HETEROCYCLIC COMPOUNDS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The invention relates to heterocyclic compounds which are suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing said compounds.

Claims

1.-19. (canceled)

20. A compound including at least one structure of the formula (I) ##STR00318## where the ring Ar.sup.a 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 is optionally substituted by one or more Ar or R radicals; and where the further symbols and indices used are as follows: Z.sup.1, Z.sup.2 is the same or different at each instance and is N or B; W.sup.1 is the same or different at each instance and is N, B, C═C(Ar), C═C(R) or C═N, where both carbon atoms of the C═C(Ar) or C═C(R) groups or the carbon atom and the nitrogen atom of the C═N group are each part of the ring Ar.sup.a, where the carbon atom of the C═N group binds to the V.sup.1 group; V.sup.1, V.sup.2 is the same or different at each instance and is —N═, —B═, ═C(Ar)— or ═C(R)—, where not more than one of the V.sup.1, V.sup.2 groups is —N═ or —B═, or the V.sup.1, V.sup.2 groups form a ring of the formula ##STR00319## where the ring Ar.sup.b 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 is optionally substituted by one or more Ar or R radicals, where the ring Ar.sup.b may form a ring system together with an X.sup.1 group or the rings Ar.sup.a and Ar.sup.b together may form a ring system, where W.sup.2 binds to the W.sup.1 group and is the same or different at each instance and is N, B, C═C(Ar), C═C(R) or C═N, where both carbon atoms of the C═C(Ar) or C═C(R) group or the carbon atom and the nitrogen atom of the C═N group are each part of the Ar.sup.b ring, where the carbon atom of the C═N group binds to the W.sup.1 group and the dotted lines represent the bonds to the W.sup.1 or Z.sup.2 group; Y is the same or different at each instance and is a bond, N(Ar), N(R), P(Ar), P(R), P(═O)Ar, P(═O)R, P(═S)Ar, P(═S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C═O, C(R).sub.2, Si(R).sub.2, Ge(R).sub.2, C═NR, C═NAr, C═C(R).sub.2, C═C(R)(Ar), O, S, Se, S═O, or SO.sub.2; 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 is optionally substituted by one or more R radicals; the Ar group here may form a ring system with at least one Ar, X.sup.1, X.sup.3, R group or a further group; X.sup.1 is the same or different at each instance and is N, CR.sup.a, or C if a ring system is formed by a bond to a ring Ar.sup.b or a further group, with the proviso that not more than two of the X.sup.1, X.sup.2 groups in one cycle are N; X.sup.2 is the same or different at each instance and is N or CR.sup.b, with the proviso that not more than two of the X.sup.1, X.sup.2 groups in one cycle are N; X.sup.3 is the same or different at each instance and is N, CR.sup.c, or C if a ring system is formed by a bond to an Ar or R group, the ring Ar.sup.a or a further group, with the proviso that not more than two of the X.sup.3 groups in one cycle are N, or two adjacent X.sup.3 groups together are S or O, where at least one X.sup.3 group is CR.sup.c or C; R, R.sup.a, R.sup.b, R.sup.c 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 in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups is optionally 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 is optionally 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 is optionally substituted by one or more R.sup.1 radicals; at the same time, two R, R.sup.a, R.sup.b, R.sup.c radicals may also together or with a further group form a ring system; 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 is optionally 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, C(═O)OAr″, C(═O)OR.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 is optionally substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C═Se, C═NR.sub.2, —C(═O)O—, —C(═O)NR.sub.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms is optionally 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 is optionally substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and is optionally 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 is optionally 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.sub.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 is optionally replaced by D, F, Cl, Br, I or CN and which is optionally 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; where at least one V.sup.1, V.sup.2, W.sup.1, W.sup.2 group is N or B.

21. The compound as claimed in claim 20, comprising at least one structure of the formula (II-1), (II-2), (II-3) and/or (II-4) ##STR00320## where Z.sup.1, Z.sup.2, Y, X.sup.1, X.sup.2 and X.sup.3 have the definitions given in claim 20; Z.sup.3 is the same or different at each instance and is N or B; W.sup.3, W.sup.4, W.sup.5, W.sup.6 is the same or different at each instance and is C(Ar) or X.sup.6; X.sup.4 is the same or different at each instance and is N, CR.sup.d, or C if a ring system is formed by a bond to an X.sup.1 group, with the proviso that not more than two of the X.sup.4, X.sup.6 groups in one cycle are N; X.sup.5 is the same or different at each instance and is N, CR.sup.e, or C if a ring system is formed by a bond to an Ar group, an X.sup.1 group or an X.sup.3 group, with the proviso that not more than two of the X.sup.5 groups in one cycle are N; X.sup.6 is the same or different at each instance and is N or Crf.sup.f C, with the proviso that not more than two of the X.sup.4, X.sup.6 groups in one cycle are N; R.sup.d, R.sup.e, R.sup.f 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 in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups is optionally 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 is optionally 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 is optionally substituted by one or more R.sup.1 radicals; at the same time, two R.sup.d, R.sup.e, R.sup.f radicals may also form a ring system together or with a further group; where the symbols Ar′ and R.sup.1 have the definitions given in claim 20.

22. The compound as claimed in claim 20, comprising at least one structure of the formulae (IIa-1), (IIa-2), (IIa-3), (IIa-4), (IIb-1), (IIb-2), (IIb-3), (IIb-4), (IIc-1), (IIc-2), (IIc-3), (IIc-4), (IId-1), (IId-2), (IId-3) and/or (IId-4) ##STR00321## ##STR00322## ##STR00323## where the symbols Z.sup.1, Z.sup.2, X.sup.1 and X.sup.2 and X.sup.3 have the definitions given in claim 20, W.sup.3, W.sup.4, W.sup.5, W.sup.6 is the same or different at each instance and is C(Ar) or X.sup.6; X.sup.4 is the same or different at each instance and is N, CR.sup.d, or C if a ring system is formed by a bond to an X.sup.1 group, with the proviso that not more than two of the X.sup.4, X.sup.6 groups in one cycle are N; X.sup.5 is the same or different at each instance and is N, CR.sup.e, or C if a ring system is formed by a bond to an Ar group, an X.sup.1 group or an X.sup.3 group, with the proviso that not more than two of the X.sup.5 groups in one cycle are N; X.sup.6 is the same or different at each instance and is N or Crf.sup.f C, with the proviso that not more than two of the X.sup.4, X.sup.6 groups in one cycle are N; R.sup.d, R.sup.e, R.sup.f 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 in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups is optionally 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 is optionally 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 is optionally substituted by one or more R.sup.1 radicals; at the same time, two R.sup.d, R.sup.e, R.sup.f radicals may also form a ring system together or with a further group; where the symbols Ar′ and R.sup.1 have the definitions given in claim 20; Z.sup.4 is N, B or Al; X.sup.7 is the same or different at each instance and is N, CR.sup.g, or C if a ring system is formed by a bond to an X.sup.1, X.sup.3 or R group or a further group, with the proviso that not more than two of the X.sup.7 groups in one cycle are N; Y.sup.a is the same or different at each instance and is C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2; R.sup.g 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 in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups is optionally 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 is optionally 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 is optionally substituted by one or more R.sup.1 radicals; at the same time, two R.sup.g radicals may also form a ring system together or with a further group, where the symbols Ar′ and R.sup.1 have the definitions given in claim 20.

23. The compound as claimed in claim 20, including at least one structure of the formula (III-1) to (III-15): ##STR00324## ##STR00325## ##STR00326## where the symbols Z.sup.1, Z.sup.2, Z.sup.3, Y, X.sup.1, X.sup.2 and X.sup.3 have the definitions given in claim 20; X.sup.4 is the same or different at each instance and is N, CR.sup.d, or C if a ring system is formed by a bond to an X.sup.1 group, with the proviso that not more than two of the X.sup.4, X.sup.6 groups in one cycle are N; X.sup.5 is the same or different at each instance and is N, CR.sup.e, or C if a ring system is formed by a bond to an Ar group, an X.sup.1 group or an X.sup.3 group, with the proviso that not more than two of the X.sup.5 groups in one cycle are N; X.sup.6 is the same or different at each instance and is N or Crf.sup.f C, with the proviso that not more than two of the X.sup.4, X.sup.6 groups in one cycle are N; R.sup.d, R.sup.e, R.sup.f 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 in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups is optionally 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 is optionally 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 is optionally substituted by one or more R.sup.1 radicals; at the same time, two R.sup.d, R.sup.e, R.sup.f radicals may also form a ring system together or with a further group; where the symbols Ar′ and R.sup.1 have the definitions given in claim 20; p is 0 or 1, where p=0 means that the Y.sup.1 group is absent; Y.sup.1 is the same or different at each instance and is a bond, N(Ar′), N(R), P(Ar′), P(R), P(═O)Ar′, P(═O)R, P(═S)Ar′, P(═S)R, B(Ar′), B(R), Al(Ar′), Al(R), Ga(Ar′), Ga(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2, where the symbols R and Ar′ have the definition set out in claim 20; Y.sup.3 is the same or different at each instance and is N(Ar′), N(R), P(Ar′), P(R), P(═O)Ar′, P(═O)R, P(═S)Ar′, P(═S)R, B(Ar′), B(R), Al(Ar′), Al(R), Ga(Ar′), Ga(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2, where the symbols R and Ar′ have the definition set out in claim 20.

24. The compound as claimed in claim 20, comprising at least one structure of the formulae (IIIa-1) to (IIIa-15), (IIIb-1) to (IIIb-15), (IIIc-1) to (IIIc-15) and/or (IId-1) to (IIId-15) ##STR00327## ##STR00328## ##STR00329## ##STR00330## ##STR00331## ##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336## ##STR00337## ##STR00338## where the symbols Z.sup.1, Z.sup.2, Y, X.sup.1, X.sup.2 and X.sup.3 have the definitions given in claim 20; Z.sup.3 is the same or different at each instance and is N or B; X.sup.4 is the same or different at each instance and is N, CR.sup.d, or C if a ring system is formed by a bond to an X.sup.1 group, with the proviso that not more than two of the X.sup.4, X.sup.6 groups in one cycle are N; X.sup.5 is the same or different at each instance and is N, CR.sup.e, or C if a ring system is formed by a bond to an Ar group, an X.sup.1 group or an X.sup.3 group, with the proviso that not more than two of the X.sup.5 groups in one cycle are N; X.sup.6 is the same or different at each instance and is N or Crf.sup.f C, with the proviso that not more than two of the X.sup.4, X.sup.6 groups in one cycle are N; R.sup.d, R.sup.e, R.sup.f 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 in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups is optionally 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 is optionally 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 is optionally substituted by one or more R.sup.1 radicals; at the same time, two R.sup.d, R.sup.e, R.sup.f radicals may also form a ring system together or with a further group; where the symbols Ar′ and R.sup.1 have the definitions given in claim 20; Z.sup.4 is N, B or Al; X.sup.7 is the same or different at each instance and is N, CR.sup.g, or C if a ring system is formed by a bond to an X.sup.1, X.sup.3 or R group or a further group, with the proviso that not more than two of the X.sup.7 groups in one cycle are N; Y.sup.a is the same or different at each instance and is C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2; R.sup.g 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 in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups is optionally 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 is optionally 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 is optionally substituted by one or more R.sup.1 radicals; at the same time, two R.sup.g radicals may also form a ring system together or with a further group, where the symbols Ar′ and R.sup.1 have the definitions given in claim 20; p is 0 or 1, where p=0 means that the Y.sup.1 group is absent; Y.sup.1 is the same or different at each instance and is a bond, N(Ar′), N(R), P(Ar′), P(R), P(═O)Ar′, P(═O)R, P(═S)Ar′, P(═S)R, B(Ar′), B(R), Al(Ar′), Al(R), Ga(Ar′), Ga(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2, where the symbols R and Ar′ have the definition set out in claim 20; Y.sup.3 is the same or different at each instance and is N(Ar′), N(R), P(Ar′), P(R), P(═O)Ar′, P(═O)R, P(═S)Ar′, P(═S)R, B(Ar′), B(R), Al(Ar′), Al(R), Ga(Ar′), Ga(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2, where the symbols R and Ar′ have the definition set out in claim 20; q is 0 or 1, where q=0 means that the Y.sup.2 group is absent; and Y.sup.2 is the same or different at each instance and is a bond, N(Ar′), N(R), P(Ar′), P(R), P(═O)Ar′, P(═O)R, P(═S)Ar′, P(═S)R, B(Ar′), B(R), Al(Ar′), Al(R), Ga(Ar′), Ga(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2, where the symbols R and Ar′ have the definition set out in claim 20.

25. The compound as claimed in claim 20, including at least one structure of the formula (IV-1) to (IV-28): ##STR00339## ##STR00340## ##STR00341## ##STR00342## ##STR00343## ##STR00344## ##STR00345## where the symbols Z.sup.1, Z.sup.2, Y, R.sup.a, R.sup.b and R.sup.c have the definitions given in claim 20; Z.sup.3 is the same or different at each instance and is N or B; R.sup.d, R.sup.e, R.sup.f 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 in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups is optionally 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 is optionally 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 is optionally substituted by one or more R.sup.1 radicals; at the same time, two R.sup.d, R.sup.e, R.sup.f radicals may also form a ring system together or with a further group; where the symbols Ar′ and R.sup.1 have the definitions given in claim 20; R.sup.g 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 in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups is optionally 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 is optionally 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 is optionally substituted by one or more R.sup.1 radicals; at the same time, two R.sup.g radicals may also form a ring system together or with a further group, where the symbols Ar′ and R.sup.1 have the definitions given in claim 20; Y.sup.1 is the same or different at each instance and is a bond, N(Ar′), N(R), P(Ar′), P(R), P(═O)Ar′, P(═O)R, P(═S)Ar′, P(═S)R, B(Ar′), B(R), Al(Ar′), Al(R), Ga(Ar′), Ga(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2, where the symbols R and Ar′ have the definition set out in claim 20; Y.sup.3 is the same or different at each instance and is N(Ar′), N(R), P(Ar′), P(R), P(═O)Ar′, P(═O)R, P(═S)Ar′, P(═S)R, B(Ar′), B(R), Al(Ar′), Al(R), Ga(Ar′), Ga(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2, where the symbols R and Ar′ have the definition set out in claim 20; m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3; j is 0, 1 or 2; and k is 0 or 1.

26. The compound as claimed in claim 21, wherein Z.sup.1 is N and at least one of the Z.sup.2 or Z.sup.3 groups is B.

27. The compound as claimed in claim 21, wherein Z.sup.1 is N and at least one of the Z.sup.2 or Z.sup.3 groups is N.

28. The compound as claimed in claim 21, wherein Z.sup.1 is B and at least one of the Z.sup.2 or Z.sup.3 groups is N.

29. The compound as claimed in claim 21, that Z.sup.1 is B and at least one of the Z.sup.2 or Z.sup.3 groups is B.

30. The compound as claimed in claim 20, wherein at least two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f, R.sup.g radicals together with the further groups to which the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f, R.sup.g radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f, R.sup.g radicals form at least one structure of the formulae (RA-1) to (RA-12): ##STR00346## ##STR00347## 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.f, R.sup.g radicals bind, and the further symbols have the following definition: Y.sup.4 is the same or different at each instance and is C(R.sup.1).sub.2, (R.sup.1).sub.2C—C(R.sup.1).sub.2, (R.sup.1)C═C(R.sup.1), NR.sup.1, NAr′, O or S; R.sup.h 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 is optionally substituted in each case by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, C═S, C═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 is optionally 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 is optionally substituted by one or more R.sup.2 radicals; at the same time, it is also possible for two R.sup.h radicals together or one R.sup.h radical together with an R.sup.1 radical or together with a further group to form a ring system; s is 0, 1, 2, 3, 4, 5 or 6; t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

31. The compound as claimed in claim 20, wherein at least two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f, R.sup.g radicals together with the further groups to which the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f, R.sup.g radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f, R.sup.g radicals form the structures of the formula (RB): ##STR00348## where R.sup.1 has the definition set out in claim 20, 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.f, R.sup.g radicals bind, the index m is 0, 1, 2, 3 or 4, and Y.sup.5 is C(R.sup.1).sub.2, NR.sup.1, NAr′, BR.sup.1, BAr′, O or S.

32. The compound as claimed in claim 20, comprising at least one structure of the formulae (VI-1) to (VI-9), where the compounds have at least one fused ring, ##STR00349## ##STR00350## where the symbols Z.sup.1, Z.sup.2, Y, R.sup.a, R.sup.b and R.sup.c have the definitions given in claim 20, Z.sup.3 is the same or different at each instance and is N or B; R.sup.d, R.sup.e, R.sup.f 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 in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups is optionally 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 is optionally 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 is optionally substituted by one or more R.sup.1 radicals; at the same time, two R.sup.d, R.sup.e, R.sup.f radicals may also form a ring system together or with a further group; where the symbols Ar′ and R.sup.1 have the definitions given in claim 20; Y.sup.3 is the same or different at each instance and is N(Ar′), N(R), P(Ar′), P(R), P(═O)Ar′, P(═O)R, P(═S)Ar′, P(═S)R, B(Ar′), B(R), Al(Ar′), Al(R), Ga(Ar′), Ga(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2, where the symbols R and Ar′ have the definition set out in claim 20; m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3; j is 0, 1 or 2.

33. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 20, wherein, in place of a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

34. A formulation comprising at least one compound as claimed in claim 20 and at least one further compound, where the further compound is selected from one or more solvents.

35. A formulation comprising the oligomer, polymer or dendrimer as claimed in claim 33 and at least one further compound, where the further compound is selected from one or more solvents.

36. A composition comprising at least one compound as claimed in claim 20 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.

37. A composition comprising the oligomer, polymer or dendrimer as claimed in claim 33 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.

38. A process for preparing the compound as claimed in claim 20, wherein a base skeleton having at least one of the Z.sup.2 groups or a precursor of one of the Z.sup.2 groups is synthesized, and the Z.sup.1 group is introduced by means of a metalation reaction, a nucleophilic aromatic substitution reaction or a coupling reaction.

39. An electronic device comprising at least one compound as claimed in claim 20.

40. An electronic device comprising the oligomer, polymer or dendrimer as claimed in claim 33.

Description

EXAMPLES

[0241] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. 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 have multiple enantiomeric, diastereomeric or tautomeric forms, one form is shown in a representative manner.

[0242] Synthesis of Synthons S:

Example S1

[0243] ##STR00146##

[0244] Preparation according to W. Wu et al., Organic Chemistry Frontiers, 2019, 6(13), 2200 using indole [120-72-9] and 2-iodo-4,6-dimethylaniline [4102-54-9], yield: 64%; purity: about 95% by .sup.1H NMR.

[0245] The following compounds can be prepared analogously:

TABLE-US-00001 Ex. Reactants Product Yield S2 [00147] [00148] 59% S3 [00149] [00150] 69% S4 [00151] [00152] 56% S5 [00153] [00154] 60% S6 [00155] [00156] 67% S7 [00157] [00158] 49%

Example S10

[0246] ##STR00159##

[0247] Preparation according to US2019/0252623, p. 62. Use of S1 rather than compound A, procedure from step 1 to 3, yield: 38%; purity: about 95% by .sup.1H NMR.

[0248] The following compounds can be prepared analogously:

TABLE-US-00002 Ex. Reactants Product Yield S11 [00160] [00161] 40% S12 [00162] [00163] 40% S13 [00164] [00165] 35% S14 [00166] [00167] 38% S15 [00168] [00169] 42% S16 [00170] [00171] 35% S17 [00172] [00173] 38% S18 [00174] [00175] 41% S19 [00176] [00177] 50%

Example S100

[0249] ##STR00178##

[0250] A mixture of 20.6 g (100 mmol) of 10H-indolo[1,2-a]benzimidazole [2345630-10-4], 31.7 g (100 mmol) of 1-bromo-2-chloro-3-iodobenzene [57012-50-7], 48.9 g (150 mmol) of cesium carbonate, anhydrous [534-17-8], 1.2 g (10 mmol) of S-proline [147-85-3], 952 mg (5 mmol) of copper(I) iodide [7681-65-4], 50 g of glass beads (diameter 3 mm) and 250 ml of DMSO is stirred at 100° C. for 14 h. After cooling, the reaction mixture is admixed with 500 ml of ethyl acetate and 500 ml of water, and the organic phase is removed, washed once with 500 ml of water and twice with 300 ml each time of saturated sodium chloride solution, and dried over magnesium sulfate. The mixture is filtered through a silica gel bed in the form of an ethyl acetate slurry, the filtrate is concentrated to dryness, the residue is boiled with 50 ml of ethanol, the solids are filtered off with suction, and these are washed twice with 10 ml of ethanol, dried under reduced pressure and recrystallized from toluene or flash-chromatographed (Torrent automated column system from A. Semrau). Yield: 19.8 g (45 mmol) 45%; purity: about 95% by .sup.1H NMR.

[0251] The following compound can prepared analogously:

TABLE-US-00003 Ex. Reactants Product Yield S101 [00179] [00180] 22% S102 [00181] [00182] 26% S103 [00183] [00184] 44% S104 [00185] [00186] 40% S105 [00187] [00188] 43% S106 [00189] [00190] 47% S107 [00191] [00192] 45% S108 [00193] [00194] 38% S109 [00195] [00196] 45% S110 [00197] [00198] 45% S111 [00199] [00200] 48% S112 [00201] [00202] 50% S113 [00203] [00204] 43% S114 [00205] [00206] 51%

Example S200

[0252] ##STR00207##

[0253] A mixture of 39.6 g (100 mmol) of S100, 13.4 g (110 mmol) of phenylboronic acid [98-80-6], 42.5 g (200 mmol) of tripotassium phosphate, anhydrous [7778-53-2], 1.83 g (6 mmol) of tri-o-tolylphosphine [6163-58-2], 225 mg (1 mmol) of palladium(II) acetate [3375-31-3], 300 ml of toluene, 100 ml of dioxane and 300 ml of water is stirred under reflux for 16 h. After cooling, the reaction mixture is admixed with 300 ml of ethyl acetate and 300 ml of water, and the organic phase is removed, washed once with 300 ml of water and twice with 200 ml each time of saturated sodium chloride solution, and dried over magnesium sulfate. The mixture is filtered through a silica gel bed in the form of an ethyl acetate slurry, the filtrate is concentrated to dryness, the residue is boiled with 50 ml of ethanol, the solids are filtered off with suction, and these are washed twice with 20 ml of ethanol, dried under reduced pressure and recrystallized from acetonitrile or purified by flash chromatography (Torrent automated column system from A. Semrau). Yield: 26.3 g (67 mmol) 67%; purity: about 95% by .sup.1H NMR.

[0254] The following compounds can be prepared analogously:

TABLE-US-00004 Ex. Reactants Product Yield S201 [00208] [00209] 46% S202 [00210] [00211] 40% S203 [00212] [00213] 60% S204 [00214] [00215] 64% S205 [00216] [00217] 71% S206 [00218] [00219] 68% S207 [00220] [00221] 65% S208 [00222] [00223] 66% S209 [00224] [00225] 70% S210 [00226] [00227] 58% S211 [00228] [00229] 55% S212 [00230] [00231] 73% S213 [00232] [00233] 71% S214 [00234] [00235] 67%

Example S300

[0255] ##STR00236##

[0256] A mixture of 39.6 g (100 mmol) of S100, 18.6 g (110 mmol) of diphenylamine [122-39-4], 14.4 g (150 mmol) of sodium tert-butoxide [865-48-5], 809 mg (4 mmol) of tri-tert-butylphosphine [13716-12-6], 449 mg (2 mmol) of palladium(II) acetate [3375-31-3] and 400 ml of toluene is stirred at 100° C. for 12 h. After cooling, 300 ml of water are added to the reaction mixture, and the organic phase is removed, washed once with 300 ml of water and twice with 200 ml each time of saturated sodium chloride solution, and dried over magnesium sulfate. The mixture is concentrated, the residue is taken up in 300 ml of ethyl acetate and filtered through a silica gel bed in the form of an ethyl acetate slurry, the filtrate is concentrated to dryness, the residue is boiled with 70 ml of ethanol, the solids are filtered off with suction, and these are washed twice with 20 ml of ethanol, dried under reduced pressure and recrystallized from acetonitrile or purified by flash chromatography (Torrent automated column system from A. Semrau). Yield: 33.5 g (69 mmol) 69%; purity: about 95% by H NMR.

[0257] The following compounds can be prepared analogously:

TABLE-US-00005 Ex. Reactants Product Yield S301 [00237] [00238] 33% S302 [00239] [00240] 30% S303 [00241] [00242] 64% S304 [00243] [00244] 58% S305 [00245] [00246] 67% S306 [00247] [00248] 65% S307 [00249] [00250] 70% S308 [00251] [00252] 68% S309 [00253] [00254] 69% S310 [00255] [00256] 36% S311 [00257] [00258] 48% S312 [00259] [00260] 34% S313 [00261] [00262] 55% S314 [00263] [00264] 45% S315 [00265] [00266] 50%

Example: Regioisomeric Dopants D1A and D1B

[0258] Step 1: Lithiation of S200

##STR00267##

[0259] A baked-out, argon-inertized four-neck flask with magnetic stirrer bar, dropping funnel, water separator, reflux condenser and argon blanketing is charged with 19.7 g (50 mmol) of S200 and 200 ml of tert-butylbenzene, and cooled to −40° C. 64.7 ml (110 mmol) of tert-butyllithium, 1.7 M in n-pentane, is added dropwise to the mixture over 10 min. The reaction mixture is allowed to warm up to room temperature and stirred at 60° C. for a further 3 h, in the course of which n-pentane is distilled off via the water separator.

[0260] Step 2: Transmetalation and Cyclization

##STR00268##

[0261] The reaction mixture is cooled back down to −40° C. 5.7 ml (60 mmol) of boron tribromide is added dropwise over a period of about 10 min. On completion of addition, the reaction mixture is stirred at RT for 1 h. Then the reaction mixture is cooled down to 0° C., and 21.0 ml (120 mmol) of di-iso-propylethylamine is added dropwise over a period of about 30 min.

[0262] Then the reaction mixture is stirred at 130° C. for 5 h. After cooling, the mixture is diluted with 500 ml of toluene and hydrolyzed by addition of 300 ml of aqueous 10% by weight potassium acetate solution, and the organic phase is removed and concentrated to dryness under reduced pressure. The oily residue is absorbed with DCM onto ISOLUTE© and hot-filtered through a silica gel bed with an n-pentane-DCM mixture (10:1). The filtrate is concentrated to dryness. The residue is subjected to flash chromatography, silica gel, n-heptane/ethyl acetate, gradient, Torrent automated column system from A. Semrau. Further purification of the separated regioisomers is effected by repeated hot extraction crystallization with DCM/acetonitrile mixtures and final fractional sublimation or heat treatment under reduced pressure. Yield: D1A: 2.39 g (6.5 mmol) 13%/D1B: 3.30 (9 mmol) 18%; purity: about 99.9% by .sup.1H NMR.

[0263] The following compounds can be prepared analogously:

TABLE-US-00006 Ex. Reactant Products Yield D2 S201 [00269] 11% D3 S202 [00270]  9% D4A S203 [00271] 17% D4B S203 [00272] 13% D5A S204 [00273] 15% D5B S204 [00274] 13% D6 S205 [00275] 32% D7 S206 [00276] 29% D8 S207 [00277] 26% D9 S208 [00278] 30% D10 S209 [00279] 28% D11 S210 [00280] 32% D12 S211 [00281] 22% D13A S212 [00282] 20% D138 S212 [00283] 19% D14A S213 [00284] 18% D148 S213 [00285] 16% D15 S214 [00286] 24% D100A S300 [00287] 20% D100B S300 [00288] 23% D101A S303 [00289] 18% D1018 S301 [00290] 24% D102A S304 [00291] 15% D102B S304 [00292] 17% D103 S305 [00293] 26% D104 S306 [00294] 29% D105 S307 [00295] 28% D106 S308 [00296] 33% D107 S309 [00297] 11% D108 S310 [00298] 17% D109A S311 [00299] 23% D109B S311 [00300] 21% D110A S312 [00301] 13% D110B S312 [00302]  9% D111A S313 [00303] 19% D1118 S313 [00304] 21% D112 S314 [00305] 28% D113 S315 [00306] 16%

[0264] Examples D103 to D107 show that the formation of a mixture can be avoided by suitable substitution, where the X.sup.5 group in particular, by way of example, comprises an alkyl group in the ortho position to the Z.sup.2 group. It is of course possible to choose any other appropriate substitution group.

[0265] Examples D112 and D113 show that the formation of a mixture can be avoided by suitable substitution, where the X.sup.4 group in particular, by way of example, comprises an alkyl group and/or a phenyl group. It is of course possible to choose any other appropriate substitution group.

[0266] Production of OLED Components

[0267] 1) Vacuum-Processed Components:

[0268] OLEDs 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).

[0269] 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 Al 4083 from Heraeus Precious Metals GmbH Germany, 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.

[0270] The OLEDs basically have the following layer structure: Substrate/hole injection layer 1 (HIL1) consisting of Ref-HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 1 (HTL1) composed of: 160 nm HTM1 for UV & blue OLEDs; 50 nm for green and yellow OLEDs; 110 nm for red OLEDs/hole transport layer 2 (HTL2) composed of: 10 nm for blue OLEDs; 20 nm for green & yellow OLEDs; 10 nm for red OLEDs/emission layer (EML): 25 nm for blue OLEDs; 40 nm for green & yellow OLEDs; 35 nm for red OLEDs/hole blocker layer (HBL) 10 nm/electron transport layer (ETL) 30 nm/electron injection layer (EIL) composed of 1 nm ETM2/and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm.

[0271] First of all, vacuum-processed OLEDs are described. For this purpose, all the materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as SMB1:D1 (95:5%) mean here that the material SMB1 is present in the layer in a proportion by volume of 95% and D1 in a proportion of 5%. Analogously, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLEDs can be found in table 1. The materials used for production of the OLEDs are shown in table 4.

[0272] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) are, as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2.

[0273] Use of compounds of the invention as materials in OLEDs:

[0274] One use of the compounds of the invention can be as dopant in the emission layer and as transport or blocker materials (HBL) in OLEDs. The compounds D-Ref.1 according to table 4 are used as a comparison according to the prior art. The results for the OLEDs are collated in table 2.

TABLE-US-00007 TABLE 1 Structure of the OLEDs Ex. EML HBL ETL Blue OLEDs (400-499 nm) D-Ref. 1 SMB1:D-Ref. 1 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D1A SMB1:D1A ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D3 SMB1:D3 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D4A SMB1:D4A ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D5A SMB1:D5A ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D7 SMB1:D7 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D9 SMB1:D9 ETM1 ETM1:ETM2 (97%:3%) (50%:50%) D-D10 SMB1:D10 ETM1 ETM1:ETM2 (92%:8%) (50%:50%) D-D11 SMB1:D11 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D13A SMB1:D13A ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D15 SMB1:D15 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D100A SMB1:D100A ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D101A SMB1:D101A ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D103 SMB1:D103 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D104 SMB1:D104 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D105 SMB1:D105 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D106 SMB1:D106 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D107 SMB2:D107 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D108 SMB1:D108 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D109A SMB1:D109A ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D110A SMB1:D110A ETM1 ETM1:ETM2 (95%:5%) (50%:50%) Green OLEDs (500-549 nm) Yellow OLEDs (550-600 nm) D-D100B SMB1:D100B ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D109B SMB1:D109B ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D112 SMB1:D ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D113 SMB1:D113 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D1B SMB1:D1B ETM1 ETM1:ETM2 (92%:8%) (50%:50%) D-D13B SMB1:D13B ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D101B SMB1:D101B ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D110B SMB1:D110B ETM1 ETM1:ETM2 (95%:5%) (50%:50%) Red OLEDs (601-800 nm) D-D4B SMB1:D4B ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D5B SMB1:D5B ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D14B SMB1:D14B ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D15 SMB1:D15 ETM1 ETM1:ETM2 (95%:5%) (50%:50%)

TABLE-US-00008 TABLE 2 Results for the vacuum-processed OLEDs at 1000 cd/m.sup.2 Ex. EQE (%) Voltage (V) Color Blue OLEDs (430-499 nm) Ref. 1 5.9 4.7 blue D-D1A 5.9 4.5 blue D-D3 6.2 4.3 blue D-D4A 6.5 4.3 blue D-D5A 6.4 4.4 blue D-D7 6.5 4.1 blue D-D9 6.8 4.3 blue D-D10 6.4 4.0 blue D-D11 6.3 4.3 blue D-D13A 6.5 4.3 blue D-D100A 6.7 4.2 blue D-D101A 7.0 4.2 blue D-D103 6.9 4.4 blue D-D104 6.2 4.5 blue D-D105 6.4 4.3 blue D-D106 6.5 4.3 blue D-D107 6.5 4.4 blue D-D108 6.5 4.2 blue D-D109A 6.7 4.2 blue D-D110A 6.3 4.1 blue Green OLEDs (500-549 nm) Yellow OLEDs (550-600 nm) D-D100B 6.4 4.2 green D-D109B 6.6 4.1 green D-D112 6.6 4.2 green D-D113 6.2 4.2 green D-D1B 7.0 4.3 yellow D-D13B 6.7 4.3 yellow D-D101B 6.8 4.2 yellow D-D110B 6.5 4.1 yellow Red OLEDs (601-800 nm) D-D4B 5.6 3.7 red D-D5B 5.8 3.8 red D-D14B 5.4 4.0 red D-D15 5.9 4.1 red

[0275] 2)

[0276] Solution-Processed Components:

[0277] 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 vapor 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.

[0278] The construction used is thus as follows: [0279] substrate, [0280] ITO (50 nm), [0281] PEDOT (20 nm), [0282] hole transport layer (HIL2) (20 nm), [0283] emission layer (92% host H1, 8% dopant) (60 nm), [0284] electron transport layer (ETM1 50%+ETM2 50%) (20 nm), [0285] cathode (Al).

[0286] Substrates used are glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm. For better processing, these are coated with the buffer (PEDOT) Clevios P VP Al 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 of the structure shown in table 4, 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.

[0287] 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 H1 (92%):D (8%) mean here that the material H1 is present in the emission layer in a proportion by weight of 92% and the dopant D in a proportion by weight of 8%. 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 60 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 4.

[0288] The materials for the electron transport layer and for the cathode are applied by thermal vapor 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 ETM1:ETM2 (50%: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 4.

TABLE-US-00009 TABLE 3 Results for the solution-processed OLEDs at 1000 cd/m.sup.2 Ex Dopant EQE (%) Voltage (V) Color Blue OLEDs (430-499 nm) Ref.-Sol. Ref.-D1 4.4 4.9 blue Sol.-D12 D12 4.8 4.5 blue Sol.-D102A D102A 4.9 4.6 blue Green OLEDs (500-549 nm) Yellow OLEDs (550-600 nm) Sol.-D102B D102B 5.7 4.2 yellow

TABLE-US-00010 TABLE 4 Structural formulae of the materials used [00307] [00308] [00309] [00310] [00311] [00312] [00313] [00314] [00315] [00316] [00317]

[0289] The compounds of the invention show higher EQE values (External Quantum Efficiencies) at reduced operating voltages compared to the reference, which leads to a distinct improvement in power efficiencies of the device and hence to lower power consumption.