INDOLO[3.2.1-JK]CARBAZOLE-6-CARBONITRILE DERIVATIVES AS BLUE FLUORESCENT EMITTERS FOR USE IN OLEDS

Abstract

The present invention relates to aromatic compounds suitable for use in electronic devices, and to electronic devices, especially organic electroluminescent devices, comprising these compounds.

Claims

1.-21. (canceled)

22. A compound comprising at least one structure of the formula (I), ##STR01172## where the symbols and indices used are as follows: X is the same or different at each instance and is N, CCN, CYR.sup.y or CR.sup.b; Y is the same or different at each instance and is CO, P(?O)R.sup.a, SO, SO.sub.2, C(O)O, C(S)O, C(O)S, C(?O)NR.sup.a, C(?O)NAr; R is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar).sub.2, N(R.sup.e).sub.2, C(?O)N(Ar).sub.2, C(?O)N(R.sup.e).sub.2, C(Ar).sub.3, C(R.sup.e).sub.3, Si(Ar).sub.3, Si(R.sup.e).sub.3, B(Ar).sub.2, B(R.sup.e).sub.2, C(?O)Ar, C(?O)R.sup.e, P(?O)(Ar).sub.2, P(?O)(R.sup.e).sub.2, P(Ar).sub.2, P(R.sup.e).sub.2, S(?O)Ar, S(?O)R.sup.e, S(?O).sub.2Ar, S(?O).sub.2R.sup.e, OSO.sub.2Ar, OSO.sub.2R.sup.e, 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 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may each be substituted by one or more R.sup.e radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.eC?CR.sup.e, C?C, Si(R.sup.e).sub.2, C?O, C?S, C?Se, C?NR.sup.e, C(?O)O, C(?O)N.sup.e, NR.sup.e, P(?O)(R.sup.e), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.e radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.e radicals, or an arylthio or heteroarylthio group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.e radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.e radicals, or an arylalkyl or heteroarylalkyl group which has 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl radical and may be substituted by one or more R.sup.e radicals; at the same time, any R radical may form a ring system with a further group; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.e radicals; at the same time, it is possible for two Ar radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R.sup.e), C(R.sup.e).sub.2, Si(R.sup.e).sub.2, C?O, C?NR.sup.e, C?C(R.sup.e).sub.2, O, S, S?O, SO.sub.2, N(R.sup.e), P(R.sup.e) and P(?O)R.sup.e; R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar).sub.2, N(R.sup.1).sub.2, C(?O)N(Ar).sub.2, C(?O)N(R.sup.1).sub.2, C(Ar).sub.3, C(R.sup.1).sub.3, Si(Ar).sub.3, Si(R.sup.1).sub.3, B(Ar).sub.2, B(R.sup.1).sub.2, C(?O)Ar, C(?O)R.sup.1, P(?O)(Ar).sub.2, P(?O)(R.sup.1).sub.2, P(Ar).sub.2, P(R.sup.1).sub.2, S(?O)Ar, S(?O)R.sup.1, S(?O).sub.2Ar, S(?O).sub.2R.sup.1, OSO.sub.2Ar, OSO.sub.2R.sup.1, 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 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be substituted in each case by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C?CR.sup.1, C?C, Si(R.sup.1).sub.2, C?O, C?S, C?Se, C?NR.sup.1, C(?O)O, C(?O)NR.sup.1, NR.sup.1, P(?O)(R.sup.1), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, two R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals may also form a ring system together or with a further group; R.sup.y is the same or different at each instance and is C(Ar).sub.3, C(R.sup.1).sub.3, Si(Ar).sub.3, Si(R.sup.1).sub.3, N(Ar).sub.2, N(R.sup.1).sub.2, 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 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be substituted in each case by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C?CR.sup.1, C?C, Si(R.sup.1).sub.2, C?O, C?S, C?Se, C?NR.sup.1, C(?O)O, C(?O)NR.sup.1, NR.sup.1, P(?O)(R.sup.1), O, S, SO or SO.sub.2, where any CH.sub.2 group bonded to the Y radical may not be replaced by C?O, C?S, C?Se, C?NR.sup.1, C(?O)O, C(?O)NR.sup.1, P(?O)(R.sup.1), SO or SO.sub.2, where any CH.sub.2 group bonded to the Y radical may optionally not be replaced by Si(R.sup.1).sub.2, C?O, C?S, C?Se, C?NR.sup.1, C(?O)O, C(?O)NR.sup.1, NR.sup.1, P(?O)(R.sup.1), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals; at the same time, two R.sup.y radicals may also form a ring system with one another, or one R.sup.y radical together with one R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radical; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, it is possible for two Ar radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R.sup.1), C(R.sup.1).sub.2, Si(R.sup.1).sub.2, C?O, C?NR.sup.1, C?C(R.sup.1).sub.2, O, S, S?O, SO.sub.2, N(R.sup.1), P(R.sup.1) and P(?O)R.sup.1; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar).sub.2, N(R.sup.2).sub.2, C(?O)Ar, C(?O)R.sup.2, P(?O)(Ar).sub.2, P(Ar).sub.2, B(Ar).sub.2, B(R.sup.2).sub.2, C(Ar).sub.3, C(R.sup.2).sub.3, Si(Ar).sub.3, Si(R.sup.2).sub.3, 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 or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2C?CR.sup.2, C?C, Si(R.sup.2).sub.2, C?O, C?S, C?Se, 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 where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two or more, R.sup.1 radicals together may form a ring system; at the same time, one or more R.sup.1 radicals may form a ring system with a further part of the compound; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, it is possible for two Ar radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R.sup.2), C(R.sup.2).sub.2, Si(R.sup.2).sub.2, C?O, C?NR.sup.2, C?C(R.sup.2).sub.2, O, S, S?O, SO.sub.2, N(R.sup.2), P(R.sup.2) and P(?O)R.sup.2; R.sup.2 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more, substituents R.sup.2 together may form a ring system.

23. The compound according to claim 22, wherein at least one of the R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals are not H.

24. The compound according to claim 22, wherein at least one of the R.sup.a, R radicals are 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 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be substituted in each case by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C?CR.sup.1, C?C, Si(R.sup.1).sub.2, C?O, C?S, C?Se, C?NR.sup.1, C(?O)O, C(?O)NR.sup.1, NR.sup.1, P(?O)(R.sup.1), O, S, SO or SO.sub.2.

25. The compound according to claim 22, wherein the R radical is an aromatic or heteroaromatic ring system which has 5 to 13 aromatic ring atoms and may be substituted by one or more R.sup.e radicals.

26. The compound according to claim 22, wherein two R.sup.a radicals together with the further groups to which the two R.sup.a radicals bind form a fused ring, an aliphatic or heteroaliphatic ring having 3 to 20 ring atoms or an aromatic or heteroaromatic ring having 5 to 13 ring atoms.

27. The compound according to claim 22, wherein two R.sup.c radicals together with the further groups to which the two R.sup.c radicals bind form a fused ring, an aliphatic or heteroaliphatic ring having 3 to 20 ring atoms or an aromatic or heteroaromatic ring having 5 to 13 ring atoms.

28. The compound according to claim 22, comprising at least one structure of the formulae (I-1) to (I-83), ##STR01173## ##STR01174## ##STR01175## ##STR01176## ##STR01177## ##STR01178## ##STR01179## ##STR01180## ##STR01181## ##STR01182## ##STR01183## ##STR01184## ##STR01185## ##STR01186## ##STR01187## ##STR01188## ##STR01189## ##STR01190## ##STR01191## ##STR01192## ##STR01193## ##STR01194## ##STR01195## ##STR01196## where the symbols R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e and R.sup.y have the definitions given in claim 22 and the further symbols and indices used are as follows: X.sup.1 is the same or different at each instance and is N or CR.sup.e, with the proviso that not more than two of the X.sup.1 groups in one cycle are N; Y.sup.1 is the same or different at each instance and is C(R.sup.e).sub.2, (R.sup.e).sub.2CC(R.sup.e).sub.2, (R.sup.e)C?C(R.sup.e), NR.sup.e, NAr, O, S, SO, SO.sub.2, Se, P(O)R.sup.e, BR.sup.e or Si(R.sup.e).sub.2; T.sup.1 is the same or different at each instance and is a fused ring, an aliphatic or heteroaliphatic ring having 3 to 20, or an aromatic or heteroaromatic ring having 5 to 13 ring atoms, which may be substituted by one or more R.sup.1 radicals, where R.sup.1 has the definition given in claim 22; n is 0, 1, 2 or 3; and m is 0, 1, 2, 3 or 4.

29. The compound according to claim 22, wherein at least two R, R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e, R.sup.y radicals together with the further groups to which the two R, R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e, R.sup.y radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e, R.sup.y radicals form at least one structure of the following formulae (Cy-1) to (Cy-10), ##STR01197## where R.sup.1 and R.sup.2 have the definitions given in claim 22, the dotted bonds represent the sites of attachment to the atoms of the groups to which the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.y radicals bind, and in addition: Z.sup.1, Z.sup.3 is the same or different at each instance and is C(R.sup.3).sub.2, O, S, NR.sup.3 or C(?O); Z.sup.2 is C(R.sup.1).sub.2, O, S, NR.sup.1 or C(?O), where two adjacent groups Z.sup.2 represent CR.sup.1?CR.sup.1 or an ortho-bonded arylene or heteroarylene group having 5 to 14 aromatic ring atoms which may be substituted by one or more R.sup.1 radicals; G is an alkylene group which has 1, 2 or 3 carbon atoms and may be substituted by one or more R.sup.1 radicals, CR.sup.l?CR.sup.1 or an ortho-bonded arylene or heteroarylene group which has 5 to 14 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar).sub.2, N(R.sup.2).sub.2, C(?O)Ar, C(?O)R.sup.2, P(?O)(Ar).sub.2, P(Ar).sub.2, B(Ar).sub.2, B(R.sup.2).sub.2, C(Ar).sub.3, C(R.sup.2).sub.3, Si(Ar).sub.3, Si(R.sup.2).sub.3, 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 or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2C?CR.sup.2, C?C, Si(R.sup.2).sub.2, C?O, C?S, C?Se, 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 where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two R.sup.3 radicals which are bonded to the same carbon atom together may form an aliphatic or aromatic ring system and thus span a spiro system; in addition, R.sup.3 may form a ring system with an R, R.sup.a, R.sup.e, R.sup.d, R.sup.e or R.sup.1 radical; with the proviso that no two heteroatoms in these groups are bonded directly to one another and no two C?O groups are bonded directly to one another.

30. The compound according to claim 22, wherein at least two R, R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e, R.sup.y radicals together with the further groups to which the two R, R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e, R.sup.y radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e, R.sup.y radicals form at least one structure of the formulae (RA-1) to (RA-13) ##STR01198## ##STR01199## where R.sup.1 has the definition set out above, the dotted bonds represent the sites of attachment to the atoms of the groups to which the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.y radicals bind, and the further symbols have the following definition: Y.sup.2 is the same or different at each instance and is C(R.sup.1).sub.2, (R.sup.1).sub.2CC(R.sup.1).sub.2, (R.sup.1)C?C(R.sup.1), NR.sup.1, NAr, O or S; R.sup.f is the same or different at each instance and is F, 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 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2C?CR.sup.2, C?C, Si(R.sup.2).sub.2, C?O, C?S, C?Se, C?NR.sup.2, C(?O)O, C(?O)NR.sup.2, NR.sup.2, P(?O)(R.sup.1), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, two R.sup.f radicals together or one R.sup.f radical together with an R.sup.1 radical or with a further group may form a ring system; r is 0, 1, 2, 3 or 4; s is 0, 1, 2, 3, 4, 5 or 6; t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; and v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

31. The compound according to claim 22, wherein at least two R, R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e, R.sup.y radicals together with the further groups to which the two R, R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e, R.sup.y radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e, R.sup.y radicals form the structures of the formulae (RB) ##STR01200## where R.sup.1 has the definition set out in claim 22, the dotted bonds represent the bonding sites via which the two R, R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e, R.sup.y radicals bind, the index m is 0, 1, 2, 3 or 4, and Y.sup.3 is C(R.sup.1).sub.2, NR.sup.1, NAr, BR.sup.1, BAr, O or S.

32. The compound according to claim 22, wherein R or Ar is the same or different at each instance and is selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which may be substituted by one or more R.sup.e radicals.

33. The compound according to claim 22, wherein the compound is symmetric in relation to the R.sup.a and R.sup.e radicals.

34. The compound according to claim 22, wherein the R.sup.e and/or R.sup.d radical represents, comprises, or forms together with an R.sup.d or R.sup.e radical, at least one group selected from C(Ar).sub.3, C(R.sup.1).sub.3, Si(Ar).sub.3, Si(R.sup.1).sub.3, B(R.sup.1).sub.2 that may be substituted by one or more R.sup.1 radicals.

35. The compound according to claim 28, wherein the compound comprises exactly two or exactly three structures of formula (I) and/or (I-1) to (I-81).

36. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 22, wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

37. A formulation comprising at least one compound according to claim 22 and at least one further compound.

38. A formulation comprising the oligomer, polymer or dendrimer according to claim 36 and at least one further compound.

39. A composition comprising at least one compound according to claim 22 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF, host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

40. A composition comprising the oligomer, polymer or dendrimer according to claim 36 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF, host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

41. The composition according to claim 39, wherein the at least one further compound is a TADF host material and/or at least one further compound is a phosphorescent emitter (triplet emitter).

42. A process for preparing the compound according to claim 22, which comprises synthesizing a base skeleton having an aromatic amino group and at least one aromatic or heteroaromatic radical is introduced.

43. An electronic device comprising at least one compound according to claim 22.

44. An electronic device comprising the oligomer, polymer or dendrimer according to claim 36.

Description

FIGURE

[0237] FIG. 1 shows the photoluminescence spectra (PL spectra) of compounds ES1, ES94 and 675, measured with a Hitachi F-4500 PL spectrometer in about 10.sup.?5 molar degassed toluene solution at room temperature (about 25? C.).

[0238] These abovementioned advantages are not accompanied by an inordinately high deterioration in the further electronic properties.

[0239] It should be pointed out that variations of the embodiments described in the present invention are covered by the scope of this invention. Any feature disclosed in the present invention may, unless this is explicitly ruled out, be exchanged for alternative features which serve the same purpose or an equivalent or similar purpose. Thus, any feature disclosed in the present invention, unless stated otherwise, should be considered as an example of a generic series or as an equivalent or similar feature.

[0240] All features of the present invention may be combined with one another in any manner, unless particular features and/or stages are mutually exclusive. This is especially true of preferred features of the present invention. Equally, features of non-essential combinations may be used separately (and not in combination).

[0241] It should also be pointed out that many of the features, and especially those of the preferred embodiments of the present invention, should themselves be regarded as inventive and not merely as some of the embodiments of the present invention. For these features, independent protection may be sought in addition to or as an alternative to any currently claimed invention.

[0242] The technical teaching disclosed with the present invention may be abstracted and combined with other examples.

[0243] The invention is illustrated in more detail by the examples which follow, without any intention of restricting it thereby. The person skilled in the art will be able to use the information given to execute the invention over the entire scope disclosed and to prepare further compounds of the invention without exercising inventive skill and to use them in electronic devices or to employ the process of the invention.

EXAMPLES

[0244] 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. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature. In the case of compounds that can show multiple configurational isomers, enantiomers, diastereomers or tautomeric forms, one form is shown in a representative manner.

1) Preparation of the Synthons

1.1) Nitriles: Example S1

[0245] ##STR00722##

[0246] S1 can be prepared in 69% yield by the above route, according to the following literature: [0247] Stages 1 and 2: W. S. Tan et al., J. Chin. Chem. Soc., 2012, 59, 399. [0248] Stage 3: J. M. Herbert et al., J. Label. Compd. Radiopharm., 2007, 50, 440.

[0249] Purification is effected by flash chromatography using an automated column system (Combi-Flash Torrent, from Axel Semrau).

[0250] The following synthons can be prepared analogously:

TABLE-US-00011 Ex. Reactant Product Yield S2 [00723] [00724] 85% S3 [00725] [00726] 83% S4 [00727] [00728] 64%

[0251] Alternative Mode of Preparation:

[0252] Alternatively, S1 to S4 can be prepared in improved yield by the following route:

##STR00729## [0253] Stages 1 and 3: Analogously to W. S. Tan et al., J. Chin. Chem. Soc., 2012, 59, 399. Stage 1 yield ?95%; stage 3 yield quantitative. [0254] Stage 2: Iodination with N-iodosuccinimide in trifluoroethanol (TFE) or hexafluoroisopropanol analogously to R.-J. Tang et al. J. Org. Chem., 2018, 83, 930. Yield 93%.

Example S1b

[0255] ##STR00730##

[0256] Analogously, the corresponding bromo triflates can be obtained by using N-bromosuccinimide. Yield over 3 stages 87%.

Example S1c

[0257] ##STR00731##

[0258] Analogously, the corresponding chloro triflates can be obtained by using N-chlorosuccinimide. Yield over 3 stages 69%.

Example S1d

[0259] ##STR00732##

[0260] Analogously, the corresponding fluoro triflates can be obtained by fluorination in stage 2 analogously to R. D. Chambers et al., J. Fluor. Chem., 2000, 102, 169. Yield over 3 stages 30%.

Example S1e

[0261] ##STR00733##

[0262] I-F exchange analogously to C. S. Hartley et al., Chem. Mater. 2004, 16, 5297. Yield 28%.

[0263] Alternatively, stage S1e can be prepared as follows:

##STR00734## [0264] Stage 1: Analogously to M. A. Zolfigol et al., Molecules 2001, 6, 614. Yield: 93%. [0265] Stage 2: G. Ralf et al. Journal fuer Praktische Chemie 1987, 329(6), 945. Yield 89%. [0266] Stage 3: Analogously to J. H. Clark et al., Chem. & Ind. 1991, 436. Yield: 38%.

Optimized Synthesis of S1e

Stage 1

[0267] To a solution, cooled to 0? C., of 29.5 g (100 mmol) of 1-cyano-4-hydroxytriptycene is added dropwise a mixture of 19.0 g of 65% by weight nitric acid and 20.0 g of 96% by weight nitric acid over the course of 1 h. The mixture is stirred for a further 30 min and then poured cautiously (foaming!) with very good stirring onto a mixture of 37.8 g (450 mmol) of sodium hydrogencarbonate and 3 l of ice-water. The organic phase is separated off, the aqueous phase is extracted three times with 200 ml each time of DCM, and the combined organic phases are dried with saturated sodium chloride solution and over magnesium sulfate. The desiccant is filtered off, the DCM is removed under reduced pressure and the residue is chromatographed (silica gel, n-heptane/EA 5:1). Yield: 31.5 g (93 mmol), 93%; purity: about 98% by .sup.1H NMR.

Stage 2

[0268] To a well-stirred mixture of 34.0 g (100 mmol) of 1-cyano-3-nitro-4-hydroxytriptycene and 93.5 ml (1 mol) of phosphoryl chloride is added 21.0 ml (120 mmol) of diisopropylethylamine (DIPEA), and the mixture is stirred under reflux for 4 h. The reaction mixture is poured gradually (exothermic, induction period!) onto 2 l of ice-water with very good stirring and stirred for a further 30 min. The aqueous phase is extracted five times with 200 ml each time of DCM, and the combined organic phases are dried with saturated sodium chloride solution and over magnesium sulfate. The desiccant is filtered off, the DCM is removed under reduced pressure and the residue is chromatographed (silica gel, n-heptane/EA 5:1). Yield: 40.1 g (89 mmol), 89%; purity: about 97% by .sup.1H NMR.

Stage 3

[0269] Analogously to J. H. Clark et al., Chem. & Ind. 1991, 436. Yield: 38%.

[0270] Alternatively, stage S1e can be prepared in improved yield as follows:

##STR00735## [0271] Stage 1: Analogously to S. Chandrappa et al., Synlett 2010, 3019. Yield: 87%. [0272] Stage 2: D. J. Milner et al., Synth. Commun., 1992, 22(1), 73. Yield: 77%.

[0273] Optimized Synthesis of S1e:

Stage 1

[0274] To a well-stirred suspension of 35.9 g (100 mmol) of 1-cyano-3-nitro-4-chlorotriptycene and 25.1 g (450 mmol) of iron powder in 700 ml EtOH is added dropwise, under reflux over 30 minutes, 75.0 ml of 37% by weight aqueous hydrochloric acid (caution: evolution of hydrogen!). The mixture is stirred at reflux for another 3 h, allowed to cool, diluted with 2 l of water and 2 l of DCM, and alkalized with cautious addition (foaming!) of solid sodium carbonate (pH ?9). The mixture is filtered with suction through Celite, the organic phase of the filtrate is separated off, the aqueous phase is extracted five times with 100 ml each time of DCM, and the combined organic phases are dried by washing twice with 300 ml each time of saturated sodium chloride solution and over magnesium sulfate. The desiccant is filtered off, the DCM is removed under reduced pressure, and the crude product is applied to Isolute and chromatographed (silica gel, n-heptane/DCM 1:1>1:2). Another chromatography step is performed if necessary until the product is obtained in white to pale beige form. Yield: 3-28.5 g (87 mmol), 87%; purity: about 98% by .sup.1H NMR.

Stage 2

[0275] To a well-stirred solution, cooled to 0? C., of 12.9 g (110 mmol) of nitrosyl tetrafluoroborate [NO][BF.sub.4] in 500 ml of DCM is added 32.9 g (100 mmol) of 1-cyano-3-amino-4-chlorotriptycene in portions over the course of 10 min. The mixture is stirred for a further 30 min, and the diazonium salt is filtered off, washed once with 100 ml of DCM/n-heptane (1:2, vv) and once with 100 ml of n-heptane and dried briefly under reduced pressure at RT. Yield: 40.6 g (97%).

[0276] The diazonium salt thus obtained is quenched in a rotating flask in a gentle argon stream at 220-230? C. until the evolution of nitrogen has ended (about 1 h). The cooled residue is extracted with 500 ml of DCM. The insoluble fractions are filtered off, the filtrate is concentrated to dryness and the residue is chromatographed (silica gel, n-heptane/DCM 2:1). Yield: 25.4 g (77 mmol); purity: about 98% by .sup.1H NMR.

[0277] The following synthons can be prepared analogously: Yield over 4 or 5 stages

TABLE-US-00012 Ex. Reactant Product Yield S2e [00736] [00737] 42% S3e [00738] [00739] 44% S4e [00740] [00741] 35%

Example S10

[0278] ##STR00742##

[0279] Procedure analogous to W. S. Tan et al., J. Chin. Chem. Soc., 2012, 59, 399. Rather than DMF, dimethylacetamide (DMAC) is used, which leads to improved yields. Yield: 66%.

[0280] Analogously to S1 (alternative mode of preparation) and S10, it is possible to prepare the following synthons:

TABLE-US-00013 Ex. Reactant Product Yield S10b S1b [00743] 68% S11 S2 [00744] 57% S12 S3 [00745] 64% S13 S4 [00746] 57% S14 [00747] [00748] 48% S15 [00749] [00750] 49% S16 [00751] [00752] 50% S17 [00753] [00754] 43%

1.2) Bicyclic Ketones

Example S50

[0281] ##STR00755##

A) Via Grignard Route

[0282] ##STR00756##

[0283] S50 can be prepared in 34% yield by the abovementioned Grignard route proceeding from the abovementioned reactants, according to the following literature: [0284] Stages 1-4: B. M. Fox et al., J. Med. Chem., 2014, 52, 3464. [0285] Stage 5: 1. Dragutan et al., Org. Prep. Proced., Int., 1975, 7, 2, 75.

[0286] The purification, especially the removal of regioisomers from the cyclization in stage 5, is effected via flash chromatography on an automated column system (Combi-Flash Torrent, from Axel Semrau).

B) Via Suzuki Route

[0287] ##STR00757##

[0288] S50 can also be prepared in 41% yield by the abovementioned Suzuki route proceeding from the abovementioned reactants, according to the following literature: [0289] Stages 1 to 3: C. Dolente et al., WO 2011/120877 [0290] Stage 4: 1. Dragutan et al., Org. Prep. Proced., Int., 1975, 7, 2, 75.

[0291] The purification, especially the removal of regioisomers from the cyclization in stage 4, is effected via flash chromatography on an automated column system (Combi-Flash Torrent, from Axel Semrau).

Example S51

[0292] ##STR00758##

C) Via Friedel-Crafts Alkylation and Acylation

[0293] ##STR00759##

[0294] S51 can be prepared in 28% yield by the abovementioned Friedel-Crafts route, according to the following literature data, except using 2-chloroanisole rather than anisole: [0295] Stage 1: Ismailov, A. G. et al, Nauch. Tr. Azerb. Un-t. Ser. Khim. N, 1979, (4), 47. [0296] Stage 2: Ismailov, A. G. et al., Zhurnal Organicheskoi Khimii, 1978, 14(4), 811. [0297] Stages 3 and 4: M. L. Maddess et al., Org. Process Res. Dev. 2014, 18, 528-538.

[0298] The purification, especially the removal of regioisomers from the cyclization in stage 2, is effected via flash chromatography on an automated column system (Combi-Flash Torrent, from Axel Semrau).

[0299] The following synthons can be prepared analogously:

TABLE-US-00014 Ex. Reactant Product Yield S52 [00760] [00761] 30% S53 [00762] [00763] 23% S54 [00764] [00765] 27% S55 [00766] [00767] 25% S56 [00768] [00769] 22% S57 [00770] [00771] 30%

Example S58

[0300] ##STR00772##

[0301] S58 can be prepared in 55% yield by the abovementioned Grignard route A) in accordance with the above-cited literature or by the Grignard route described by G. M. Castanedo et al., J. Med. Chem., 2017, 60, 627, by using 1-bromo-2-chloro-4-iodobenzene rather than 1-bromo-2-fluoro-4-iodobenzene.

1.3) Synthesis of the Substituted Iodochloropyridines

Synthesis Scheme Using the Example of a Homoadamantane Enamine

[0302] ##STR00773##

[0303] Stages 1 to 5 are conducted analogously to syntheses known from the literature: [0304] Stages 1 to 4: M. Adachi et al., Tetrahedron Letters, 37 (49), 8871, 1996; EP 0 556 008 B1. [0305] Stage 5: J. D. Eckelbarger et al., U.S. Pat. No. 8,835,409; E. A. Krasnokutskaya et al., Synthesis, 2007, 1, 81.

A) Synthesis of Enamines

[0306] The enamines can be prepared by the process detailed in WO 2020/06466, page 108, from the ketones shown and morpholine in yields of about 60-80%, or are known from the literature.

TABLE-US-00015 Reactant Product Ex. Ketone / morpholine Enamine S100 [00774] [00775] S101 [00776] [00777] S102 [00778] [00779] S103 [00780] [00781] S104 [00782] [00783] S105 [00784] [00785] S106 [00786] [00787] S107 [00788] [00789] S108 [00790] [00791] S109 [00792] [00793] S110 [00794] [00795] S111 [00796] [00797] S112 [00798] S113 [00799] [00800] S114 [00801] [00802] S115 [00803] S116 [00804] S117 [00805] [00806] S118 [00807] [00808] S119 [00809] [00810] S120 [00811] [00812] S121 [00813] [00814] S122 [00815]

B) Synthesis of the Substituted Pyridines

Stage 1: Example S200

[0307] ##STR00816##

[0308] A mixture of 23.3 g (100 mmol) of S100 (analogously for the other 6- and 7-membered enamines), 22.6 g (120 mmol) of 4-(aminomethylene)-2-phenyl-5(4H)-oxazolone [3674-51-9], 47.3 ml (500 mmol) of acetic anhydride [108-24-7] and 150 ml of toluene is stirred at 100? C. for 4 h (5-membered enamines are converted in o-xylene at 130? C./4 h in an autoclave). The mixture is concentrated completely under reduced pressure, 70 ml of methanol is added to the oil, the mixture is stirred for a further 3 h, and the crystallized product is filtered off with suction, washed once with 25 ml of ice-cold methanol and dried under reduced pressure. The crude product thus obtained is converted further without purification. Yield: 26.2 g (78 mmol), 78% E,Z isomer mixture; purity: about 95% by .sup.1H NMR.

Stage 2: Example S300

[0309] ##STR00817##

[0310] A mixture of 33.4 g (100 mmol) S200 and 200 ml of 1-methyl-2-pyrrolidinone (NMP) is stirred at 200-205? C. for 1.5 h. The mixture is allowed to cool to about 100? C., the NMP is largely removed under reduced pressure, the glassy, viscous residue is taken up in 100 ml of warm acetonitrile, stirred at room temperature for a further 12 h, and the crystallite product is filtered off and dried under reduced pressure. Yield: 25.1 g (75 mmol), 75%; purity: about 95% by .sup.1H NMR.

Stage 3: Example S400

[0311] ##STR00818##

[0312] To a suspension of 33.4 g (100 mmol) of S300 in a mixture of 150 ml of N,N-dimethylformamide (DMF), under ice-salt cooling (about ?10? C.), is added dropwise 14.0 ml (150 mmol) of phosphoryl chloride in 50 ml of DMF, and then the mixture is stirred at room temperature for a further 16 h. The reaction mixture is poured cautiously onto 1000 ml of ice-water and stirred for a further 10 min, 200 ml of dichloromethane (DCM) is added, the mixture is stirred for a further 10 min, and the organic phase is removed. The aqueous phase is basified (pH 8-9) with cautious addition of conc. aqueous ammonia solution, the aqueous phase is extracted three times with 200 ml each time of ethyl acetate, and the combined ethyl acetate extracts are washed twice with 200 ml each time of ice-water, once with 200 ml of saturated sodium hydrogencarbonate solution and twice with 100 ml each time of saturated sodium chloride solution. The mixture is dried over a mixture of magnesium sulfate and sodium carbonate, the desiccant is filtered off, the organic phase is concentrated under reduced pressure and the residue is recrystallized once from acetonitrile with addition of ethyl acetate (EA). Yield: 24.7 g (81 mmol), 81%; purity: about 95% by .sup.1H NMR.

Stage 4: Example S500

[0313] ##STR00819##

[0314] A mixture of 30.4 g (100 mmol) of S400, 100 ml of 3 N sulfuric acid and 200 ml of dioxane is stirred at 100? C. for 1.5 h. After cooling, the reaction mixture is diluted with 1000 ml of ice-water and then adjusted to pH ?7.5 with 3 N NaOH while cooling with ice. The aqueous phase is extracted three times with 200 ml each time of DCM, and the combined organic phases are washed twice with 200 ml of water and once with 200 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness and the solids are recrystallized from methanol. Yield: 23.1 g (93 mmol), 93%; purity: about 95% by .sup.1H NMR.

Stage 5: Example S600

[0315] ##STR00820##

Variant 1

[0316] 24.9 g (100 mmol) of S500 is introduced with good stirring into 500 ml of concentrated hydrochloric acid cooled to 3-5? C. To the suspension is added dropwise, with good stirring over the course of 15 min, a cooled solution of 10.4 g (150 mmol) of sodium nitrite in 50 ml of water, and then the mixture is stirred at 5? C. for about a further 20 min. The diazonium solution thus obtained is poured into a well-stirred solution, cooled to 5? C., of 90.0 g (600 mmol) of potassium iodide in 5000 ml of water to which 1000 ml of DCM has been added (caution: foaming!). After evolution of nitrogen has ended (about 25 min), sodium bisulfite solution is added until decolorization, and the pH is adjusted cautiously to ?7.5 with 5 N NaOH under very good cooling. The mixture is diluted with a further 1500 ml of DCM, the organic phase is removed, the aqueous phase is re-extracted twice with 500 ml each time of DCM, and the combined organic phases are washed twice with 500 ml each time of water and twice with 500 ml each time of saturated sodium chloride solution and then dried over magnesium sulfate. After the DCM has been removed under reduced pressure, the residue is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 22.9 g (63 mmol), 63%; purity: about 97% by .sup.1H NMR.

Variant 2

[0317] To a solution of 24.9 g (100 mmol) of S500 in 500 ml of acetonitrile is added 57.1 g (300 mmol) of p-toluenesulfonic acid monohydrate [6192-52-5] in portions, and then the mixture is cooled to 10? C. in an ice bath. To the suspension is added in portions, with good stirring and ice cooling, a solution of 13.9 g (200 mmol) of sodium nitrite and 37.5 g (250 mmol) of potassium iodide in 60 ml of water, and the mixture is stirred at 10? C. for 15 min. The mixture is then allowed to warm up to room temperature and stirred for a further 70 min. Then the mixture is diluted with 1500 ml of water, adjusted to pH 9.5 by adding saturated sodium hydrogen carbonate solution and admixed with 200 ml of 2M sodium bisulfite solution. The precipitated crude product is filtered off with suction, washed twice with 50 ml each time of water and briefly dried by suction. The crude product is dissolved in 500 ml of DCM, the solution is dried over sodium sulfate, the desiccant is filtered off with suction and the crude product is applied to Isolute. Purification is effected by flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 25.0 g (72 mmol), 72%; purity: about 97% by 1H NMR.

[0318] The following pyridines can be obtained analogously to stages 1 to 5. Yield over five stages (stages 1-5):

TABLE-US-00016 Ex. Enamine Product Yield S601 S101 [00821] 28% S602 S102 [00822] 25% S603 S103 [00823] 30% S604 S104 [00824] 23% S605 S105 [00825] 24% S606 S106 [00826] 26% S607 S107 [00827] 19% S608 S108 [00828] 32% S609 S109 [00829] 19% S610 S110 [00830] 15% S611 S111 [00831] 23% S612 S112 [00832] 21% S613 S113 [00833] 20% S614 S114 [00834] 20% S615 S115 [00835] 22% S616 S116 [00836] 18% S617 S117 [00837] 23% S618 S118 [00838] 21% S619 S119 [00839] 18% S620 S120 [00840] 19% S621 S121 [00841] 17% S622 S122 [00842] 24%

1.4) Synthesis of Anilines

Example 700

[0319] ##STR00843##

[0320] Procedure analogous to S. Bhagwanth et al., Tetrahedron Letters 50 (2009) 1582. Starting materials: 38.g (100 mmol) of bromide; glass beads are added to the mechanically stirred reaction mixture. Yield: 21.6 g (67 mmol), 67%; purity: about 97% by 1H NMR.

TABLE-US-00017 Ex. Reactants Product Yield S701 [00844] [00845] 55% S702 [00846] [00847] 61% S703 [00848] [00849] 64% S704 [00850] [00851] 60% S705 [00852] [00853] 70%

1.5) Synthesis of the Symmetrically Substituted Amines

Example A1

[0321] ##STR00854##

Variant 1: Buchwald Coupling

[0322] Procedure analogous to the following literature: [0323] P. B. Tiruveedhula et al., Organic & Biomolecular Chemistry, 13 (43), 10705, 2015. K Revunova et al., Polyhedron, 2013, 52, 1118.

[0324] A mixture of 60.9 g (110 mmol) of S1, 4.57 ml (50 mmol) of aniline, 65.2 g (200 mmol) of caesium carbonate, 2.18 g (3.5 mmol) of rac-BINAP [98327-87-8], 561 mg (2.5 mmol) of palladium(II) acetate, 500 ml of toluene and 50 g of glass beads (diameter 3 mm) is stirred first at 60? C. for 4 h and then at 100? C. for 12-16 h. The reaction mixture is allowed to cool to 60? C., and the salts are filtered off through a Celite bed in the form of a toluene slurry. The filtrate is concentrated to dryness, the residue is extracted by boiling with 200 ml of methanol, and the solids are filtered off, washed twice with 50 ml each time of methanol, dried under reduced pressure and subjected to flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 31.2 g (33 mmol), 66%; purity: about 95% by .sup.1H NMR.

[0325] Alternatively, it is possible to use other phosphines (e.g. tri-tert-butylphosphine, di-tert-butylmethylphosphine, SPhos, XPhos, AmPhos, etc.) and bases (e.g. alkoxides such as sodium tert-butoxide).

Variant 2: Jourdan-Ullmann Coupling

[0326] Procedure analogous to the following literature: [0327] Y.-L-Tasi et al., J. Luminesc., 2007, 127, 41.

[0328] A mixture of 60.9 g (110 mmol) of S1, 4.57 ml (50 mmol) of aniline, 27.6 g (200 mmol) of potassium carbonate, 42.7 g (300 mmol) of sodium sulfate, 954 mg (15 mmol) of copper powder, 500 ml of nitrobenzene and 1000 g of glass beads (diameter 3 mm) is stirred first at 160? C. for 12-16 h. The reaction mixture is allowed to cool to 60? C., and the salts are filtered off through a Celite bed in the form of a toluene slurry. The filtrate is concentrated to dryness, the residue is extracted by boiling with 200 ml of methanol, and the solids are filtered off, washed twice with 50 ml each time of methanol, dried under reduced pressure and subjected to flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 27.9 g (29.5 mmol), 59%; purity: about 95% by .sup.1H NMR.

1.6) Synthesis of the Asymmetrically Substituted Amines

Example A500

[0329] ##STR00855##

[0330] A mixture of 27.7 g (50 mmol) of S1, 4.57 ml (50 mmol) of aniline, 65.2 g (200 mmol) of caesium carbonate, 2.18 g (3.5 mmol) of rac-BINAP [98327-97-8], 561 mg (2.5 mmol) of palladium(II) acetate, 500 ml of toluene and 50 g of glass beads (diameter 3 mm) is stirred at 60? C. until conversion is complete (TLC monitoring, typically 2-4 h). Then 18.0 g (50 mmol) of S600 is added; the temperature is increased to 100? C. On completion of conversion (TLC monitoring, typically 12-16 h), the reaction mixture is allowed to cool to 60? C., and the salts are filtered off through a Celite bed in the form of a toluene slurry. The filtrate is concentrated to dryness, the residue is extracted by boiling with 200 ml of methanol, and the solids are filtered off, washed twice with 50 ml each time of methanol, dried under reduced pressure and subjected to flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 21.0 g (28 mmol), 56%; purity: about 95% by .sup.1H NMR.

[0331] Asymmetric amines obtained in this way can be converted as described in 2.) to the inventive emitters EAS.

2.) Synthesis of the Inventive Emitters

2.1) Synthesis of the Symmetrically Substituted Emitters

Example ES1

[0332] ##STR00856##

Variant 1

[0333] Procedure analogous to the following literature: [0334] T. Kader et al., Chem. Eur. J., 2019, 25, 4412-4425.

[0335] A mixture of 47.2 g (50 mmol) of A1, 27.6 g (200 mmol) of potassium carbonate, 1.72 g (3 mmol) of (NHC)Pd(allyl)Cl [478980-03-9], 50 g of glass beads (diameter 3 mm) and 500 ml of N,N-dimethylacetamide (DMAc) is heated to 150? C. with good stirring for 16 h. After cooling to 80? C., 1000 ml of water is added dropwise, the precipitated solids are filtered off with suction, and these are washed twice with 100 ml each time of water and twice with 50 ml each time of methanol, and dried under reduced pressure. The crude product is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau, DCM: 2% MeOH), and then purified by repeated hot extraction crystallization (DCM:acetonitrile 1:3 to 2:1) and subsequent fractional sublimation or by heat treatment under high vacuum. Yield: 14.9 g (23 mmol), 46%; purity: >99.9% by HPLC.

[0336] Rather than (NHC)Pd(allyl)CI, it is also possible to use 4 mmol of [(tBu).sub.3PH][BF.sub.4] and 2 mmol of Pd(OAc).sub.2.

Variant 2

[0337] Procedure analogous to the following literature: [0338] A. W. Jones et al., Adv. Synth. Catal. 2015, 357, 945.

[0339] A mixture of 47.2 g (50 mmol) A1, 3.1 g (10 mmol) of palladium(II) pivalate [106224-36-6], 27.8 g (120 mmol) of silver(I) oxide [20667-12-3], 9.6 g (120 mmol) of copper(II) oxide [1317-38-0], 50 g of glass beads (diameter 3 mm) and 200 ml of pivalic acid (PivOH) is heated to 130? C. with good stirring for 24 h. After cooling to 80? C., 1000 ml of water is added dropwise, the precipitated solids are filtered off with suction, and these are washed twice with 100 ml each time of water and twice with 50 ml each time of methanol, and dried under reduced pressure. The crude product is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau, DCM: 2% MeOH), then purified by repeated hot extraction crystallization (DCM:acetonitrile 1:3 to 2:1) and subsequent fractional sublimation or by heat treatment under high vacuum. Yield: 12.3 g (19 mmol), 38%; purity: >99.9% by HPLC.

[0340] Analogously to stages 1.4 and 2.1, it is possible to prepare the following emitters ES: yield over two stages:

TABLE-US-00018 Nitrile Ex. Amine Product Yield ES2 [00857] [00858] 36% ES3 [00859] [00860] 38% ES4 [00861] [00862] 35% ES5 [00863] [00864] 33% ES6 [00865] [00866] 36% ES7 [00867] [00868] 40% ES8 [00869] [00870] 33% ES9 [00871] [00872] 3% ES10 [00873] [00874] 37% ES11 [00875] [00876] 35% ES12 [00877] [00878] 37% ES13 [00879] [00880] 39% ES14 [00881] [00882] 30% ES15 [00883] [00884] 32% ES16 [00885] [00886] 35% ES17 [00887] [00888] 38% ES18 [00889] [00890] 33% ES19 [00891] [00892] 35% ES20 [00893] [00894] 34% ES21 [00895] [00896] 34% ES22 [00897] [00898] 35% ES23 [00899] [00900] 32% ES24 [00901] [00902] 33% ES25 [00903] [00904] 39% ES26 [00905] [00906] 34% ES27 [00907] [00908] 36% ES28 [00909] [00910] 37% ES29 [00911] [00912] 31% ES30 [00913] [00914] 33% ES31 [00915] [00916] 35% ES32 [00917] [00918] 34% ES33 [00919] [00920] 29% ES34 [00921] [00922] 40% ES35 [00923] [00924] 38% ES36 [00925] [00926] 39% ES37 [00927] [00928] 34% ES38 [00929] [00930] 36% ES39 [00931] [00932] 35% ES40 [00933] [00934] 37% ES41 [00935] [00936] 38% ES42 [00937] [00938] 37% ES43 [00939] [00940] 28% ES44 [00941] [00942] 33% ES45 [00943] [00944] 35% ES46 [00945] [00946] 38% ES47 [00947] [00948] 26% ES48 [00949] [00950] 39% ES49 [00951] [00952] 29% ES50 [00953] [00954] 37% ES51 [00955] [00956] 35% ES52 [00957] [00958] 33% ES53 [00959] [00960] 35% ES54 [00961] [00962] 31% ES55 [00963] [00964] 38% ES56 [00965] [00966] 36% ES57 [00967] [00968] 37% ES58 [00969] [00970] 35% ES59 [00971] [00972] 30% ES60 [00973] [00974] 28% ES61 [00975] [00976] 36% ES62 [00977] [00978] 38% ES63 [00979] [00980] 27% ES64 [00981] [00982] 32% ES65 [00983] [00984] 21% ES66 [00985] [00986] 22% ES67 [00987] [00988] 19% ES68 [00989] [00990] 12% ES69 [00991] [00992] 21% ES70 [00993] [00994] 20% ES71 [00995] [00996] 18%

2.2) Synthesis of the Asymmetrically Substituted Emitters EAS

Example EAS1

[0341] ##STR00997##

Variant 1

[0342] Procedure analogous to the following literature: [0343] T. Kader et al., Chem. Eur. J., 2019, 25, 4412-4425.

[0344] A mixture of 37.5 g (50 mmol) of A500, 27.6 g (200 mmol) of potassium carbonate, 1.72 g (3 mmol) of (NHC)Pd(allyl)Cl [478980-03-9], 50 g of glass beads (diameter 3 mm) and 500 ml of N,N-dimethylacetamide (DMAc) is heated to 140? C. with good stirring for 16 h. After cooling to 80? C., 1000 ml of water is added dropwise, the precipitated solids are filtered off with suction, and these are washed twice with 100 ml each time of water and twice with 50 ml each time of methanol, and dried under reduced pressure. The crude product is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau, DCM: 2% MeOH), which also separates isomers that occur. Finally, the emitters thus obtained are purified by repeated hot extraction crystallization (DCM:acetonitrile 1:3 to 2:1) and subsequent fractional sublimation or by heat treatment under high vacuum. Yield: 14.0 g (25 mmol), 50%; purity: >99.9% by HPLC.

[0345] Rather than (NHC)Pd(allyl)CI, it is also possible to use 4 mmol of [(tBu).sub.3PH][BF.sub.4] and 2 mmol of Pd(OAc).sub.2.

[0346] Analogously to stages 1.5 and 2.2, it is possible to prepare the following emitters EAS; yield over two stages:

TABLE-US-00019 Synthons S Ex. Amine Product Yield EAS2A [00998] [00999] 17% EAS2B [01000] 17% EAS3A [01001] [01002] 19% EAS3B [01003] 17% EAS4A [01004] [01005] 19% EAS4B [01006] 15% EAS5 [01007] [01008] 33% EAS6 [01009] [01010] 30% EAS7 [01011] [01012] 35% EAS8 [01013] [01014] 30% EAS9 [01015] [01016] 32% EAS10 [01017] [01018] 22% EAS11 [01019] [01020] 33% EAS12 [01021] [01022] 25% EAS13 [01023] [01024] 39% EAS14 [01025] [01026] 38% EAS15A [01027] [01028] 17% EAS15B [01029] 19% EAS16 [01030] [01031] 37% EAS17 [01032] [01033] 37% EAS18 [01034] [01035] 22% EAS19 [01036] [01037] 20% EAS20 [01038] [01039] 31% EAS21A [01040] [01041] 20% EAS21B [01042] [01043] 15% EAS22 [01044] [01045] 36% EAS23A [01046] [01047] 18% EAS23B [01048] [01049] 19% EAS24A [01050] [01051] 19% EAS24B [01052] [01053] 20% EAS25 [01054] [01055] 34% EAS26 [01056] [01057] 23% EAS27 [01058] [01059] 35% EAS28 [01060] [01061] 34% EAS29 [01062] [01063] 33% EAS30A [01064] [01065] EAS30B [01066] 34% ESA31 [01067] [01068] 30% EAS32A [01069] [01070] 19% EAS32B [01071] 17% EAS33A [01072] [01073] 19% EAS33B [01074] 16% EAS34 [01075] [01076] 35% EAS35 [01077] [01078] 35% EAS36 [01079] [01080] 30% EAS37 [01081] [01082] 36% EAS38 [01083] [01084] 35% EAS39 [01085] [01086] 37% EAS40A [01087] [01088] 19% EAS40B [01089] 21% EAS41 [01090] [01091] 35% EAS42 [01092] [01093] 20% EAS43 [01094] [01095] 25% EAS44 [01096] [01097] 28%

[0347] Alternative Synthesis Routes:

[0348] The compounds of the invention, in some cases with improved yields, can be prepared by the following alternative synthesis routes:

2.3) Alternative Method A

[0349] Stepwise construction by two consecutive Buchwald couplings, followed by a Pd-catalysed intramolecular cyclization using the example of ES1:

##STR01098##

Stage 1): Buchwald Coupling 1

[0350] ##STR01099##

[0351] A mixture of 43.7 g (100 mmol) of S10, 9.13 ml (100 mmol) of aniline [62-53-3], 20.2 g (210 mmol) of sodium tert-butoxide [865-48-5], 1.11 g (2 mmol) of bisdiphenylphosphinoferrocene (dppf) [12150-46-8], 499 mg (2 mmol) of palladium(II) acetate, 500 ml of toluene and 50 g of glass beads (diameter 3 mm) is stirred under gentle reflux until conversion is complete (about 1 h). The reaction mixture is allowed to cool to 60? C., 300 ml of water is added, and the organic phase is removed and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a silica gel bed in the form of a toluene slurry and washed through with 500 ml of ethyl acetate, and the filtrate is concentrated to dryness. The residue is purified by chromatography (silica gel, cyclohexane/EA, Combi-Flash Torrent from A. Semrau). Yield: 32.7 g (81 mmol), 81%; purity: about 97% by .sup.1H NMR.

Stage 2: Buchwald Coupling 2

[0352] ##STR01100##

[0353] A mixture of 40.4 g (100 mmol) of stage 1), 43.7 g (100 mmol) of S10, 20.2 g (210 mmol) of sodium tert-butoxide [865-48-5], 725 mg (2.5 mmol) of tri-tert-butylphosphonium tetrafluoroborate [131274-22-1], 449 mg (2 mmol) of palladium(II) acetate, 500 ml of toluene and 50 g of glass beads (diameter 3 mm) is stirred under gentle reflux until conversion is complete (about 12 h). The reaction mixture is allowed to cool to 60? C., 300 ml of water is added, and the organic phase is removed and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a silica gel bed in the form of a toluene slurry and washed through with 500 ml of ethyl acetate, and the filtrate is concentrated to dryness. The residue is purified by chromatography (silica gel, cyclohexane/EA, Combi-Flash Torrent from A. Semrau). Yield: 55.6 g (77 mmol), 77%; purity: about 97% by .sup.1H NMR.

Stage 3): Cyclization

[0354] A mixture of 71.7 g (100 mmol) of stage 2), 41.5 g (300 mmol) of potassium carbonate, 725 mg (2.5 mmol) of tri-tert-butylphosphonium tetrafluoroborate [131274-22-1], 449 mg (2 mmol) of palladium(II) acetate, 1000 ml of dimethylacetamide and 50 g of glass beads (diameter 3 mm) is stirred at 150? C. until conversion is complete (about 12 h). After cooling to 80? C., 2000 ml of water is added dropwise, the precipitated solids are filtered off with suction, and these are washed twice with 200 ml each time of water and twice with 50 ml each time of methanol, and dried under reduced pressure. The crude product is subjected to flash chromatography (RP silica gel, acetonitrile/THF, Combi-Flash Torrent from A. Semrau), then purified by repeated hot extraction crystallization (DCM:acetonitrile 1:3 to 3:1) and subsequent fractional sublimation or by heat treatment under high vacuum. Yield: 36.5 g (56 mmol), 56%; purity: >99.9% by HPLC.

[0355] The alternative method A is suitable not just for construction of symmetrically substituted units, but specifically also for construction of asymmetrically substituted emitters, through use of two different iodochlorobenzonitriles in stage 1) and stage 2).

[0356] The following compounds can be prepared analogously:

TABLE-US-00020 Ex. Reactants Product Yield ES72 [01101] [01102] 13% ES73 [01103] [01104] 37% ES74 [01105] [01106] 38% ES75 [01107] [01108] 34% ES76 [01109] [01110] 29% ES77 [01111] [01112] 35% ES78 [01113] [01114] 41% ES79 [01115] [01116] 30% EAS45A [01117] [01118] 19% EAS45B [01119] 10%

2.4) Alternative Method B

Stepwise AminationCyclization Via a Carbazole Intermediate

[0357] ##STR01120## [0358] Stage 1: Standard Buchwald coupling method for preparation of secondary amines from an aniline and the iodochlorobenzonitrile, for example analogously to U. Masanobu, et al., J. Am. Chem. Soc., 2004, 126(28), 8755 or P. B. Tiruveedhula, et al., Org. & Biomol. Chem., 2015, 13(43), 10705. Typical yields 70-95%. [0359] Stage 2: Intramolecular cyclization to the carbazole analogously to P. B. Tiruveedhula, et al., Org. & Biomol. Chem., 2015, 13(43), 10705 or F. Chen et al., RSC Adv., 2015, 5, 51512. When asymmetrically substituted anilines are used, the regioisomeric carbazoles are isolated as a mixture and converted further. Typical yields 60-90%. [0360] Stage 3: Standard Buchwald coupling method for preparation of N-arylated carbazoles; alternatively, it is possible to conduct an Ullmann coupling, for example analogously to J. H. Cho et al., Bull. Korean Chem. Soc., (2011), 32(7), 2461. Typical yields 40-80%. [0361] Stage 4: Intramolecular cyclization, analogously to stage 2, for example analogously to T. Kader et al., Chem. Europ. J., 2019, 25(17), 4412 or analogously to U.S. Pat. No. 9,000,421 B1, using tricyclohexylphosphonium tetrafluoroborate or with NHC-Pd complexes, for example allyl[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]chloropalladium(II). Typical yields 50-80%.

[0362] Alternatively, it is possible to construct the carbazole intermediates as follows:

##STR01121## [0363] Stage 1: Standard Buchwald coupling method for preparation of secondary amines from an aniline and the iodochlorobenzonitrile, for example analogously to U. Masanobu, et al., J. Am. Chem. Soc., 2004, 126(28), 8755 or P. B. Tiruveedhula, et al., Org. & Biomol. Chem., 2015, 13(43), 10705. Typical yields 70-95%. [0364] Stage 2: see above. [0365] Stage 3 can preferably also be performed with 3-chloro-4-triflate- or 3-fluoro-4-chlorobenzonitriles as follows:

##STR01122## [0366] Stage 3: analogously to WO2019063288. Typical yields 60-80%. [0367] Stage 4: see above.

Optimized Synthesis of ES94

Stage 1

[0368] ##STR01123##

[0369] A well-stirred mixture of 32.9 g (100 mmol) of 1-cyano-3-amino-4-chlorotriptycene (see page 228), 20.7 g (100 mmol) of 2-bromonaphthalene, 28.8 g (300 mmol) of sodium tert-butoxide, 1.11 g (2 mmol) of dppf, 225 mg (1 mmol) of palladium(II) acetate in 500 ml of toluene is heated under reflux for 1 h. The mixture is allowed to cool to 70? C., 500 ml of water is added, the mixture is stirred for a further 10 min, and the organic phase is separated off and washed twice with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a Celite bed in the form of a toluene slurry, the filtrate is concentrated under reduced pressure, the residue is dissolved in 300 ml of DCM, and the latter is removed under reduced pressure, with replacement of the DCM distilled off by simultaneous addition of EtOH. The crystallized product is filtered off with suction, washed three times with 50 ml each time of EtOH and dried under reduced pressure. Yield: 42.3 g (93 mmol), 93%; purity: about 98% by .sup.1H NMR.

Stage 2

[0370] ##STR01124##

[0371] A well-stirred mixture of 45.4 g (100 mmol) of the amine, 500 mmol of potassium carbonate, 1.16 g (4 mmol) of tri-tert-butylphosphonium tetrafluoroborate, 449 mg (2 mmol) of palladium(II) acetate, 100 g of glass beads (diameter 3 mm) and 1000 ml of dimethylacetamide (DMAC) is stirred at 150? C. for 1 h. The mixture is filtered while still hot through a Celite bed in the form of a DMAC slurry, the filtrate is concentrated to dryness, the residue is dissolved in 500 ml of DCM, and the latter is removed under reduced pressure, with replacement of the DCM distilled off by simultaneous addition of 300 ml of EtOH. The crystallized product is filtered off with suction, washed three times with 50 ml each time of EtOH and dried under reduced pressure. Yield: 32.9 g (78 mmol), 78%; purity: about 98% by .sup.1H NMR.

Stages 3 and 4: One-Pot Reaction

[0372] ##STR01125##

[0373] A well-stirred mixture of 20.9 g (50 mmol) of the carbazole, 19.6 g (50 mmol) of S1e, 34.6 g (250 mmol) of potassium carbonate, 100 g of glass beads (diameter 3 mm) and 500 ml of DMAC is stirred at 150? C. for 20 h. The reaction mixture is allowed to cool to RT, 1.16 g (4 mmol) of tri-tert-butylphosphonium tetrafluoroborate and 449 mg (2 mmol) of palladium(II) acetate are added, and the mixture is stirred at 150? C. for another 7 h. The mixture is filtered while still hot through a Celite bed in the form of a DMAC slurry, the filtrate is concentrated to dryness, the residue is dissolved in 500 ml of DCM, and the latter is removed under reduced pressure, with replacement of the DCM distilled off by simultaneous addition of 300 ml of EtOH. The crystallized crude product is filtered off with suction, washed three times with 50 ml each time of EtOH and dried under reduced pressure. The crude product is purified by hot crystallization extraction five times (DCM:acetonitrile 2:1) and subsequent fractional sublimation under high vacuum (T ?300? C., p ?10.sup.?5 mbar). Yield: 20.0 g (29 mmol), 58%; purity: >99.9% by HPLC.

[0374] The alternative method B is suitable not just for construction of symmetrically substituted units, but specifically also for regiodirectional construction of asymmetrically substituted emitters, through use of two different iodochlorobenzonitriles in stage 1) and stage 3) or 3-fluoro-4-triflate- or 3-fluorochlorobenzonitrile in stage 3).

[0375] The following compounds can be prepared analogously:

TABLE-US-00021 Ex. Reactants Product Yield ES80 S10 stages 1 & 3 S700 [01126] 30% ES80 S10 stage 1 ES80 37% S1d stage 3 S700 ES80 S10 stage 1 ES80 54% S1e stage 3 S700 ES81 S14 stages 1 & 3 S701 [01127] 28% ES82 S10 stages 1 & 3 S702 [01128] 20% ES83 S10 stages 1 & 3 S703 [01129] 27% ES83 S10 stage 1 ES83 35% S1d stage 3 S703 ES83 S10 stage 1 ES83 52% S1e stage 3 S703 ES84 S13 stages 1 & 3 S704 [01130] 29% ES84 S13 stage 1 ES84 49% S4e stage 3 S704 EAS46A S10 stage 1 S14 stage 3 S705 [01131] 19% EAS46B [01132] 6%

2.5) Alternative Method C

Construction by Suzuki Coupling of 2,6-bisboranylanilines with the Halobenzonitriles and Subsequent Double Cyclizing Buchwald Amination

[0376] ##STR01133## [0377] Stage 1: Borylation analogously to A. Osichow et al., Organomet. 2013, 32(18), 5239. Typical yields 60-90%. [0378] Stage 2: Regioselective Suzuki coupling on the chloro triflates or chloro bromides/iodides; preferably used Hal.sup.1/Hal.sup.2 combinations are OTf/Cl or I/Cl or Br/Cl analogously to M. 1. Dawson et al., Journal of Medicinal Chemistry, 2007, 50(11), 2622 or WO2021121371. Typical yields 50-80%. [0379] Stage 3: Cyclization analogously to US 2017/0324045. Typical yields 30-60%.

[0380] The following compounds can be prepared analogously:

TABLE-US-00022 Ex. Reactants Product Yield ES85 [01134] [01135] 31% ES86 [01136] [01137] 34% ES87 [01138] [01139] 36%

2.6) Alternative Method D

Construction from 3-fluoro-4-halobenzonitriles by Suzuki Coupling and Intramolecular Cyclization Via S.SUB.N.2Ar Reaction

[0381] ##STR01140## [0382] Stage 1: Balz-Schiemann reaction analogously to G. Balz et al., Chem. Ber., 1927, 5, 1186 or via NOBF.sub.4 analogously to D. J. Milner et al., Synth. Commun., 1992, 22, 73. See also optimized synthesis of 1e. Typical yields 30-85%. [0383] Stage 2: Suzuki coupling on the 3-fluoro-4-halobenzonitriles. Typical yields 40-80%. [0384] Stage 3: Intramolecular cyclization via S.sub.N2Ar reaction, for example analogously to CN108727396. Typical yields 40-80%.

[0385] The following compounds can be prepared analogously:

TABLE-US-00023 Ex. Reactants Product Yield ES88 [01141] [01142] 34% ES89 [01143] [01144] 14% ES90 [01145] [01146] 32%

2.7) Alternative Method E

Construction from 2,6-dichloroanilines by Buchwald Coupling and Pd-Catalysed Intramolecular Cyclization

[0386] ##STR01147## [0387] Stage 1 and stage 2: for example analogously to US 2021/0005826.

[0388] Typical yields over the two stages 20-50%.

[0389] The following compounds can be prepared analogously:

TABLE-US-00024 Ex. Reactants Product Yield ES91 [01148] [01149] 48% ES92 [01150] [01151] 46% ES93 [01152] [01153] 22%

[0390] Measurement of Photoluminescence Spectra (PL Spectra):

[0391] FIG. 1 shows PL spectra of inventive compounds ES1, ES94 and comp. 675 (see page 204), measured with a Hitachi F-4500 PL spectrometer in about 10.sup.?5 molar degassed toluene solution at room temperature (about 25? C.).

[0392] The PL spectra have very narrow emission bands with low FWHM values (<0.18 eV) and lead to particularly pure-colour emission. Moreover, in the long-wave emission flank, they often have a shoulder or secondary maximum respectively having less than 40% of the intensity of the main maximum. In top-emission OLED components, this leads to a favourably low viewing angle dependence of the colour impression, compared to prior-art narrowband boron-containing emitters that often have no such shoulders or secondary maxima and show greater viewing angle dependence of the colour impression.

[0393] Production of OLED Components

[0394] 1) Vacuum-Processed Components

[0395] One use of the compounds of the invention is as dopant in the emission layer in fluorescence and hyperfluorescence OLED components.

[0396] OLEDs (organic light emitting diodes) of the invention and OLEDs according to the prior art are produced by a general method according to WO 2004/058911, which is adapted to the circumstances described here (variation in layer thickness, materials used).

[0397] In the examples which follow, the results for various OLEDs are presented. Cleaned glass plates (cleaning in Miele laboratory glass washer, Merck Extran detergent) coated with structured ITO (indium tin oxide) of thickness 50 nm are pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and, within 30 min, for improved processing, coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS? P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and then baked at 180? C. for 10 min. These coated glass plates form the substrates to which the OLEDs are applied. After the production, the OLEDs are encapsulated for protection against oxygen and water vapour. The exact layer structure of the electroluminescent OLEDs can be found in the examples. The materials required for production of the OLEDs are shown in table 10.

[0398] 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 Im/W) and the external quantum efficiency (EQE, measured in percent) are, as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics. The electroluminescent spectra are recorded at a luminance of 100 or 1000 cd/m.sup.2, and these are used to infer the emission colour and the EL-FWHM values (ELectroluminescence-Full Width Half Maximumwidth of the EL emission spectra at half the peak height in eV; for better comparability over the entire spectral range).

[0399] Fluorescence OLED Components:

[0400] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer (EML) always consists of at least one matrix material (host material) SMB and an emitting dopant (emitter) ES or EAS which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as SMB:ES or EAS (97:3%) mean here that the material SMB is present in the layer in a proportion by volume of 97% and ES or EAS in a proportion of 3%.

[0401] Analogously, the electron transport layer may also consist of a mixture of two materials, for example here of ETM1 (50%) and ETM2 (50%); see table 1. The materials used for production of the OLEDs are shown in table 10. The compounds D-Ref.1 (see table 10) are used as a comparison according to the prior art.

[0402] Blue Fluorescence OLED Components BF:

[0403] The OLEDs basically have the following layer structure:

[0404] Substrate [0405] hole injection layer 1 (HIL1) composed of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm [0406] hole transport layer 1 (HTL1) composed of HTM1, 160 nm [0407] hole transport layer 2 (HTL2), see table 1 [0408] emission layer (EML), see table 1 [0409] electron transport layer (ETL2), see table 1 [0410] electron transport layer (ETL1) composed of ETM1 (50%) and ETM2 (50%), 30 nm electron injection layer (EIL) composed of ETM2, 1 nm [0411] cathode composed of aluminium, 100 nm

TABLE-US-00025 TABLE 1 Structure of blue fluorescence OLED components Ex. HTL2 EML ETL2 Ref-BF1 HTM2 SMB1:Ref.- D1 (97:3%) ETM1 10 nm 20 nm 10 nm Ref-BF2 HTM2 SMB1:Ref.- D2 (97:3%) ETM1 10 nm 20 nm 10 nm BF1 HTM2 SMB1:ES44 (97:3%) ETM1 10 nm 20 nm 10 nm BF2 HTM2 SMB2:ES44 (95:5%) ETM1 10 nm 20 nm 10 nm BF3 HTM2 SMB3:ES56 (97:3%) ETM1 10 nm 20 nm 10 nm BF4 HTM2 SMB1:ES9 (97:3%) ETM1 10 nm 20 nm 10 nm BF5 HTM2 SMB1:ES10 (95:5%) ETM1 10 nm 20 nm 10 nm BF6 HTM2 SMB1:ES11 (97:3%) ETM1 10 nm 20 nm 10 nm BF7 HTM2 SMB1:ES21 (97:3%) ETM1 10 nm 20 nm 10 nm BF8 HTM2 SMB1:ES37 (97:3%) ETM1 10 nm 20 nm 10 nm BF9 HTM2 SMB1:ES40 (97:3%) ETM1 10 nm 20 nm 10 nm BF10 HTM2 SMB1:ES59 (97:3%) ETM1 10 nm 20 nm 10 nm BF11 HTM2 SMB1:61 (97:3%) ETM1 10 nm 20 nm 10 nm BF12 HTM2 SMB1:EAS2A (96:4%) ETM1 10 nm 20 nm 10 nm BF13 HTM2 SMB1:EAS2B (96:4%) ETM1 10 nm 20 nm 10 nm BF14 HTM2 SMB1:EAS3A (97:3%) ETM1 10 nm 20 nm 10 nm BF15 HTM2 SMB1:EAS15B (97:3%) ETM1 10 nm 20 nm 10 nm BF16 HTM2 SMB1:EAS42 (97:3%) ETM1 10 nm 20 nm 10 nm BF17 HTM2 SMB1:ES 73 (97:3%) ETM1 10 nm 20 nm 10 nm BF18 HTM2 SMB1:ES78 (95:5%) ETM1 10 nm 20 nm 10 nm BF19 HTM2 SMB1:EAS46A (97:3%) ETM1 10 nm 20 nm 10 nm BF20 HTM2 SMB1:ES94 (97:3%) ETM1 10 nm 20 nm 10 nm

TABLE-US-00026 TABLE 2 Results EQE (%) Voltage (V) EL-FWHM Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 Colour [eV] Ref-BF1 6.3 4.5 blue 0.17 Ref-BF2 7.9 4.3 blue 0.43 BF1 8.4 4.3 blue 0.15 BF2 7.9 4.2 blue 0.15 BF3 8.2 4.2 blue 0.15 BF4 6.6 4.4 deep blue 0.13 BF5 7.9 4.6 blue 0.15 BF6 7.3 4.4 deep blue 0.13 BF7 8.3 4.3 blue 0.15 BF8 8.0 4.4 blue 0.16 BF9 8.6 4.5 blue 0.15 BF10 7.9 4.3 blue 0.13 BF11 8.8 4.3 blue 0.15 BF12 7.6 4.4 blue 0.14 BF13 7.9 4.4 blue 0.15 BF14 8.3 4.3 blue 0.16 BF15 7.8 4.3 blue 0.15 BF16 7.7 4.4 blue 0.14 BF17 7.6 4.4 blue 0.14 BF18 8.1 4.3 blue 0.16 BF19 8.5 4.3 blue 0.15 BF20 8.9 4.2 blue 0.13

[0412] Hyperphosphorescence OLED Components:

[0413] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer(s) (EML) always consist(s) of at least one matrix material (host material) TMM, a (phosphorescent) sensitizer PS and a fluorescent emitter ES or EAS. The matrix material (host material) TMM may consist of two components that are evaporated as a mixture (premixed host, e.g. TMM2), the components and the composition is likewise shown in table 10. Sensitizers and fluorescent emitter ES or EAS are added to the host material TMM in a particular proportion by volume by coevaporation. Details given in such a form as TMM:PS(5%):ES or EAS(3%) mean here that the material TMM is present in the layer in a proportion by volume of 92%, PS in a proportion of 5% and ES or EAS in a proportion of 3%.

[0414] Blue Hyperphosphorescence OLED Components BH:

[0415] The OLEDs basically have the following layer structure: [0416] substrate [0417] hole injection layer 1 (HIL1) composed of HTM2 doped with 5% NDP-9 (commercially available from Novaled), 20 nm [0418] hole transport layer 1 (HTL1) composed of HTM2, 30 nm [0419] hole transport layer 2 (HTL2), see table 3 [0420] emission layer (EML), see table 3 [0421] electron transport layer (ETL2), see table 3 [0422] electron transport layer (ETL1) composed of ETM1 (50%) and ETM2 (50%), 20 nm [0423] electron injection layer (EIL) composed of ETM2, 1 nm [0424] cathode composed of aluminium, 100 nm

TABLE-US-00027 TABLE 3 Construction of blue hyperphosphorescence OLED components Ex. HTL2 EML ETL2 BH1 HTM3 TMM1:PS1(7%):ES37(1.5%) ETM3 10 nm 25 nm 10 nm BH2 HTM3 TMM1:PS1(7%):ES37(2%) ETM3 10 nm 25 nm 10 nm BH3 HTM3 TMM1:PS1(7%):EAS19(2%) ETM3 10 nm 25 nm 10 nm BH4 HTM3 TMM1:PS3(7%):ES80(2%) ETM3 10 nm 25 nm 10 nm BH5 HTM3 TMM1:PS3(7%):EAS46(2%) ETM3 10 nm 25 nm 10 nm BH6 HTM3 TMM1:PS3(7%):EAS42(2%) ETM3 10 nm 25 nm 10 nm

TABLE-US-00028 TABLE 4 Results EQE (%) Voltage (V) EL-FWHM Ex. 100 cd/m.sup.2 100 cd/m.sup.2 Colour [eV] BH1 13.4 3.4 blue 0.16 BH2 11.1 3.4 blue 0.16 BH3 12.8 3.3 blue 0.17 BH4 20.1 3.2 blue 0.17 BH5 23.4 3.2 blue 0.16 BH6 21.2 3.3 blue 0.17

[0425] Green Hyperphosphorescence OLED Components GH:

[0426] The OLEDs basically have the following layer structure: [0427] substrate [0428] hole injection layer 1 (HIL1) composed of HTM2 doped with 5% NDP-9 (commercially available from Novaled), 20 nm [0429] hole transport layer 1 (HTL1) composed of HTM2, 30 nm [0430] hole transport layer 2 (HTL2), see table 5 [0431] emission layer (EML), see table 5 [0432] electron transport layer (ETL2), see table 5 [0433] electron transport layer (ETL1) composed of ETM1 (50%) and ETM2 (50%), 30 nm [0434] electron injection layer (EIL) composed of ETM2, 1 nm [0435] cathode composed of aluminium, 100 nm

TABLE-US-00029 TABLE 5 Construction of green hyperphosphorescence OLED components Ex. HTL2 EML ETL2 GH1 HTM3 TMM1:PS1(8%):ES39(2%) ETM3 10 nm 25 nm 10 nm GH2 HTM3 TMM1:PS3(8%):ES39(2%) ETM3 10 nm 25 nm 10 nm

TABLE-US-00030 TABLE 6 Results EQE (%) Voltage (V) EL-FWHM Ex. 100 cd/m.sup.2 100 cd/m.sup.2 Colour [eV] GH1 19.3 3.4 green 0.16 GH2 22.4 3.3 green 0.16

[0436] Orange-Red Hyperphosphorescence OLED Components RH:

[0437] The OLEDs basically have the following layer structure: [0438] substrate [0439] hole injection layer 1 (HIL1) composed of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm [0440] hole transport layer 1 (HTL1) composed of HTM1, 30 nm [0441] hole transport layer 2 (HTL2), see table 7 [0442] emission layer (EML), see table 7 [0443] electron transport layer (ETL2), see table 7 [0444] electron transport layer (ETL1) composed of ETM1 (50%) and ETM2 (50%), 45 nm [0445] electron injection layer (EIL) composed of ETM2, 1 nm [0446] cathode composed of aluminium, 100 nm

TABLE-US-00031 TABLE 7 Construction of orange-red hyperphosphorescence OLED components Ex. HTL2 EML ETL2 RH1 HTM2 TMM2:PS2(8%):ES67(2%) ETM1 10 nm 20 nm 10 nm

TABLE-US-00032 TABLE 8 Results EQE (%) Voltage (V) EL-FWHM Ex. 100 cd/m.sup.2 100 cd/m.sup.2 Colour [eV] RH1 20.2 3.2 red 0.15

[0447] 2) Solution-Processed Components:

[0448] The production of solution-based OLEDs is fundamentally described in the literature, for example in WO 2004/037887 and WO 2010/097155. The examples that follow combined the two production processes (application from the gas phase and solution processing), such that layers up to and including emission layer were processed from solution and the subsequent layers (hole blocker layer/electron transport layer) were applied by vapour deposition under reduced pressure. For this purpose, the previously described general methods are matched to the circumstances described here (layer thickness variation, materials) and combined as follows.

[0449] The construction used is thus as follows: [0450] substrate [0451] ITO, 50 nm [0452] PEDOT, 20 nm [0453] hole transport layer HIL-Sol, composed of HTM-Sol, 20 nm [0454] emission layer composed of SMB4(97%) and ES(3%) or EAS(3%), 50 nm [0455] electron transport layer (ETL1) composed of ETM1 (50%) and ETM2 (50%), 25 nm [0456] cathode composed of aluminium, 100 nm

[0457] Substrates used are glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm. For better processing, these are coated with the buffer (PEDOT) Clevios P VP AI 4083 (Heraeus Clevios GmbH, Leverkusen); PEDOT is at the top. Spin-coating is effected under air from water. The layer is subsequently baked at 180? C. for 10 minutes. The hole transport layer and the emission layer are applied to the glass plates thus coated. The hole transport layer is the polymer HTM-Sol of the structure shown in table 10, which was synthesized according to WO 2010/097155. The polymer is dissolved in toluene, such that the solution typically has a solids content of about 5 g/I when, as is the case here, the layer thickness of 20 nm typical of a device is to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere, argon in the present case, and baked at 180? C. for 60 min.

[0458] The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). Details given in such a form as SMB4 (97%) and ES or EAS (3%) mean here that the material SMB4 is present in the emission layer in a proportion by weight of 97% and the dopant ES or EAS in a proportion by weight of 3%. The mixture for the emission layer is dissolved in toluene or chlorobenzene. The typical solids content of such solutions is about 18 g/I when, as here, the layer thickness of 50 nm which is typical of a device is to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere, argon in the present case, and baked at 140 to 160? C. for 10 minutes. The materials used are shown in table 10.

[0459] The materials for the electron transport layer and for the cathode are applied by thermal vapour deposition in a vacuum chamber. The electron transport layer, for example, may consist of more than one material, the materials being added to one another by co-evaporation in a particular proportion by volume. Details given in such a form as ETMF (50%) and ETM2 (50%) mean here that the ETM1 and ETM2 materials are present in the layer in a proportion by volume of 50% each. The materials used in the present case are shown in table 10.

TABLE-US-00033 TABLE 9 Results for the solution-processed OLEDs at 1000 cd/m.sup.2 EL- EQE Voltage FWHM Ex. Dopant (%) (V) Colour [eV] Sol-BF1 ES15 7.8 4.4 blue 0.15

TABLE-US-00034 TABLE 10 Structural formulae of the materials used [01154] HTM1 [1365840-52-3] [01155] HTM2 [1450933-44-4] [01156] HTM3 [1401068-29-8] [01157] SMB1 [1087346-88-0] [01158] SMB2 [667940-34-3] [01159] SMB3 [1627916-48-6] [01160] SMB4 [1818872-85-3] [01161] TMM1/ETM3 [1201800-83-0] [01162] TMM2 [1643476-29-2] (40%) [01163] [1822310-86-0] (60%) [01164] Ref.-D1 [1805802-42-9] [01165] Ref.-D2 [2222555-03-3] [01166] PS1 [1541114-98-0] [01167] PS2 [2245865-85-2] [01168] PS3 [1615218-73-9] [01169] ETM1 [1233200-52-6] [01170] ETM2 [25387-93-3] [01171] HTM-Sol

[0460] The abbreviations of the inventive compounds that are used in the tables set out above in relation to the OLED components relate to the abbreviations provided in the above synthesis examples.

[0461] By comparison with the references, the inventive compounds shown narrower electroluminescence spectra, recognizable by the smaller or equal EL-FWHM values (ELectroluminescence-Full Width Half Maximumwidth of the EL emission spectra in eV at half the peak height). Narrower electroluminescence spectra lead to a distinct improvement in colour purity (lower CIE y values). Moreover, EQE values (External Quantum Efficiencies) are distinctly greater and operating voltages are lower compared to the reference, which leads to a distinct improvement in power efficiencies of the device and hence to lower power consumption.

[0462] Production of Components for Colour Conversion

[0463] The compounds of the invention can be used for colour conversion. For this purpose, compounds are incorporated into a composition which is then processed by known methods (spin-coating, slit-coating, screenprinting, nozzle printing, inkjet printing, etc.) to give pixels or two-dimensional layers. The compositions typically consist of crosslinkable components (monomers, oligomers, polymers), for example based on acrylates, acrylamide, polyesters, silicones etc., and one or more thermally or photochemically activatable starter components. It is additionally possible to introduce further components such as organic auxiliaries (antioxidants, stabilizers, levelling aids, viscosity moderators, etc.) or inorganic fillers (SiO.sub.2, TiO.sub.2, Al.sub.2O.sub.3, etc.).

[0464] General Production Procedure for the Composition and Derived Layers:

[0465] 0.5 g of the inventive compound ES or EAS, 0.2 g of titanium dioxide (TiO.sub.2 ToyoColor, from Toyo Ink Group) and 10 g of OE-6550 Optical Encapsulant (from Dow Corning) are homogenized at 40? C. with very good stirring (magnetic stirrer) under the action of ultrasound (ultrasound bath). Layers of layer thickness about 15 m are produced by knife-coating and then cured by baking under a nitrogen atmosphere (150? C., 1 hour).

[0466] Spectral Measurement of the Layers:

[0467] Fluorescence spectra and EQE values (external quantum efficiency, EQE=photons emitted/photons are absorbed) of the layers are ascertained in a fluorescence spectrometer (09920, Hamamatsu photonics) with an Ulbricht sphere and fibre optics (excitation wavelength OWL: 420-440 nm for blue, 450 nm for green, yellow and red emitters, reference measurement under air at room temperature).

[0468] Results

[0469] Table 11 summarizes the results:

TABLE-US-00035 FWHM EQE Ex. Material Colour [eV] [%] CCG1 ES39 deep green 0.16 26.4 CCG2 ES65 yellow 0.15 26.8 CCG3 ES66 yellow 0.14 27.6 CCG4 ES84 green 0.15 29.6 CCR2 ES67 red 0.15 25.0 CCB3 ES5 deep blue 0.14 25.2 CCB4 ES13 blue 0.15 27.4 CCB5 ES16 blue 0.15 25.6 CCB6 ES17 blue 0.15 27.3 CCB7 ES19 blue 0.14 28.6 CCB8 ES20 deep blue 0.14 24.3 CCB9 ES22 deep blue 0.15 24.0 CCB10 ES26 deep blue 0.15 26.7 CCB11 ES29 blue 0.15 32.1 CCB12 ES32 blue 0.16 34.0 CCB13 ES33 blue 0.15 29.4 CCB14 ES35 blue 0.15 30.1 CCB15 ES36 deep blue 0.15 29.6 CCB16 ES45 deep blue 0.14 21.6 CCB17 ES46 blue 0.14 33.5 CCB18 ES53 blue 0.14 30.3 CCB19 ES57 blue 0.15 31.4 CCB20 EAS5 deep blue 0.15 29.9 CCB21 EAS16 deep blue 0.17 25.8 CCB22 EAS25 deep blue 0.16 24.9 CCB23 EAS33A deep blue 0.15 26.8 CCB24 EAS39 deep blue 0.15 27.8 CCB25 EAS40B blue 0.15 31.0 CCB26 EAS42 blue 0.15 30.3 CCB27 ES72 blue 0.19 31.4 CCB28 ES74 blue 0.14 29.9 CCB29 ES75 blue 0.14 30.4 CCB30 ESA45A blue 0.15 29.1 CCB31 ES80 blue 0.14 28.9 CCB32 ES81 blue 0.18 28.7 CCB33 ES85 blue 0.15 30.3 CCB34 ES89 deep blue 0.16 31.2