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.-25. (canceled)

26. A compound of the formula (1), ##STR00253## where X.sup.1 stands, on each occurrence, identically or differently, for CR.sup.1 or N; X.sup.2 stands, on each occurrence, identically or differently, for CR.sup.2 or N; X.sup.A stands, on each occurrence, identically or differently, for CR.sup.A or N; Y is a single bond or a divalent bridge selected from —C(R.sup.Y).sub.2—, —C(R.sup.Y).sub.2—C(R.sup.Y).sub.2—, —O—, —S—, —S(═O).sub.2— and —C(═O)—; R.sup.B stands on each occurrence, identically or differently, for CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, N(R).sub.2, Si(R).sub.3,2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon 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, or an aromatic or heteroaromatic ring system 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, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms, which may be substituted by one or more R radicals; R.sup.Y stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, NO.sub.2, N(R).sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon 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, or an aromatic or heteroaromatic ring system 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, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms, which may be substituted by one or more R radicals; where two adjacent substituents R.sup.Y may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R′; R.sup.1, R.sup.2, R.sup.A stand on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, 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 cyclic alkyl, alkoxy or thioalkyl groups 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 system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms, which may be substituted by one or more R radicals; where two adjacent radicals selected from R.sup.1, R.sup.2, R.sup.A may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, 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, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, 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 cyclic alkyl, alkoxy or thioalkyl groups 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 system 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 radicals R may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, 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 24 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 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 C atoms.

27. The compound according to claim 26, wherein the compound is selected from compounds of formula (2), ##STR00254## where the symbols have the same meaning as in claim 26.

28. The compound according to claim 26, wherein the compound is selected from compounds of formula (3), ##STR00255## where the symbols have the same meaning as in claim 26.

29. The compound according to claim 26, wherein R.sup.B stands on each occurrence, identically or differently, for a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon 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, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms, which may be substituted by one or more R radicals.

30. The compound according to claim 26, wherein R.sup.B stands on each occurrence, identically or differently, for a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, each of which may be substituted by one or more radicals R, where one or more H atoms may be replaced by D, F, Cl or CN, or an aromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms, which may be substituted by one or more R radicals.

31. The compound according to claim 26, wherein R.sup.B is selected on each occurrence, identically or differently, from branched or cyclic alkyl groups represented by the general following formula (RS-a) ##STR00256## wherein R.sup.22, R.sup.23, R.sup.24 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.25, and where two of radicals R.sup.22, R.sup.23, R.sup.24 or all radicals R.sup.22, R.sup.23, R.sup.24 may be joined to form a (poly)cyclic alkyl group, which may be substituted by one or more radicals R.sup.25; R.sup.25 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms; with the proviso that at each occurrence at least one of radicals R.sup.22, R.sup.23 and R.sup.24 is other than H, with the proviso that at each occurrence all of radicals R.sup.22, R.sup.23 and R.sup.24 together have at least 4 carbon atoms and with the proviso that at each occurrence, if two of radicals R.sup.22, R.sup.23, R.sup.24 are H, the remaining radical is not a straight-chain; or from branched or cyclic alkoxy groups represented by the general following formula (RS-b) ##STR00257## wherein R.sup.26, R.sup.27, R.sup.28 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.25 as defined above, and where two of radicals R.sup.26, R.sup.27, R.sup.28 or all radicals R.sup.26, R.sup.27, R.sup.28 may be joined to form a (poly)cyclic alkyl group, which may be substituted by one or more radicals R.sup.25 as defined above; with the proviso that at each occurrence only one of radicals R.sup.26, R.sup.27 and R.sup.28 may be H; or from aralkyl groups represented by the general following formula (RS-c) ##STR00258## wherein R.sup.29, R.sup.30, R.sup.31 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32, and where two or all of radicals R.sup.29, R.sup.30, R.sup.31 may be joined to form a (poly)cyclic alkyl group or an aromatic ring system, each of which may be substituted by one or more radicals R.sup.32; R.sup.32 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms; with the proviso that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is other than H and that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is or contains an aromatic ring system having at least 6 aromatic ring atoms; or from aromatic ring systems represented by the general following formula (RS-d) ##STR00259## wherein R.sup.40 to R.sup.44 is at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32, and where two or more of radicals R.sup.40 to R.sup.44 may be joined to form a (poly)cyclic alkyl group or an aromatic ring system, each of which may be substituted by one or more radicals R.sup.32 as defined above.

32. The compound according to claim 26, wherein R.sup.2 and R.sup.A stand on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, N(Ar).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups 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 system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms, which may be substituted by one or more R radicals.

33. The compound according to claim 26 wherein R.sup.2 and R.sup.A stand on each occurrence, identically or differently, for H, D, F, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups 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, O or S and where one or more H atoms may be replaced by D, F, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms, which may be substituted by one or more R radicals.

34. The compound according to claim 26, wherein R.sup.2 and R.sup.A stand on each occurrence, identically or differently, for H, D, F, CN; or for a group of formula (RS-a), a group of formula (RS-b), a group of formula (RS-c) or a group of formula (RS-d), where the groups of formulae (RS-a), (RS-b), (RS-c) and (RS-d) have the same definition as in claim 31; or for a group of formula (ArL-1), ##STR00260## where the dashed bond in formula (ArL-1) indicates the bonding to the structure of formula (1), where Ar.sup.2, Ar.sup.3 stand on each occurrence, identically or differently, for 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; and where m is an integer selected from 1 to 10.

35. The compound according to claim 26, wherein the compound is selected from compounds of formula (4), ##STR00261## where the symbols have the same meaning as in claim 26.

36. The compound according to claim 31, wherein R.sup.B and R.sup.A are on each occurrence, identically or differently, selected from the groups of formulae (RS-a), (RS-b), (RS-c) and (RS-d), where the groups of formulae (RS-a), (RS-b), (RS-c) and (RS-d) have the same definition as in claim 31.

37. The compound according to claim 26, wherein the compound is selected from compounds of formula (5) or (6), ##STR00262## wherein the group R.sup.A has the same meaning as in claim 26, and wherein, in formula (5), R.sup.40, R.sup.42, R.sup.44 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32; R.sup.32 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms; with the proviso that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is other than H and that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is or contains an aromatic ring system having at least 6 aromatic ring atoms; or from aromatic ring systems represented by the general following formula (RS-d) ##STR00263## wherein R.sup.40 to R.sup.44 is at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32, and where two or more of radicals R.sup.40 to R.sup.44 may be joined to form a (poly)cyclic alkyl group or an aromatic ring system, each of which may be substituted by one or more radicals R.sup.32 as defined above; with the proviso that at least one of R.sup.40, R.sup.42, R.sup.44 is other than H; or ##STR00264## wherein, in formula (6), R.sup.41, R.sup.43 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32; with the proviso that at least one of R.sup.41, R.sup.43 is other than H.

38. Compound according to claim 37, wherein R.sup.42 is at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32; R.sup.40, R.sup.44 are at each occurrence, identically or differently, selected from an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32; R.sup.32 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms; with the proviso that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is other than H and that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is or contains an aromatic ring system having at least 6 aromatic ring atoms; or from aromatic ring systems represented by the general following formula (RS-d) ##STR00265##

39. The compound according to claim 26, wherein the compound is selected from the compounds of formulae (5-1), (5-2) and (5-3), ##STR00266## where the group R.sup.A has the same meaning as in claim 26, and where in each of formulae (5-1), (5-2) and (5-3) the phenyl groups indicated with —R.sup.32 are unsubstituted or substituted with one or more radicals R.sup.32; R.sup.42 and R.sup.44 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32; R.sup.32 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms; with the proviso that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is other than H and that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is or contains an aromatic ring system having at least 6 aromatic ring atoms; or from aromatic ring systems represented by the general following formula (RS-d) ##STR00267## wherein R.sup.40 to R.sup.44 is at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32, and where two or more of radicals R.sup.40 to R.sup.44 may be joined to form a (poly)cyclic alkyl group or an aromatic ring system, each of which may be substituted by one or more radicals R.sup.32 as defined above.

40. The compound according to claim 26, wherein the compound is selected from the compounds of formulae (5-1-1Y) to (5-3-Y7), ##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## where the groups R.sup.A, R.sup.Y and R have the same meaning as in claim 26, and where in each of formulae (5-1-Y1) to (5-3-Y7), the phenyl groups indicated with —R.sup.32 are unsubstituted or substituted with one or more radicals R.sup.32; R.sup.42 and R.sup.44 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32; R.sup.32 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms; with the proviso that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is other than H and that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is or contains an aromatic ring system having at least 6 aromatic ring atoms; or from aromatic ring systems represented by the general following formula (RS-d) ##STR00274## wherein R.sup.40 to R.sup.44 is at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32, and where two or more of radicals R.sup.40 to R.sup.44 may be joined to form a (poly)cyclic alkyl group or an aromatic ring system, each of which may be substituted by one or more radicals R.sup.32 as defined above.

41. The compound according to claim 37, wherein the groups R.sup.40, R.sup.42, R.sup.44 are at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, R.sup.32 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms; with the proviso that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is other than H and that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is or contains an aromatic ring system having at least 6 aromatic ring atoms; or from aromatic ring systems represented by the general following formula (RS-d) ##STR00275## wherein R.sup.40 to R.sup.44 is at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32, and where two or more of radicals R.sup.40 to R.sup.44 may be joined to form a (poly)cyclic alkyl group or an aromatic ring system, each of which may be substituted by one or more radicals R.sup.32 as defined above.

42. A process for the preparation of the compound according to claim 26, comprising the following steps: (i) cyclisation reaction of a triarylamine compound substituted by at least one boronic acid or ester group, in the presence of a halide compound, so that the boron atom of the boronic acid or ester group forms a six-membered ring with an adjacent aromatic or heteroaromatic group present in the triarylamine and where the boron atom is further substituted by a halogen; (ii) substitution reaction between the halogenated boron compound obtained in step (i) and a metal organyl reactant so that the halogen group on the boron atom is replaced by an organic group.

43. A polymer, oligomer or dendrimer containing one or more compounds according to claim 26, where the bond(s) to the polymer, oligomer or dendrimer may be localised at any positions in formula (1) which is substituted by R.sup.1, R.sup.2, R.sup.A, R.sup.B or R.

44. A formulation comprising at least one compound according to claim 26 and at least one solvent.

45. An Electronic device comprising at least one compound according to claim 26, 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-sensitized organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

46. An organic electroluminescent device comprising at least one compound according to claim 26, wherein the compound is employed as an emitter in an emitting layer.

47. The organic electroluminescent device according to claim 46, wherein the compound is employed as a fluorescent emitter in an emitting layer, wherein the emitting layer comprises at least one further component selected from matrix materials.

48. The organic electroluminescent device according to claim 46, wherein the compound is employed as an emitter showing Thermally Activated Delayed Fluorescence in an emitting layer, wherein the emitting layer comprises at least one further component selected from matrix materials.

49. The organic electroluminescent device according to claim 46, wherein the compound is employed as a fluorescent emitter in an emitting layer, wherein the emitting layer comprises at least one sensitizer selected from phosphorescent compounds and thermally activated delayed fluorescence compounds.

50. The organic electroluminescent device according to claim 49, wherein the emitting layer further comprises at least one organic functional material selected from matrix materials.

Description

A) SYNTHESES EXAMPLES

Example 1: Compound 1

[0197] Amine [1] [850264-79-8]

##STR00123##

[0198] Synthesized according to literature. Journal of Polymer Science Part A Polymer Chemistry Volume: 57 Issue 1 (2019) 70-76.

[0199] Bromide [2]

##STR00124##

[0200] A flask under Ar atmosphere is charged with amine [1] [850264-79-8] (5.0 g, 10.6 mmol, 1.0 equiv.), 1,3-dibromo-2-fluorobenzene [1435-54-7] (2.8 g, 10.6 mmol, 1.0 equiv.), potassium phosphate (4.5 g, 21.2 mmol, 2.0 equiv.) and N,N-dimethyl acetamide (250 mL). The mixture is refluxed for 2 h. The mixture is cooled to room temperature (rt). Water (250 mL) is added. The forming precipitate is collected. The desired product is isolated as white solid (7.0 g, 9.9 mmol, 94%).

[0201] Compound 1 [3]

##STR00125##

[0202] A flask under Ar atmosphere is charged with bromide [2] (500 mg, 0.7 mmol, 1.0 equiv.) and tert-butylbenzene (20 mL). The mixture is cooled down to −41° C. Then tert-butyllithium (1.7 M in pentane, 1.9 mL, 3.2 mmol, 4.5 equiv.) is added. The reaction mixture is allowed to warm to rt. Then the reaction mixture is heated to 100° C. for 1 h. The reaction mixture is cooled back to −41° C. and BBr.sub.3 (0.2 mL, 1.8 mmol, 2.5 equiv.) is added. The reaction mixture is allowed to warm to 0° C. The reaction mixture is stirred for 1 h at this temperature, before N,N-diisopropylethylamine (0.3 mL, 1.4 mmol, 2.4 equiv.) is added. The reaction mixture is refluxed for 16 h. Then the reaction mixture is cooled down to −78° C. and 2-Mesitylmagnesium bromide (700 mg, 3.0 mmol, 4.3 equiv.) is added. The resulting mixture is allowed to warm to rt. The solvent is removed, and the crude product is purified by column chromatography. The desired product is isolated as yellow solid (50 mg, 0.07 mmol, 10%).

Example 2: Compound 2

2-Bromo-1-fluoro-4-phenylbenzene [9]

[0203] ##STR00126##

[0204] A Schlenk flask was charged with 2-bromo-1-fluoro-4-iodobenzene (3.0 g, 10 mmol), phenyl boronic acid (1.3 g, 11 mmol), and sodium carbonate (2.1 g, 20 mmol) under argon. Toluene (9 ml), water (6 ml), ethanol (3 ml), Pd(OAc).sub.2 (23 mg, 0.1 mmol), and PPh.sub.3 (79 mg, 0.3 mmol) were added. It was heated to 50° C. for 1.5 h, to 60° C. for 18 h, and to 80° C. for 23 h. It was subjected to extractive work-up with water/dichloromethane. The residue was passed through silica with n-hexane. Yield: 2.44 g (97%).

9-(2-Bromo-4-phenylphenyl)-3,6-bis(4-phenylphenyl)carbazole [10]

[0205] ##STR00127##

[0206] A Schlenk flask was charged with [1] (3.6 g, 7.5 mmol), [9] (1.9 g, 7.6 mmol), and K.sub.3PO.sub.4 (3.2 g, 15 mmol) under argon. Dimethylacetamide (75 ml) was added, and it was heated to reflux for 18 h. More [9] (˜200 mg) was added and refluxing was continued for 2 h. It was diluted with water and the precipitated solid filtered off and washed with water. It was dried under air and washed with methanol and dichloromethane. The filtrate was evaporated and the residue was subjected to column chromatography (SiO.sub.2, dichloromethane/n-hexane 1:2). Yield: 2.3 g (43%).

3,6-bis(4-phenylphenyl)-9-[4-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole [11]

[0207] ##STR00128##

[0208] [10] (774 mg, 1.1 mmol), B.sub.2pin.sub.2 (559 mg, 2.2 mmol), and CsF (501 mg, 3.3 mmol) were dissolved in dry THF (8 ml) under argon. PdCl.sub.2(PCy.sub.3).sub.2 (41 mg, 0.06 mmol) was added and it was heated to reflux for 2 h. The solvent was evaporated, the residue stirred with dichloromethane, and it was filtered. The filtrate was evaporated, and the residue was subjected to column chromatography (SiO.sub.2, n-hexane/ethyl acetate 10:1). Yield: 829 mg (100%)

2-bromo-1,3,5-triphenylbenzene [12]

[0209] ##STR00129##

[0210] Bromine (3.2 g, 20 mmol) was slowly added to a stirred suspension of 1,3,5-triphenylbenzene (5.1 g, 17 mmol) in dichloromethane (30 ml) and acetic acid (6 ml). It was stirred at 40° C. for 16 h. Water (30 ml) was added and excess bromine was quenched with solid Na.sub.2SO.sub.3. It was alkalised with 25% NHaaq and layers were separated. The organic layer was washed with 0.1 M NHaaq, dried with MgSO.sub.4 and evaporated. The residue was recrystallized from tBuOMe and ethanol. The precipitated solid was filtered off and washed with ethanol. Yield: 5.97 g (93%).

[0211] Compound 2 [13]

##STR00130##

[0212] A Schlenk tube was charged with [11] (420 mg, 0.56 mmol) and AlCl.sub.3 (373 mg, 2.8 mmol) under argon. Dry toluene (3 ml) and DIPEA were added and it was heated to 100° C. for 2 h. The solvent was removed in vacuo and THF (3 ml) was added. A solution of lithiated [12] (10 mmol in diethyl ether) was added dropwise at −72° C.

[0213] The cooling was removed, and it was stirred at room temperature overnight. The solvent was removed in vacuo and it was filtered through silica with dichloromethane. The residue was subjected to column chromatography (SiO.sub.2, dichloromethane/n-hexane, gradient). Yield: 35 mg (6.7%)

[0214] Compound 3 [14]

##STR00131##

[0215] [14] was synthesized in analogy to [13] using lithiated 2-bromo-1,3,5-trimethylbenzene and [11] as starting materials.

[0216] Further structures can be synthesized using the following synthetic route:

##STR00132##

[0217] Compounds [4] are either commercially available or can be synthesized in Suzuki cross-coupling reactions using Pd(PPh.sub.3).sub.4 in analogy to CN107721979A.

TABLE-US-00001 Ar.sub.1—B(OH).sub.2 Compound [4] [00133] CAS: 694-80-4 [00134] [00135] CAS: 98-80-6 [00136] [00137] CAS: 5122-94-1 [00138] [00139] CAS: 5720-05-8 [00140] [00141] CAS: 5980-97-2

[0218] Compounds [6] are either commercially available or can be synthesized in Suzuki cross-coupling reactions in analogy to Amine [1].

TABLE-US-00002 Compound [5] Ar.sub.2—B(OH).sub.2 Compound [6] [00142] CAS: 86-74-8 [00143] [00144] [00145] CAS: 6825-20-3 CAS: 98-80-6 [00146] [00147] [00148] CAS: 6825-20-3 CAS: 5122-94-1 Amine [1] [00149] [00150] [00151] CAS: 6825-20-3 CAS: 5980-97-2 [00152] [00153] [00154] CAS: 6825-20-3 CAS: 4688-76-0 [00155] CAS: 194-59-2 [00156] CAS: 135-67-1 [00157] [00158] [00159] CAS: 832734-16-4 CAS: 5122-94-1 [00160] CAS: 578-95-0 [00161] CAS: 1209-66-1 [00162] CAS: 29875-73-8 [00163] CAS: 6267-02-3 [00164] CAS: 92638-81-8

[0219] Compounds [7] can be synthesized in Ullmann cross-coupling reactions in analogy to WO2016195441A1.

TABLE-US-00003 Compound [4] Compound [6] Compound [7] [00165] [00166] [00167] [00168] [00169] [00170] [00171] [00172] [00173] [00174] [00175] [00176] [00177] [00178] [00179] [00180] [00181] [00182] [00183] [00184] [00185] [00186] [00187] [00188] CAS: 194-59-2 [00189] [00190] [00191] CAS: 135-67-1 [00192] [00193] [00194] [00195] [00196] [00197] CAS: 578-95-0 [00198] [00199] [00200] CAS: 1209-66-1 [00201] [00202] [00203] CAS: 29875-73-8 [00204] [00205] [00206] CAS: 6267-02-3 [00207] [00208] [00209] CAS: 92638-81-8

[0220] Compounds [8] can be synthesized in analogy to compound 1 [3].

TABLE-US-00004 Compound [7] Ar.sub.3—M Compound [8] [00210] [00211] [00212] M = MgBr, CAS: 2633-66-1 [00213] [00214] [00215] M = MgBr, CAS: 36719-77-4 [00216] [00217] [00218] M = MgBr, CAS: 2633-66-1 [00219] [00220] [00221] M = MgBr, CAS: 2633-66-1 [00222] [00223] [00224] M = MgBr, CAS: 36719-77-4 [00225] [00226] [00227] M = MgBr, CAS: 2633-66-1 [00228] [00229] [00230] M = MgBr, CAS: 2633-66-1 [00231] [00232] [00233] M = MgBr, CAS: 36719-77-4 [00234] [00235] [00236] M = MgBr, CAS: 36719-77-4 [00237] [00238] [00239] M = MgBr, CAS: 2633-66-1 [00240] [00241] [00242] M = MgBr, CAS: 36719-77-4 [00243] [00244] [00245] M = MgBr, CAS: 36719-77-4 [00246] [00247] [00248] M = MgBr, CAS: 36719-77-4 [00249] [00250] [00251] M = MgBr, CAS: 36719-77-4

B) Fabrication of OLEDs

[0221] The compounds of the present invention can be used as triplet matrix material in the light emitting layer of an OLED or as fluorescent emitter in the light emitting layer of an OLED.

Determination of peak emission wavelength X.sub.max

[0222] To determine the peak emission wavelength of the fluorescent emitter, the fluorescent emitter is dissolved in toluene. A concentration of 1 mg/100 mL is used. The solution is excited in a fluorescence spectrometer Hitachi F4500 with a to the material matching wavelength. The measurement is carried out at room temperature. The peak emission wavelength λ.sub.max is the wavelength of the first maximum of the emission spectrum (FIG. 1). Typically, the first maximum is also the global maximum of the spectrum.

[0223] The peak emission wavelength λ.sub.max of the compounds [8] depicted above is in the range of 400 nm to 500 nm.

Determination of the spectral broadness (full width at half maximum (FWHM))

[0224] To determine the spectral broadness of the fluorescent emitter, the values for the wavelengths (X1, X2) (see FIG. 1) which are at half the maximum of the peak emission wavelength (y=0.5) are subtracted. The full width at half maximum is calculated according to formula (1):

FWHM=X2−X1  (1)

[0225] According to the described methods the following properties for the fluorescent emitters are obtained and depicted in the following table:

TABLE-US-00005 Material λ.sub.max FWHM [nm] CIE-y Ex-1-3-2 478 37 0.19  Compound 1 442 31 0.045 Compound 2 456 30 0.070 Compound 3 451 33 0.061

[0226] Properties of Ex-1-3-2 as depicted below are shown in WO18047639A1 from JNC. Inventive Compounds 1-3 show a narrower spectrum and have thus a higher colour purity.

[0227] Chemical structure of Ex-1-3-2 from WO18047639A1:

##STR00252##