COMPOUNDS THAT CAN BE USED IN AN ORGANIC ELECTRONIC DEVICE AS ACTIVE COMPOUNDS

Abstract

The invention relates to compounds that can be used in an organic electronic device as an active compound, in particular for use in electronic devices. The invention further relates to a method for producing the compounds according to the invention, and to electronic devices comprising same.

Claims

1.-19. (canceled)

20. A compound usable with preference as active compound in an organic electronic device, wherein the compound has at least one aromatic or heteroaromatic ring system which has 5 to 60 carbon atoms and is fused to an aliphatic polycyclic ring system having at least 3 rings.

21. The compound as claimed in claim 20, wherein the largest cycle of the aliphatic polycyclic ring system having at least 3 rings has not more than 14 atoms in the corresponding ring.

22. The compound as claimed in claim 20, comprising at least one structure of the formulae (I) to (XVIII): ##STR00370## ##STR00371## ##STR00372## where the symbols used are as follows: Y is the same or different at each instance and is O, S, C(R).sub.2, CArR, C(Ar).sub.2, Si(Ar).sub.2, SiArR or Si(R).sub.2, NR or NAr; X is the same or different at each instance and is N or CR; 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.1).sub.2, C(═O)N(Ar).sub.2, C(═O)N(R.sup.1).sub.2, Si(Ar).sub.3, Si(R.sup.1).sub.3, B(OAr).sub.2, B(OR.sup.1).sub.2, C(═O)Ar, C(═O)R.sup.1, P(═O)(Ar).sub.2, P(═O)(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 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 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 may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S or CONR.sup.1, or an aromatic or heteroaromatic ring system which has 5 to 40 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 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, two R radicals together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic 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 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 silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined to one another 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, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.2).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.2, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, B(OR.sup.2).sub.2, Si(Ar.sup.1).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 or alkynyl 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, Ge(R.sup.2).sub.2, Sn(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 40 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 40 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 40 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, adjacent R.sup.1 radicals together may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; Ar.sup.1 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, nonaromatic R.sup.2 radicals; at the same time, it is possible for two Ar.sup.1 radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined to one another 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 H, D, F, Cl, Br, I, CN, B(OR.sup.3).sub.2, NO.sub.2, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.3).sub.2, N(R.sup.3).sub.2, NO.sub.2, P(═O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.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, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2 and 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 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more, adjacent substituents R.sup.2 together may also may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; R.sup.3 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 having 5 to 30 aromatic ring atoms 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 adjacent substituents R.sup.3 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; the index s is 0, 1, 2, 3, 4, 5 or 6; the index t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; and the index v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

23. The compound as claimed in claim 22, comprising at least one structure of the formulae (Ia) to (XVIIIa): ##STR00373## ##STR00374## ##STR00375## wherein Y is the same or different at each instance and is O, S, C(R).sub.2, CArR, C(Ar).sub.2, Si(Ar).sub.2, SiArR or Si(R).sub.2, NR or 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.1).sub.2, C(═O)N(Ar).sub.2, C(═O)N(R.sup.1).sub.2, Si(Ar).sub.3, Si(R.sup.1).sub.3, B(OAr).sub.2, B(OR.sup.1).sub.2, C(═O)Ar, C(═O)R.sup.1, P(═O)(Ar).sub.2, P(═O)(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 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 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 may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S or CONR.sup.1, or an aromatic or heteroaromatic ring system which has 5 to 40 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 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, two R radicals together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic 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 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 silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined to one another 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, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.2).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.2, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, B(OR.sup.2).sub.2, Si(Ar.sup.1).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 or alkynyl 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, Ge(R.sup.2).sub.2, Sn(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 40 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 40 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 40 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, adjacent R.sup.1 radicals together may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; Ar.sup.1 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, nonaromatic R.sup.2 radicals; at the same time, it is possible for two Ar.sup.1 radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined to one another 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 H, D, F, Cl, Br, I, CN, B(OR.sup.3).sub.2, NO.sub.2, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.3).sub.2, N(R.sup.3).sub.2, NO.sub.2, P(═O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.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, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2 and 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 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more, adjacent substituents R.sup.2 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; R.sup.3 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 having 5 to 30 aromatic ring atoms 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 adjacent substituents R.sup.3 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; the index s is 0, 1, 2, 3, 4, 5 or 6; the index t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; the index v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; the index o is 0, 1 or 2; the index n is 0, 1, 2, or 3; the index m is 0, 1, 2, 3 or 4; and the index 1 is 0, 1, 2, 3, 4, 5 or 6.

24. The compound as claimed in claim 20, wherein the compound comprises at least two aliphatic polycyclic ring systems having at least 3 rings.

25. The compound as claimed in claim 20, wherein the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which an aliphatic polycyclic ring system having at least 3 rings is fused is selected from phenyl, ortho-, meta- or para-biphenyl, terphenyl, quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, pyrenyl, triazinyl, imidazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1-, 2-, 3- or 4-carbazolyl, 1- or 2-naphthyl, anthracenyl, phenanthrenyl and/or triphenylenyl, each of which may be substituted by one or more R and/or R.sup.1 radicals.

26. The compound as claimed in claim 20, wherein the aliphatic polycyclic ring system which has at least 3 rings and is fused to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms forms a substructure of the formulae (N-1) to (N-6) ##STR00376## wherein R.sup.1 is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.2).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.2, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, B(OR.sup.2).sub.2, Si(Ar.sup.1).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 or alkynyl 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, Ge(R.sup.2).sub.2, Sn(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 40 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 40 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 40 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, adjacent R.sup.1 radicals together may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; Ar.sup.1 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, nonaromatic R.sup.2 radicals; at the same time, it is possible for two Ar.sup.1 radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined to one another 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 H, D, F, Cl, Br, I, CN, B(OR.sup.3).sub.2, NO.sub.2, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.3).sub.2, N(R.sup.3).sub.2, NO.sub.2, P(═O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.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, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2 and 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 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more, adjacent substituents R.sup.2 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; R.sup.3 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 having 5 to 30 aromatic ring atoms 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 adjacent substituents R.sup.3 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; the index s is 0, 1, 2, 3, 4, 5 or 6; the index t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; the index v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; and the dotted lines represent the bonds of the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which the aliphatic polycyclic ring system having at least 3 rings is fused.

27. The compound as claimed in claim 20, wherein the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which an aliphatic polycyclic ring system having at least 3 rings is fused forms a substructure of the formulae (Ar-1) to (Ar-66) ##STR00377## ##STR00378## ##STR00379## ##STR00380## ##STR00381## ##STR00382## ##STR00383## ##STR00384## ##STR00385## ##STR00386## ##STR00387## wherein X′ is N or CR.sup.1; Y′ is selected from O, S, C(R.sup.1).sub.2, Si(R.sup.1).sub.2, NR.sup.1 and NAr.sup.1; U is selected from O, S, C(R.sup.1).sub.2, N(R.sup.1), B(R.sup.1), Si(R.sup.1).sub.2, C═O, S═O, SO.sub.2, 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, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.2).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.2, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, B(OR.sup.2).sub.2, Si(Ar.sup.1).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 or alkynyl 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, Ge(R.sup.2).sub.2, Sn(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 40 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 40 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 40 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, adjacent R.sup.1 radicals together may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; Ar.sup.1 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, nonaromatic R.sup.2 radicals; at the same time, it is possible for two Ar.sup.1 radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined to one another 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 H, D, F, Cl, Br, I, CN, B(OR.sup.3).sub.2, NO.sub.2, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.3).sub.2, N(R.sup.3).sub.2, NO.sub.2, P(═O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.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, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2 and 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 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more, adjacent substituents R.sup.2 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; R.sup.3 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 having 5 to 30 aromatic ring atoms 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 adjacent substituents R.sup.3 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; and the aliphatic polycyclic ring system having at least 3 rings binds to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms at the respective positions identified by o to form a ring.

28. The compound as claimed in claim 20, wherein the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which an aliphatic polycyclic ring system having at least 3 rings is fused forms a substructure of the formulae (Ar′-1) to (Ar′-65) ##STR00388## ##STR00389## ##STR00390## ##STR00391## ##STR00392## ##STR00393## ##STR00394## ##STR00395## ##STR00396## ##STR00397## ##STR00398## where R.sup.1 is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.2).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.2, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, B(OR.sup.2).sub.2, Si(Ar.sup.1).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 or alkynyl 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, Ge(R.sup.2).sub.2, Sn(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 40 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 40 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 40 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, adjacent R.sup.1 radicals together may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; Ar.sup.1 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, nonaromatic R.sup.2 radicals; at the same time, it is possible for two Ar.sup.1 radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined to one another 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 H, D, F, Cl, Br, I, CN, B(OR.sup.3).sub.2, NO.sub.2, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.3).sub.2, N(R.sup.3).sub.2, NO.sub.2, P(═O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.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, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2 and 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 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more, adjacent substituents R.sup.2 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; R.sup.3 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 having 5 to 30 aromatic ring atoms 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 adjacent substituents R.sup.3 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; Y′ is selected from O, S, C(R.sup.3).sub.2, Si(R.sup.1).sub.2, NR.sup.1 and NAr.sup.1, U is selected from O, S, C(R.sup.3).sub.2, N(R.sup.3), B(R.sup.3), Si(R.sup.1).sub.2, C═O, S═O, SO.sub.2, P(R.sup.3) and P(═O)R.sup.1, the index o is 0, 1 or 2, the index n is 0, 1, 2 or 3, the index m is 0, 1, 2, 3 or 4, and the index l is 0, 1, 2, 3, 4, 5 or 6, and the aliphatic polycyclic ring system having at least 3 rings binds to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms at the respective positions identified by o to form a ring.

29. The compound as claimed in claim 20, wherein the compound comprises a hole transport group, where the Ar group present in a Y group or an R group comprises and represents a hole transport group, or, in a structure of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and/or (Ar′-1) to (Ar′-53), ##STR00399## ##STR00400## ##STR00401## ##STR00402## ##STR00403## ##STR00404## ##STR00405## ##STR00406## ##STR00407## ##STR00408## ##STR00409## ##STR00410## ##STR00411## ##STR00412## ##STR00413## ##STR00414## ##STR00415## ##STR00416## ##STR00417## ##STR00418## ##STR00419## ##STR00420## ##STR00421## wherein X′ is N or CR.sup.1; Y′ is selected from O, S, C(R.sup.1).sub.2, Si(R.sup.1).sub.2, NR.sup.1 and NAr.sup.1; U is selected from O, S, C(R.sup.1).sub.2, N(R.sup.1), B(R.sup.1), Si(R.sup.1).sub.2, C═O, S═O, SO.sub.2, 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, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.2).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.2, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, B(OR.sup.2).sub.2, Si(Ar.sup.1).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 or alkynyl 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, Ge(R.sup.2).sub.2, Sn(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 40 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 40 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 40 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, adjacent R.sup.1 radicals together may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; Ar.sup.1 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, nonaromatic R.sup.2 radicals; at the same time, it is possible for two Ar.sup.1 radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined to one another 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 H, D, F, Cl, Br, I, CN, B(OR.sup.3).sub.2, NO.sub.2, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.3).sub.2, N(R.sup.3).sub.2, NO.sub.2, P(═O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.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, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2 and 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 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more, adjacent substituents R.sup.2 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; R.sup.3 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 having 5 to 30 aromatic ring atoms 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 adjacent substituents R.sup.3 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; Y′ is selected from O, S, C(R.sup.3).sub.2, Si(R.sup.1).sub.2, NR.sup.1 and NAr.sup.1; U is selected from O, S, C(R.sup.1).sub.2, N(R.sup.1), B(R.sup.1), Si(R.sup.1).sub.2, C═O, S═O, SO.sub.2, P(R.sup.1) and P(═O)R.sup.1, the index s is 0, 1, 2, 3, 4, 5 or 6; the index t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; the index v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; the index o is 0, 1 or 2, the index n is 0, 1, 2, or 3, the index m is 0, 1, 2, 3 or 4, and the index l is 0, 1, 2, 3, 4, 5 or 6; and the aliphatic polycyclic ring system having at least 3 rings binds to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms at the respective positions identified by o to form a ring.

30. The compound as claimed in claim 20, wherein the compound comprises an electron transport group, where, in the structure of the formulae (I) to (XVIII), ##STR00422## ##STR00423## ##STR00424## Y is the same or different at each instance and is O, S, C(R).sub.2, CArR, C(Ar).sub.2, Si(Ar).sub.2, SiArR or Si(R).sub.2, NR or NAr; X is the same or different at each instance and is N or CR; 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.1).sub.2, C(═O)N(Ar).sub.2, C(═O)N(R.sup.1).sub.2, Si(Ar).sub.3, Si(R.sup.1).sub.3, B(OAr).sub.2, B(OR.sup.1).sub.2, C(═O)Ar, C(═O)R.sup.1, P(═O)(Ar).sub.2, P(═O)(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 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 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 may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S or CONR.sup.1, or an aromatic or heteroaromatic ring system which has 5 to 40 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 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, two R radicals together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic 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 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 silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined to one another 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, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.2).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.2, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, B(OR.sup.2).sub.2, Si(Ar.sup.1).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 or alkynyl 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, Ge(R.sup.2).sub.2, Sn(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 40 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 40 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 40 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, adjacent R.sup.1 radicals together may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; Ar.sup.1 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, nonaromatic R.sup.2 radicals; at the same time, it is possible for two Ar.sup.1 radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined to one another 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 H, D, F, Cl, Br, I, CN, B(OR.sup.3).sub.2, NO.sub.2, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.3).sub.2, N(R.sup.3).sub.2, NO.sub.2, P(═O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.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, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2 and 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 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more, adjacent substituents R.sup.2 together may also may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; R.sup.3 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 having 5 to 30 aromatic ring atoms 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 adjacent substituents R.sup.3 together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; the index s is 0, 1, 2, 3, 4, 5 or 6; the index t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; the index v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; the Ar group present in a Y group or an R group comprises and represents an electron transport group, or, in a structure of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and/or (Ar′-1) to (Ar′-53), ##STR00425## ##STR00426## ##STR00427## ##STR00428## ##STR00429## ##STR00430## ##STR00431## ##STR00432## ##STR00433## ##STR00434## ##STR00435## ##STR00436## ##STR00437## ##STR00438## ##STR00439## ##STR00440## ##STR00441## ##STR00442## ##STR00443## ##STR00444## ##STR00445## ##STR00446## where X′ is N or CR.sup.1; Y′ is O, S, C(R.sup.1).sub.2, Si(R.sup.1).sub.2, NR.sup.1 or NAr.sup.1; U is O, S, C(R.sup.1).sub.2, N(R.sup.1), B(R.sup.1), Si(R.sup.1).sub.2, C═O, S═O, SO.sub.2, P(R.sup.1) or P(═O)R.sup.1; Y is the same or different at each instance and is O, S, C(R).sub.2, CArR, C(Ar).sub.2, Si(Ar).sub.2, SiArR or Si(R).sub.2, NR or NAr; X is the same or different at each instance and is N or CR; 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.1).sub.2, C(═O)N(Ar).sub.2, C(═O)N(R.sup.1).sub.2, Si(Ar).sub.3, Si(R.sup.1).sub.3, B(OAr).sub.2, B(OR.sup.1).sub.2, C(═O)Ar, C(═O)R.sup.1, P(═O)(Ar).sub.2, P(═O)(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 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 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 may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S or CONR.sup.1, or an aromatic or heteroaromatic ring system which has 5 to 40 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 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, two R radicals together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; the index o is 0, 1 or 2; the index n is 0, 1, 2, or 3; the index m is 0, 1, 2, 3 or 4; and the index l is 0, 1, 2, 3, 4, 5 or 6; and the aliphatic polycyclic ring system having at least 3 rings binds to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms at the respective positions identified by o to form a ring; and R.sup.1 group comprises and represents an electron transport group, where the electron conductor groups comprise at least 2 nitrogen atoms in one six-membered ring or in two fused six-membered rings.

31. The compound as claimed in claim 20, wherein the ring via which the aliphatic polycyclic ring system having at least 3 rings is fused to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms comprises six ring atoms and at least two nonadjacent nitrogen atoms.

32. The compound as claimed in claim 20, wherein the ring via which the aliphatic polycyclic ring system having at least 3 rings is fused to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms comprises six ring atoms and at least one nitrogen atom and no further ring system is fused to that ring.

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

34. 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 (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

35. A formulation comprising at least one compound as claimed in claim 20 and at least one solvent.

36. An electronic device fluorescent emitter, emitter that exhibits TADF (thermally activated delayed fluorescence), host material, electron transport material, electron injection material, hole-conducting material, hole injection material, electron blocker material, hole blocker material and/or wide bandgap material which comprises at least one compound as claimed in claim 20.

37. A fluorescent emitter (singlet emitter), host material, hole-conducting material and/or electron transport material which comprises at least one compound as claimed in claim 20.

38. A process for preparing the compound as claimed in claim 20 which comprises a coupling reaction, a compound comprising at least one aliphatic polycyclic ring system having at least 3 rings is joined to a compound comprising at least one aromatic or heteroaromatic group.

39. An electronic device comprising at least one compound as claimed in claim 20, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells and organic laser diodes.

Description

EXAMPLES

[0289] 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 display multiple tautomeric forms, one tautomeric form is shown representatively.

1) Synthesis of the Synthons S

Example S1

[0290] ##STR00223##

[0291] A well-stirred mixture of 27.2 g (100 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-97-4], 32.4 g (100 mmol) of 2-(6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1801624-63-4], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolyl-phosphine, 225 mg (1 mmol) of palladium(II) acetate, 350 ml of toluene, 80 ml of dioxane and 300 ml of water is heated under reflux for 16 h. After cooling, the organic phase is separated from the aqueous phase and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and then dried over magnesium sulfate. The desiccant is filtered off using a silica gel bed in the form of a toluene slurry, and the filtrate is concentrated to dryness. The glassy residue is recrystallized from iso-propanol. Yield: 30.8 g (78 mmol) 78%. Purity by .sup.1H MMR about 97%.

[0292] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00062 Reactants Bromide Ex. Ketone/electrophile Product Yield S10 [00224] [00225] 81% [00226] S11 [00227] [00228] 78% [00229]

Example S2

[0293] ##STR00230##

[0294] To a well-stirred solution of 39.5 g (100 mmol) of S1 in 500 ml of dichloromethane is added dropwise, in the dark over the course of 3 h, a mixture of 3.1 ml (120 mmol) of bromine and 100 ml of dichloromethane. After the addition has ended, the mixture is stirred under reflux for 4 h and at room temperature for 8 h. 200 ml of sat. sodium sulfite solution is added to destroy excess bromine, and the organic phase is separated off, washed with 500 ml of water and 300 ml of sat. sodium hydrogencarbonate solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness and the red viscous residue is recrystallized from about 500 ml of iso-propanol. Yield: 32.7 g (69 mmol) 69%. Purity by .sup.1H MMR about 95%.

[0295] The following compound can be prepared analogously:

TABLE-US-00063 Reactants Bromide Ketone/ Ex. electrophile Product Yield S12 S10 [00231] 46%

Example S3

[0296] ##STR00232##

[0297] Preparation analogous to S2, except that 6.4 ml (240 mmol) of bromine is used. Also added to the solution of S1 dichloromethane is 100 mg of iron powder. Yield: 33.7 g (61 mmol) 61%. Purity by .sup.1H NMR about 97%.

[0298] The following compound can be prepared analogously:

TABLE-US-00064 Reactants Bromide Ketone/ Ex. electrophile Product Yield S13 S11 [00233] 43%

Example S4

[0299] ##STR00234##

[0300] To a well-stirred solution, cooled to ˜78° C., of 27.6 g (50 mmol) of S3 in 500 ml of THF is added dropwise 65.6 ml (105 mmol) of n-BuLi in hexane, 1.6 M, and the mixture is stirred for a further 30 min. A mixture of 5.1 ml (55 mmol) of dimethylcarbamoyl chloride [79-44-7] (caution: toxic, carcinogenic) and 50 ml of THF is slowly added dropwise, and the mixture is stirred for a further 30 min and then allowed to gradually warm up to room temperature. After 2 h at room temperature, 200 ml of sat. ammonium chloride solution is added, the mixture is extended with 300 ml of ethyl acetate, the aqueous phase is separated off and the organic phase is concentrated to dryness. The residue is taken up in 250 ml of dichloromethane (DCM), washed three times with 300 ml of water and once with 300 ml of sat. sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness under reduced pressure, and the residue is recrystallized from acetonitrile. Yield: 18.1 g (43 mmol) 85%, Purity by .sup.1H NMR about 97%,

Example S5

[0301] ##STR00235##

[0302] To a well-stirred solution, cooled to −78° C., of 47.4 g (100 mmol) of S2 in 500 ml of THF is added dropwise 85.6 ml (105 mmol) of n-BuLi in hexane, 1.8 M, and the mixture is stirred for a further 3 h. Then a solution of 27.2 g (105 mmol) of 2-bromo-9-fluorenone [3096-58-3] in 300 ml of THF is slowly added dropwise, and the mixture is stirred for a further 30 min and then allowed to gradually warm up to room temperature. After 2 h at room temperature, the THF is removed under reduced pressure, the residue is taken up in 500 ml of glacial acetic acid, 30 ml of cone, hydrochloric acid is added, and the mixture is heated under reflux for 3 h. The mixture is left to cool down to 80° C., 500 ml of water is slowly added dropwise, and the precipitated product is filtered off with suction while the mixture is still warm, washed with 100 ml of water and then three times with 100 ml each time of methanol, and dried under reduced pressure. Yield: 56.8 g (89 mmol) 89%. Purity by .sup.1H MMR about 97%.

[0303] In an analogous manner, it is possible to prepare the compounds below.

TABLE-US-00065 Reactants Bromide Ex. Ketone/electrophile Product Yield S6 S2   [00236] [00237] 86% S7 [00238] [00239] 79% S8 S3   [00240] [00241] 83% S9 S3 S4 [00242] 80% S15 S12   [00243] [00244] 78%

Example S20

[0304] ##STR00245##

[0305] A well-stirred mixture of 28.3 g (100 mmol) of (2-bromo-4-chlorophenyl)phenylamine [2149611-39-0], 32.4 g (100 mmol) of 2-(6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1801624-63-4], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolyl-phosphine, 225 mg (1 mmol) of palladium(II) acetate, 350 ml of toluene, 60 ml of dioxane and 300 ml of water is heated under reflux for 16 h. After cooling, the organic phase is separated from the aqueous phase and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and then dried over magnesium sulfate. The desiccant is filtered off using a silica gel bed in the form of a toluene slurry, and the filtrate is concentrated to dryness. The residue is recrystallized from acetonitrile with addition of a little ethyl acetate. The secondary amine thus obtained is dissolved in 300 ml of DMF, 45.4 g (250 mmol) of copper(II) acetate and 2.24 g (10 mmol) of palladium(II) acetate are added, and the mixture is stirred at for 4 h. The DMF is largely removed under reduced pressure, the residue is taken up in 500 ml of DCM, 300 ml of cone, ammonia solution is added, the mixture is stirred at room temperature for 1 h, and the organic phase is separated off and washed three times with 100 ml of cone, ammonia solution and once with sat. sodium chloride solution, and dried over magnesium sulfate. The magnesium sulfate is filtered off using a silica gel bed in the form of a DCM slurry, the filtrate is concentrated to dryness, and the residue is recrystallized from acetonitrile/eethyl acetate. Yield: 18.7 g (47 mmol) 47%. Purity by .sup.1H NMR about 95%.

Example S25

[0306] ##STR00246##

[0307] A well-stirred mixture of 27.2 g (100 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-97-4], 18.4 g (110 mmol) of carbazole [86-74-8], 41.5 g (300 mmol) of potassium carbonate, 1.9 g (10 mmol) of copper(I) iodide [7681-65-4], 100 g of glass beads (diameter 3 mm) and 300 ml of dimethylacetamide is heated under reflux for 30 h. While the mixture is still warm, the salts are filtered off with suction by means of a Celite bed in the form of a dimethylacetamide slurry, the filtrate is concentrated to dryness, the residue is taken up in 300 ml of DCM and filtered through a silica gel column (10×30 cm), and the core fraction is extracted. The evaluate is freed of the DCM under reduced pressure; the residue is recrystallized of acetonitrile. Yield: 33.4 g (88 mmol) 88%. Purity by .sup.1H NMR about 99%.

Example S26

[0308] ##STR00247##

[0309] To a well-stirred solution, cooled to 0° C., of 38.0 g (100 mmol) of S25 in 500 ml of DCM is added dropwise, in the dark, a solution of 17.8 g (100 mmol) of N-bromosuccinimide in 300 ml of dichloromethane, and then the mixture is stirred at room temperature for a further 12 h. The reaction solution is washed once with 200 ml of sat. sodium hydrogencarbonate solution, three times with 200 ml each time of water and once with 200 ml of sat. sodium chloride solution, and then dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated and the residue is chromatographed by flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 33.0 g (72 mmol) 72%. Purity by .sup.1H NMR about 95%.

Example S30

[0310] ##STR00248##

[0311] A well-stirred mixture of 17.3 g (100 mmol) of 2-bromophenol [95-96-7], 32.4 g (100 mmol) of 2-(6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1801624-63-4], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolyl-phosphine, 225 mg (1 mmol) of palladium(II) acetate, 350 ml of toluene, 60 ml of ethanol and 300 ml of water is heated under reflux for 16 h. After cooling, 60 ml of 10 N aqueous HCl is added, the organic phase is separated from the aqueous phase and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and then dried over magnesium sulfate. The desiccant is filtered off using a silica gel bed in the form of a toluene slurry, and the filtrate is concentrated to dryness. The residue is recrystallized from iso-propanol with addition of a little ethyl acetate. The phenol thus obtained is dissolved in 800 ml of mesitylene, and the well-stirred solution is admixed with 27.8 g (200 mmol) of potassium carbonate, 100 g of 3 A molecular sieve, 9.3 g (50 mmol) of sodium 2,4,6-trimethylbenzoate [32642-28-7], 1.82 g (10 mmol) of 4,5-diazafluoren-9-one [50890-67-0], 4.26 g (10 mmol) of 1,3-bis[2,8-bis(1-methylethyl)phenyl]-1H-imidazolium chloride [250235-32-6] and 1.12 g (5 mmol) of palladium(II) acetate, and then the mixture is heated to 120° C. with introduction of a gentle stream or air for 16 h. While the mixture is still warm, it is filtered with suction through a silica gel bed in the form of a mesitylene slurry, the mesitylene is removed under reduced pressure, and the residue is recrystallized from acetonitrile. Yield: 15.6 g (54 mmol) 54%.

[0312] Purity by .sup.1H NMR about 95%.

Example S31

[0313] ##STR00249##

[0314] To a well-stirred mixture, cooled to −78° C., of 33.2 g (100 mmol) of S30 and 500 ml of THF is added dropwise 65.6 ml (105 mmol) of n-BuLi in hexane, 1.6 M, and the mixture is stirred at −78° C. for 60 min and then at −40° C. for 30 min. After cooling again to −78° C., a mixture of 20.7 g (110 mmol) of triisopropyl borate [5419-55-8] and 50 ml of THF is added rapidly with good stirring, and the mixture is stirred for a further 30 min. The reaction mixture is allowed to warm up to room temperature, 100 ml of sat. ammonium chloride solution is added, the mixture is stirred for a further 15 min, and the organic phase is separated off, extended with 500 ml of ethyl acetate and washed three times with 300 ml each time of water and once with 200 ml of sat. sodium chloride solution. The organic phase is concentrated to dryness under reduced pressure and the residue is recrystallized from acetonitrile with addition of a little water. Yield: 18.9 g (57 mmol), 57%. Purity by .sup.1H NMR about 95%.

Example S35

[0315] ##STR00250##

[0316] A well-stirred mixture of 35.6 g (100 mmol) of 2,3-dibromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-66-7], 26.9 g (300 mmol) of copper(I) cyanide, 50 g of glass beads (diameter 3 mm) and 300 of NMP is heated to 170° C. for 18 h. While the mixture is still warm, it is filtered with suction through a Celite bed in the form of an NMP slurry, the filtrate is concentrated to dryness under reduced pressure and the residue is extracted by stirring in 300 ml of boiling MeOH. The crude product is extracted twice with hot acetonitrile. Yield: 15.0 g (60 mmol) 60%. Purity by .sup.1H NMR about 95%.

Example S36

[0317] ##STR00251##

[0318] To a well-stirred solution, cooled to −100° C., of 35.6 g (100 mmol) of 2,3-dibromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-66-7] in 1000 ml of THF is added dropwise 235 ml (400 mmol) of t-BuLi, 1.7 M in pentane, and the mixture is stirred for a further 30 min. Then a solution of 24.8 g (100 mmol) of S35 in 300 ml of THF is slowly added dropwise, and the mixture is stirred for a further 1 h, allowed to warm up to room temperature and quenched by addition of 50 ml of methanol. The THF is removed under reduced pressure, the residue is taken up in 300 ml of NMP, 30 ml of cone, hydrochloric acid is added, and the mixture is heated to about 150° C. for 4 h. After cooling, the mixture is extended with 500 ml of ethyl acetate, and the organic phase is washed three times with 500 ml each time of water and once with 300 ml of sat. sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness under reduced pressure, and the yellow residue is recrystallized twice from acetonitrile. Yield: 19.4 g (43 mmol) 43%. Purity by .sup.1H NMR about 95%.

[0319] In an analogous manner, it is possible to prepare the compounds below.

TABLE-US-00066 Ex. Reactants Product Yield S37 S35   [00252] [00253] 47%

Example S38

[0320] ##STR00254##

[0321] To a suspension of 44.9 g (100 mmol) of S36 in 500 ml of glacial acetic acid are added 100 ml of aqueous hydriodic acid (57% by weight) and 200 ml of aqueous hypophosphorous acid (50% by weight), and the mixture is heated under reflux for 18 h. The precipitated solids are filtered off with suction, washed five times with 300 ml each time of hot water, and extracted by stirring with 300 ml of hot ethanol, washed with another 300 ml of hot ethanol and dried under reduced pressure. Yield; 38.6 g (92 mmol) 92%. Purity by .sup.1H NMR about 95%.

[0322] The following compounds can be prepared analogously:

TABLE-US-00067 Ex. Reactants Product Yield S39 S37 [00255] 72%

Example S40

[0323] ##STR00256##

[0324] To a solution of 41.9 g (100 mmol) of S38 in 500 ml of dichloromethane is added in portions, with good stirring and in the dark, 19.6 g (110 mmol) of N-bromosuccinimide, and the mixture is stirred at room temperature for 6 h. The reaction mixture is washed once with 300 ml of sat. sodium hydrogencarbonate solution, three times with 300 ml each time of water and once with 300 ml of sat. sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness and the solids are crystallized from acetonitrile/ethyl acetate. Yield: 50.2 g (87 mmol) 87%. Purity by .sup.1H NMR about 98%.

[0325] The following compounds can be prepared analogously:

TABLE-US-00068 Ex. Reactants Product Yield S41 S37 [00257] 84%

2) Synthesis of the Amines A

Example A1

[0326] ##STR00258##

[0327] To a solution of 63.6 g (100 mmol) of S5 and 38.6 g (120 mmol) of bis-p-biphenylamine [102113-98-4] in 500 ml of toluene are added 4.0 ml (4.0 mmol) of a 1.0 M tri-tert-butylphosphine solution in toluene, 449 mg (2 mmol) of palladium acetate and 16.0 g of sodium tert-butoxide (166 mmol), and the mixture was heated under reflux for 3 h. The reaction mixture is cooled down to room temperature, extended with toluene and filtered through a Celite bed. The filtrate is concentrated under reduced pressure and the residue is crystallized from ethyl acetate/n-heptane. The crude product is extracted three times with hot acetonitrile and purified by zone sublimation under reduced pressure twice (p˜10.sup.−5 mbar, T˜310° C.). Yield: 63.1 g (72 mmol), 72%, Purity by HPLC>99.9%.

[0328] The following compounds can be prepared analogously:

TABLE-US-00069 Ex. Reactants Product Yield A2  S5   [00259] [00260] 70% A3  S5   [00261] [00262] 68% A4  S5   [00263] [00264] 75% A5  S5   [00265] [00266] 73% A6  S5   [00267] [00268] 65% A7  S5   [00269] [00270] 69% A8  S5   [00271] [00272] 74% A9  S5   [00273] [00274] 74% A10 S5   [00275] [00276] 70% A11 S6   [00277] [00278] 66% A12 S6   [00279] [00280] 61% A13 S7   [00281] [00282] 78% A14 S7   [00283] [00284] 75% A15 S7   [00285] [00286] 71% A16 S7   [00287] [00288] 72% A17 S7   [00289] [00290] 70% A18 S7   [00291] [00292] 76% A19 S8   [00293] [00294] 44% A20 S8   [00295] [00296] 41% A21 S9   [00297] [00298] 48% A30 S15   [00299] [00300] 67% A31 S15   [00301] [00302] 65% S40 S13 (50 mmol)   [00303] [00304] 56%

Example A22

[0329] ##STR00305##

[0330] A well-stirred mixture of 63.6 g (100 mmol) of S5, 57.6 g (110 mmol) of N-[1,1′-biphenyl]-2-yl-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-[1,1′-biphenyl]-4-amine [1608462-54-9], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 500 ml of toluene, 100 ml of dioxane and 400 ml of water is heated under reflux for 16 h. After cooling, the organic phase is separated from the aqueous phase and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and then dried over magnesium sulfate. The desiccant is filtered off using a silica gel bed in the form of a toluene slurry, and the filtrate is concentrated to dryness. The glassy residue is recrystallized from ethyl acetate/iso-propanol. The crude product is extracted three times with hot toluene and purified by zone sublimation under reduced pressure twice (p˜10.sup.−5 mbar, T˜330° C.). Yield: 86.8 g (70 mmol), 70%. Purity by HPLC>99.9%.

[0331] The following compounds can be prepared analogously:

TABLE-US-00070 Ex. Reactants Product Yield A23 S5   [00306] [00307] 68% A24 S5   [00308] [00309] 71% A25 S5   [00310] [00311] 75% A26 S8   [00312] [00313] 73% A27 S15   [00314] [00315] 69% A28 S15   [00316] [00317] 73%

3) Synthesis of the Carbazoles C

Example C1

[0332] ##STR00318##

[0333] A well-stirred mixture of 44.2 g (100 mmol) of S26, 36.9 g (100 mmol) of 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole [1126522-69-7], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 350 ml of toluene, 80 ml of dioxane and 300 ml of water is heated under reflux for 16 h. After cooling, the aqueous phase is separated off and the organic phase is concentrated to dryness. The residue is taken up in 500 ml of DCM, and the organic phase is washed once with 300 ml of water and once with 300 ml of sat. sodium chloride solution, and then dried over magnesium sulfate. The desiccant is filtered off using a silica gel bed in the form of a DCM slurry, and the filtrate is concentrated to dryness. The residue is extracted by stirring with hot butyl acetate/iso-propanol, then extracted three times with hot toluene and purified by zone sublimation under reduced pressure (p˜10.sup.−5 mbar, T˜320° C.). Yield: 40.0 g (66 mmol), 66%. Purity by HPLC>99.9%.

[0334] The following compounds can be prepared analogously:

TABLE-US-00071 Ex. Reactants Product Yield C2 S26   [00319] [00320] 64% C3 S26   [00321] [00322] 70% C4 S26   [00323] [00324] 65% C5 S26   [00325] [00326] 73% C6 S26   [00327] [00328] 71% C7 S26   [00329] [00330] 51% C8 S20 Use of 2 mmol S-Phos rather than tri-o-tolylphosphine   [00331] [00332] 57% C9 S20 Use of 2 mmol S-Phos rather than tri-o-tolylphosphine   [00333] [00334] 64% C10 S20 Use of 2 mmol S-Phos rather than tri-o-tolylphosphine   [00335] [00336] 70% C11 S20 Use of 2 mmol S-Phos rather than tri-o-tolylphosphine   [00337] [00338] 68% C12 S20 Use of 2 mmol S-Phos rather than tri-o-tolylphosphine S31 [00339] 59%

4) Synthesis of the Triazines T

Example T1

[0335] ##STR00340##

[0336] A well-stirred mixture of 42.0 g (100 mmol) of (2,4-bis([1,1′-biphenyl]-3-yl)-6-chloro-1,3,5-triazine [1205748-61-3], 32.4 g (100 mmol) of 2-(6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1801624-63-4], 31.9 g (150 mmol) of tripotassium phosphate, 821 mg (2 mmol) of S-Phos, 225 mg (1 mmol) of palladium(II) acetate, 400 ml of toluene, 80 ml of dioxane and 300 ml of water is heated under reflux for 16 h. After cooling, the organic phase is separated from the aqueous phase and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and then dried over magnesium sulfate. The desiccant is filtered off using a silica gel bed in the form of a toluene slurry, and the filtrate is concentrated to dryness. The residue is extracted by stirring with hot iso-propanol, then extracted five times with hot acetonitrile and purified by zone sublimation under reduced pressure (p˜ 10.sup.−5 mbar, T˜310° C.). Yield: 37.8 g (65 mmol), 65%. Purity by HPLC>99.9%.

[0337] The following compounds can be prepared analogously:

TABLE-US-00072 Ex. Reactants Product Yield T2 S26   [00341] [00342] 64% T3 S26   [00343] [00344] 55% T4 S26   [00345] [00346] 57% T5 S26   [00347] [00348] 49%

5) Synthesis of the Host Materials for Singlet Emitters SH

Example SH1

[0338] ##STR00349##

[0339] A well-stirred mixture of 45.6 g (100 mmol) of S41, 37.8 g (220 mmol) of 1-naphthylboronic acid [13922-41-3], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 400 ml of toluene, 80 ml of dioxane and 300 ml of water is heated under reflux for 16 h. After cooling, the aqueous phase is separated off and the organic phase is concentrated to dryness. The residue is taken up in 500 ml of DCM, and the organic phase is washed once with 300 ml of wafer and once with 300 ml of sat. sodium chloride solution, and then dried over magnesium sulfate. The desiccant is filtered off using a silica gel bed in the form of a DCM slurry, and the filtrate is concentrated to dryness. The residue is extracted by stirring with hot butyl acetate/iso-propanol, then extracted five times with hot toluene and purified by zone sublimation under reduced pressure (p˜10.sup.−5 mbar, T˜320° C.). Yield: 31.9 g (58 mmol) 58%, syn/anti isomer mixture. Purity by HPLC>99.9%.

6) Synthesis of the Singlet Emitters S

Example SE1

[0340] ##STR00350##

[0341] Procedure analogous to A1, except that, rather than S5, 28.8 g (50 mmol) of S40 and 31.0 g (110 mmol) of 4-(1,1-dimethylethyl)-N-[4-(1,1-dimethylethyl)phenyl]phenylamine [4627-22-9] is used. Purification by hot extraction with cyclohexane five times and zone sublimation under reduced pressure (p˜10.sup.−5 mbar, T˜330° C.). Yield: 26.0 g (53 mmol) 53%. Purity by HPLC>99.9%.

[0342] The following compounds can be prepared analogously:

TABLE-US-00073 Ex. Reactants Product Yield SE2 S40   [00351] [00352] 48%

7) Synthesis of the Spiro Materials H

[0343] The following compounds can be prepared analogously to S5:

TABLE-US-00074 Reactants Bromide Ex. Ketone/electrophile Product Yield H1 S2 S4 [00353] 91% H2 S2   [00354] [00355] 78% H3 S3, 25 mmol SiCl.sub.4, 12 mmol [10026-04-7] [00356] 54%

Production of the OLED Devices

1) Vacuum-Processed Devices:

[0344] 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).

[0345] In the examples which follow, the results for various OLEDs are presented. Cleaned glass plaques (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 mlnutes (PR-100 UV ozone generator from UVP) and, within 30 mln, for improved processing, coated 50 with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ P VP Al 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and then baked at 180° C. for 10 min. These coated glass plaques form the substrates to which the OLEDs are applied.

[0346] The OLEDs basically have the following layer structure: substrate/hole injection layer 1 (HIL1) consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 1 (HTL1)/hole transport layer 2 (HTL2)/emission layer (EML)/hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm.

[0347] 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 TMM1:TMM2:Ir(L1) (55%:35%: 10%) mean here that the material TMM1 is present in the layer in a proportion by volume of 55%, TMM2 in a proportion of 35% and Ir(L1) in a proportion of 10%. 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.

[0348] 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) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics, and also the lifetime are determined. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom. The lifetime LT90 is defined as the time after which the luminance in operation has dropped to 90% of the starting luminance with a starting brightness of 10 000 cd/m.sup.2.

[0349] The OLEDs can initially also be operated at different starting luminances. The values for the lifetime can then be converted to a figure for other starting luminances with the aid of conversion formulae known to those skilled in the art.

Use of Compounds of the Invention as Materials in Phosphorescent OLEDs

[0350] The compounds of the invention can be used inter alia as HTM (hole transport material), TMM (triplet matrix material), ETM (electron transport material) and as emitter materials in the emission layer in OLEDs. The compounds 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-00075 TABLE 1 Structure of the OLEDs HTL1 HTL2 HBL thick- thick- EML thick- ETL Ex ness ness thickness ness thickness Ref. HTM1 HTM2 TMM1:TMM2:Ir ETM1 ETM1:ETM2 D1 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 mm Ref. HTM1 HTM2 TMM1:TMM2:Ir ETM1 ETM1:ETM2 D2 210 nm 10 nm -Ref2 l0 nm (50%:50%) (40%:50%:10%) 30 nm 30 nm D1 HTM1 Al TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D2 HTM1 A2 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D3 HTM1 A3 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D4 HTM1 A4 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D5 HTM1 A5 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D6 HTM1 A6 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D7 HTM1 A7 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D8 HTM1 A8 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D9 HTM1 A10 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D10 HTM1 A13 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D11 HTM1 A14 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D12 HTM1 A16 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D13 HTM1 A17 TMM1:TMM2:Ir ETM1 ETM1:ETM 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D14 HTM1 A19 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D15 HTM1 A20 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D16 HTM1 A30 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D17 HTM1 A31 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D18 A9 HTM2 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D19 A11 HTM2 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D20 A12 HTM2 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D21 A40 HTM2 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D22 HTM1 A22 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.2 10 nm (50%:50%) (40%:50%:10%) 30 nm 30 nm D23 HTM1 A23 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.2 10 nm (50%:50%) (40%:50%:10%) 30 nm 30 nm D24 HTM1 A24 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.2 10 nm (50%:50%) (40%:50%:10%) 30 nm 30 nm D25 HTM1 A25 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.2 10 nm (50%:50%) (40%:50%:10%) 30 nm 30 nm D26 HTM1 A26 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.2 10 nm (50%:50%) (40%:50%:10%) 30 nm 30 nm D27 HTM1 A27 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.2 l0 nm (50%:50%) (40%:50%:10%) 30 nm 30 nm D28 HTM1 A28 TMM1:TMM2:Ir ETM1 ETM1:ETM2 210 nm 10 nm -Ref.2 10 nm (50%:50%) (40%:50%:10%) 30 nm 30 nm D29 HTM1 HTM2 TMM1:C1:Ir- ETM1 ETM1:ETM2 210 nm 10 nm Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D30 HTM1 HTM2 TMM1:C3:Ir- ETM1 ETM1:ETM2 210 nm 10 nm Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D31 HTM1 HTM2 TMM1:C4:Ir- ETM1 ETM1:ETM2 210 nm 10 nm Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D32 HTM1 HTM2 TMM1:C5:Ir- ETM1 ETM1:ETM2 210 nm 10 nm Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D33 HTM1 A13 TMM1:C12:Ir- ETM1 ETM1:ETM2 210 nm 10 nm Ref.1 10 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D34 HTM1 HTM2 TMM1:TMM2:Ir Ti T1:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D35 HTM1 HTM2 TMM1:TMM2:Ir T2 T2:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D36 HTM1 HTM2 TMM1:TMM2:Ir T3 T3:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D37 HTM1 HTM2 TMM1:TMM2:Ir ETM1 T4:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D38 HTM1 HTM2 TMM1:TMM2:Ir T5 T5:ETM2 210 nm 10 nm -Ref.1 l0 nm (50%:50%) (45%:40%:15%) 30 nm 30 nm D39 HTM1 HTM2 SH1:BD-Ref.1 --- ETM1:ETM2 160 nm 10 nm (94%:6%) (50%:50%) 20 nm 30 nm D40 HTM1 HTM2 SH1:SE1 --- ETM1:ETM2 200 nm 10 nm (94%:6%) (50%:50%) 25 nm 30 nm

TABLE-US-00076 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) CIE x/y LT90 (h) Ex. 1000 cd/m2 1000 cd/m2 1000 cd/m2 10000 cd/m2 Green and yellow OLEDs Ref.D1 19.2 3.3 0.33/0.62 310 Ref.D2 18.1 3.2 0.41/0.58 440 D1 19.4 3.3 0.33/0.62 330 D2 20.0 3.2 0.32/0.62 310 D3 19.5 3.2 0.33/0.62 340 D4 19.0 3.1 0.33/0.63 330 D5 19.4 3.3 0.33/0.62 350 D6 20.3 3.3 0.33/0.62 300 D7 18.7 3.1 0.32/0.61 360 D8 19.7 3.1 0.33/0.62 330 D9 19.5 3.3 0.33/0.62 340 D10 20.0 3.1 0.32/0.62 330 D11 19.2 3.0 0.33/0.62 350 D12 19.4 3.2 0.33/0.62 340 D13 19.2 3.3 0.33/0.62 370 D14 19.7 3.2 0.32/0.61 320 D15 18.9 3.3 0.33/0.62 350 D16 20.1 2.9 0.33/0.62 380 D17 19.7 3.0 0.33/0.62 390 D18 19.3 3.5 0.33/0.62 320 D19 20.0 2.8 0.33/0.62 310 D20 20.4 2.9 0.33/0.62 380 D21 20.2 2.8 0.32/0.62 370 D22 18.2 3.0 0.41/0.58 450 D23 18.0 2.8 0.41/0.58 470 D24 19.1 2.9 0.41/0.58 510 D25 18.7 2.9 0.41/0.58 470 D26 19.0 3.0 0.41/0.58 450 D27 19.3 2.8 0.41/0.58 460 D28 19.2 2.9 0.41/0.58 500 D29 19.7 3.1 0.33/0.62 390 D30 19.6 3.1 0.33/0.62 380 D31 19.7 3.1 0.33/0.62 370 D32 20.0 3.2 0.32/0.62 420 D33 19.3 3.1 0.32/0.62 360 D34 19.4 3.2 0.33/0.62 340 D35 19.3 3.1 0.33/0.62 350 D36 19.4 3.2 0.33/0.62 340 D37 19.5 3.4 0.33/0.62 360 D38 19.7 3.2 0.33/0.62 370 Blue and green OLEDs D39 7.2 4.2 0.15/0.09 300h D40 8.6 3.7 0.29/0.62 ---

2. Solution-Processed Devices:

A: From Soluble Functional Materials of Low Molecular Weight

[0351] The materials of the invention can also be processed from solution and in that case lead to OLEDs which are much simpler in terms of process technology compared to the vacuum-processed OLEDs, but nevertheless have good properties. The production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in WO 2004/037887). The structure is composed of substrate/ITO/hole injection layer (60 nm)/interlayer (20 nm)/emission layer (60 nm)/hole blocker layer (10 nm)/electron transport layer (40 nm)/cathode. For this purpose, substrates from Technoprint (soda-lime glass) are used, to which the ITO structure (indium tin oxide, a transparent conductive anode) is applied. The substrates are cleaned in a cleanroom with DI water and a detergent (Deconex 15 PF) and then activated by a UV/ozone plasma treatment. Thereafter, likewise in a cleanroom, a 20 nm hole injection layer is applied by spin-coating. The required spin rate depends on the degree of dilution and the specific spin-coater geometry. In order to remove residual water from the layer, the substrates are baked on a hotplate at 200° C. for 30 minutes. The interlayer used serves for hole transport; in this case, HL-X from Merck is used. The interlayer may alternatively also be replaced by one or more layers which merely have to fulfill the condition of not being leached off again by the subsequent processing step of EML deposition from solution. For production of the emission layer, the triplet emitters of the invention are dissolved together with the matrix materials in toluene or chlorobenzene. The typical solids content of such solutions is between 16 and 25 g/l 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 solution-processed devices contain an emission layer of Matrix1: Matrix2:Ir-Ref.3 and optionally Ir-Ref.4. Optionally, a Matrix3 is additionally used (see table 3). The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 160° C. for 10 min. Vapor-deposited atop the latter are the hole blocker layer (10 nm ETM1) and the electron transport layer (40 nm ETM1 (50%)/ETM2 (50%)) (vapor deposition systems from Lesker or the like, typical vapor deposition pressure 5×10.sup.−6 mbar). Finally, a cathode of aluminum (100 nm) (high-purity metal from Aldrich) is applied by vapor deposition. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited are yet to be optimized; table 3 summarizes the data obtained. The lifetime LT50 is defined as the time after which the luminance in operation drops to 50% of the starting luminance with a starting brightness of 1000 cd/m.sup.2.

TABLE-US-00077 TABLE 3 Results with materials processed from solution Matrix1 Voltage Matrix2 EQE (%) (V) Matrix3 1000 1000 LT50 (h) Ex. Ir-Ref.3 cd/m.sup.2 cd/m.sup.2 CIE x/y 1000 cd/m.sup.2 Sol-D1 TMM3(20%) 21.0 4.3 0.34/0.62 310000 TMM4(60%) Ir-Ref.3 (20%) Sol-D2 TMM3(26%) 20.9 3.9 0.34/0.62 330000 TMM4(50%) A15 (8%) Ir-Ref.3 (16%) Sol-D3 TMM3(30%) 21.2 3.9 0.35/0.62 350000 TMM4(48%) A18 (6%) Ir-Ref.3 (16%) Sol-D4 TMM3(30%) 21.5 3.8 0.34/0.62 330000 TMM4(48%) A21 (6%) Ir-Ref.3 (16%) Sol-D5 TMM3(30%) 21.3 4.2 0.35/0.62 340000 TMM4(48%) C6 (6%) Ir-Ref.3 (16%) Sol-D6 TMM3(30%) 21.1 4.1 0.35/0.62 330000 TMM4(48%) C7 (6%) Ir-Ref.3 (16%) Sol-D7 C8 (20%) 21.4 4.1 0.35/0.62 370000 TMM4(56%) — Ir-Ref.3 (24%) Sol-D8 C9 (20%) 21.0 4.0 0.34/0.62 350000 TMM4(56%)   Ir-Ref.3 (24%) 20.8 3.9 0.35/0.62 340000 Sol-D9 TMM3(38%) TMM4(40%) C10 (6%) Ir-Ref.3 (16%) Sol-D10 TMM3(20%) 21.6 4.2 0.34/0.62 360000 C11(20%) TMM4(52%) H1 (8%) Ir-Ref.3 (20%) Sol-D11 TMM3(10%) 18.1 5.7 0.67/0.33 300000 C11(20%) TMM4(34%) Ir-Ref.3 (30%) Ir-Ref.4 (6%)

TABLE-US-00078 TABLE 4 Structural formulae of the materials used [00357] HTM1 [136463-07-5] [00358] HTM2 [1450933-43-3] [00359] TMM1 [1257248-13-7] [00360] TMM1 [1357150-54-9] [00361] TMM3 [1616231-60-7] [00362] TMM4 [1246496-85-4] [00363] ETM1 = M10 [1233200-52-6] [00364] ETM2 [25387-93-3] [00365] Ir-Ref.1 [1989606-01-0] [00366] Ir-Ref.2 [1989605-56-2] [00367] Ir-Ref.3 [2170173-12-1] [00368] BD-Ref.1 [1883835-29-7] [00369] Ir-Ref.4 [1989604-92-3]