [00463] 56% 18a [00464] [00465] [00466] 59% 19a [00467] [00468] [00469] 57% 20a [00470] [00471] [00472] 81% 21a [00473] [00474] [00475] 53% 22a [00476] [00477] [00478] 75% 23a [00479] [00480] [00481] 76% 24a [00482] [00483] [00484] 76% 25a [00485] [00486] [00487] 79% 26a [00488] [00489] [00490] 73% 27a [00491] [00492] [00493] 80% 28a [00494] [00495] [00496] 81% 29a [00497] [00498] [00499] 66% 30a [00500] [00501] [00502] 59% 31a [00503] [00504] [00505] 67% 32a [00506] [00507] [00508] 81% 33a [00509] [00510] [00511] 78% 34a [00512] [00513] [00514] 81% 35a [00515] [00516] [00517] 83% 36a [00518] [00519] [00520] 80% 37a [00521] [00522] [00523] 79% 38a [00524] [00525] [00526] 86% 39a [00527] [00528] [00529] 79% 40a [00530] [00531] [00532] 91% 41a [00533] [00534] [00535] 99% 42a [00536] [00537] [00538] 87% 43a [00539] [00540] [00541] 87% 44a [00542] [00543] [00544] 80% 45a [00545] [00546] [00547] 83% 46a [00548] [00549] [00550] 78% 47a [00551] [00552] [00553] 67%

[0158] b) Buchwald

##STR00554##

[0159] 20.4 g (50 mmol) of 9-phenyl-3,3′-bis-9H-carbazole and 16 g (54 mmol) of 3-bromo-2-phenyl-2λ.sup.4-2,1-benzothiazine-2-oxide are dissolved in 400 ml of toluene in an argon atmosphere. Then, 1.0 g (5 mmol) of tri-tert-butyl-phosphine is added to the reaction mixture, which is stirred in an argon atmosphere. Then, 0.6 g (2 mmol) of Pd(OAc)2 is added to the reaction mixture, which is stirred in an argon atmosphere, after which 9.5 g (99 mmol) of sodium-tert-butanolate are added to the mixture. The reaction mixture is stirred under reflux for 24 hours. After cooling, the organic phase is separated, washed three times with 200 ml water, dried over MgSO4, filtered and finally, the solvent is removed under vacuum. The residue is purified by column chromatography over silica gel (eluent: DCM/Heptane (1:3)). The residue is hot extracted with toluene and recrystallized from toluene/n-heptane and finally sublimated in high vacuum. The yield is 29 g (45 mmol), corresponding to 90% of the theory.

[0160] The following compounds can be produced analogously:

TABLE-US-00006 Educt 1 Educt 2 Product Yield  1b [00555] [00556] [00557] 71%  2b [00558] [00559] [00560] 82%  3b [00561] [00562] [00563] 67%  4b [00564] [00565] [00566] 73%  5b [00567] [00568] [00569] 65%  6b [00570] [00571] [00572] 85%  7b [00573] [00574] [00575] 81%  8b [00576] [00577] [00578] 77%  9b [00579] [00580] [00581] 69% 10b [00582] [00583] [00584] 84% 11b [00585] [00586] [00587] 83% 12b [00588] [00589] [00590] 83% 13b [00591] [00592] [00593] 85% 14b [00594] [00595] [00596] 76% 15b [00597] [00598] [00599] 84% 16b [00600] [00601] [00602] 73% 17b [00603] [00604] [00605] 72% 18b [00606] [00607] [00608] 70% 19b [00609] [00610] [00611] 73% 20b [00612] [00613] [00614] 66% 21b [00615] [00616] [00617] 69% 22b [00618] [00619] [00620] 72% 23b [00621] [00622] [00623] 79% 24b [00624] [00625] [00626] 77% 25b [00627] [00628] [00629] 70%

[0161] c) Bromination

##STR00630##

[0162] 65 g (190 mmol) of the compound with the CAS number [2132388-80-6] are suspended in 1800 mL of DMF. Then, 34 g (190 mmol) of NBS are added portion wise to this suspension, which is stirred for 2 hours in the dark. Water/ice is then added, the solid is separated and washed with ethanol. The isomers are separated by recrystallization. The yield is 57 g (134 mmol), corresponding to 72% of the theory.

[0163] The following compounds can be produced analogously:

TABLE-US-00007 Educt 1 Product Yield 1c [00631] [00632] 76% 2c [00633] [00634] 81%

B) DEVICE EXAMPLES

[0164] The use of the inventive materials in OLEDs is presented in the following examples.

[0165] Glass plates coated with structured ITO (indium tin oxide, 50 nm) are treated with an oxygen plasma followed by an argon plasma before coating. These plasma-treated glass plates form the substrates on which the OLEDs are applied.

[0166] In principle, the OLEDs have the following layer structure: substrate/optional interlayer (IL)/hole injection layer (HIL)/hole transport layer (HTL)/electron blocking layer (EBL)/emission layer (EML)/optional hole blocking layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by a 100 nm thick aluminium layer. The exact structure of the OLEDs is shown in Tables 1a to 1 c. The materials used for the OLED fabrication are listed in Table 2. The data of the OLEDs are listed in Tables 2a to 2c. The materials used for the fabrication of the OLEDs are listed in Table 3.

[0167] 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 IC1:EG1:TER1 (45%:45%:10%) here means that the material IC1 is present in the layer in a proportion by volume of 45%, EG1 is present in the layer in a proportion by volume of 45% and TER1 is present in the layer in a proportion by volume of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

[0168] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectra and the external quantum efficiency (EQE, measured in %) are determined as a function of luminance, calculated from current-voltage-luminance characteristics assuming a Lambertian radiation characteristic. The electroluminescence spectra are determined at a brightness of 1000 cd/m.sup.2 and the CIE 1931 x and y colour coordinates are determined. The value EQE 1000 corresponds to the external quantum efficiency at 1000 cd/m.sup.2.

[0169] In the examples E1 to E6, the inventive materials are used as matrix materials in the emission layer of green phosphorescent OLEDs.

TABLE-US-00008 TABLE 1a Structure of the OLEDs Ex. HIL HTL EBL EML HBL ETL EIL E1 HATCN SpMA1 SpMA2 IC1:21b:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (59%:29%:12%) 30 nm 10 nm (50%:50%) 30 nm 1 nm E2 HATCN SpMA1 SpMA2 IC1:30a:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (59%:29%:12%) 30 nm 10 nm (50%:50%) 30 nm 1 nm E3 HATCN SpMA1 SpMA2 IC1:47a:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (59%:29%:12%) 30 nm 10 nm (50%:50%) 30 nm 1 nm E4 HATCN SpMA1 SpMA2 IC1:a:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (59%:29%:12%) 30 nm 10 nm (50%:50%) 30 nm 1 nm E5 HATCN SpMA1 SpMA2 25b:IC2:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (44%:44%:12%) 30 nm 10 nm (50%:50%) 30 nm 1 nm E6 HATCN SpMA1 SpMA2 41a:IC2:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (29%:59%:12%) 30 nm 10 nm (50%:50%) 30 nm 1 nm

[0170] Very good results for the external quantum efficiency are obtained for all compounds according to the invention, at operating voltages U1000 in the range of 4V.

TABLE-US-00009 TABLE 2a Data of the OLEDs Ex. EQE 1000 (%) CIE x/y at 1000 cd/m.sup.2 E1 22 0.36/0.61 E2 21 0.35/0.61 E3 22 0.35/0.61 E4 20 0.35/0.61 E5 23 0.35/0.61 E6 20 0.36/0.61

[0171] Further inventive materials are used in the examples E7 and E9 as matrix material in the emission layer of red phosphorescent OLEDs.

TABLE-US-00010 TABLE 1b Structure of the OLEDs Ex. HIL HTL EBL EML HBL ETL EIL E7 HATCN SpMA1 SpMA2 b:TER5 ST2 ST2:LiQ LiQ 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm 1 nm E8 HATCN SpMA1 SpMA2 1b:TER5 ST2 ST2:LiQ LiQ 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm 1 nm E9 HATCN SpMA1 SpMA2 28a:TER5 ST2 ST2:LiQ LiQ 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm 1 nm

[0172] Very good results for the external quantum efficiency are obtained for the three compounds in accordance with the invention, at operating voltages U1000 in the range of 4-5 V.

TABLE-US-00011 TABLE 2b Data of the OLEDs Ex. EQE 1000 (%) CIE x/y at 1000 cd/m.sup.2 E7 22 0.67/0.33 E8 22 0.67/0.33 E9 19 0.67/0.33

[0173] Further inventive materials are used in the examples E10 and E11 as ETM (Electron -transport Material) in the ETL or as HBM (Hole-Blocking Material) in the HBL of blue fluorescent OLEDs. The inventive compounds can also be used as ETM and HBM in phosphorescent OLEDs.

TABLE-US-00012 TABLE 1c Structure of the OLEDs Bsp. HIL HTL EBL EML HBL ETL EIL E10 HATCN SpMA1 SpMA2 M2:SEB — 25b:LiQ LiQ 5 nm 195 nm 10 nm (95%:5%) 20 nm (50%:50%) 30 nm 1 nm E11 HATCN SpMA1 SpMA2 M2:SEB a ST2 LiQ 5 nm 195 nm 10 nm (95%:5%) 20 nm 10 nm 20 nm 3 nm

[0174] Very good results for the external quantum efficiency are obtained for the two compounds in accordance with the invention, at operating voltages U1000 in the range of 4-5 V.

TABLE-US-00013 TABLE 2c Data of the OLEDs Ex. EQE 1000 (%) CIE x/y bei 1000 cd/m.sup.2 E10 9 0.14/0.15 E11 9 0.14/0.15

TABLE-US-00014 TABLE 3 Structures of the materials for the fabrication of the OLEDs [00635] HATCN [00636] SpMA1 [00637] SpMA2 [00638] ST2 [00639] LiQ [00640] TEG1 [00641] TER5 [00642] SEB [00643] IC1 [00644] IC2 [00645] M2 [00646] 21b [00647] 30a [00648] 47a [00649] a [00650] 25b [00651] 41a [00652] b [00653] 1b [00654] 28a