Compounds having valerolactam structures

Abstract

The present invention describes compounds comprising at least one structural element having at least three fused aromatic or heteroaromatic rings (AR) and at least one structural element having an aromatic or heteroaromatic valerolactam (AV), especially for use in electronic devices. The invention further relates to a process for preparing the compounds of the invention and to electronic devices comprising these.

Claims

1. An oligomer, polymer, or dendrimer comprising one or more compounds comprising at least one structure of formula (II): ##STR00392## wherein X is the same or different in each instance and is N or CR.sup.1, with the proviso that not more than two X in one cycle are N; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.2).sub.2, CHO, C(═O)R.sup.2, CR.sup.2═C(R.sup.2).sub.2, CN, C(═O)OR.sup.2, C(═O)N(R.sup.2).sub.2, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, NO.sub.2, P(═O)(R.sup.2).sub.2, OSO.sub.2R.sup.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, 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 is optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally 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 having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 radicals, or a combination of these systems; and wherein two or more R.sup.1 substituents together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.3).sub.2, CHO, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, CN, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, 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 is optionally substituted by one or more R.sup.3 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Si(R.sup.2).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S′C═Se′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 wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.3 radicals, or a combination of these systems; and wherein two or more R.sup.2 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; R.sup.3 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein hydrogen atoms are optionally replaced by F; and wherein two or more R.sup.3 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; and L.sup.1 is a bond or an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.1 radicals, wherein one or more bonds of the compound to the polymer, oligomer, or dendrimer are present.

2. An electronic device comprising at least one compound comprising at least one structure of formula (II): ##STR00393## wherein X is the same or different in each instance and is N or CR.sup.1, with the proviso that not more than two X in one cycle are N; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.2).sub.2, CHO, C(═O)R.sup.2, CR.sup.2═C(R.sup.2).sub.2, CN, C(═O)OR.sup.2, C(═O)N(R.sup.2).sub.2, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, NO.sub.2, P(═O)(R.sup.2).sub.2, OSO.sub.2R.sup.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, 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 is optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally 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 having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 radicals, or a combination of these systems; and wherein two or more R.sup.1 substituents together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.3).sub.2, CHO, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, CN, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, 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 is optionally substituted by one or more R.sup.3 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Si(R.sup.2).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S′C═Se′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 wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.3 radicals, or a combination of these systems; and wherein two or more R.sup.2 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; R.sup.3 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein hydrogen atoms are optionally replaced by F; and wherein two or more R.sup.3 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; and L.sup.1 is a bond or an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.1 radicals, 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.

3. An oligomer, polymer, or dendrimer comprising one or more compounds of the structure of formula (Ia): ##STR00394## wherein R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.2).sub.2, CHO, C(═O)R.sup.2, CR.sup.2═C(R.sup.2).sub.2, CN, C(═O)OR.sup.2, C(═O)N(R.sup.2).sub.2, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, NO.sub.2, P(═O)(R.sup.2).sub.2, OSO.sub.2R.sup.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, 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 is optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally 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 having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 radicals, or a combination of these systems; and wherein two or more R.sup.1 substituents together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.3).sub.2, CHO, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, CN, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, 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 is optionally substituted by one or more R.sup.3 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Si(R.sup.2).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S C═Se C═NR.sup.3—C(═O)O—C(═O)NR.sup.3— NR.sup.3P(═O)(R.sup.3)—O—S—SO, or SO.sub.2 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.3 radicals, or a combination of these systems; and wherein two or more R.sup.2 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; R.sup.3 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein hydrogen atoms are optionally replaced by F; and wherein two or more R.sup.3 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; and L.sup.1 is a bond or an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.1 radicals; l is 0, 1, 2, 3, 4, or 5; and m is 0, 1, 2, 3, or 4, wherein one or more bonds of the compound to the polymer, oligomer, or dendrimer are present.

4. An electronic device comprising at least one compound of the structure of formula (Ia): ##STR00395## wherein R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.2).sub.2, CHO, C(═O)R.sup.2, CR.sup.2═C(R.sup.2).sub.2, CN, C(═O)OR.sup.2, C(═O)N(R.sup.2).sub.2, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, NO.sub.2, P(═O)(R.sup.2).sub.2, OSO.sub.2R.sup.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, 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 is optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally 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 having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 radicals, or a combination of these systems; and wherein two or more R.sup.1 substituents together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.3).sub.2, CHO, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, CN, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, 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 is optionally substituted by one or more R.sup.3 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Si(R.sup.2).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S C═Se C═NR.sup.3—C(═O)O—C(═O)NR.sup.3—NR.sup.3P(═O)(R.sup.3)—O—S—SO, or SO.sub.2 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.3 radicals, or a combination of these systems; and wherein two or more R.sup.2 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; R.sup.3 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein hydrogen atoms are optionally replaced by F; and wherein two or more R.sup.3 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; and L.sup.1 is a bond or an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.1 radicals; l is 0, 1, 2, 3, 4, or 5; and m is 0, 1, 2, 3, or 4, 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.

5. A composition comprising at least one compound of the structure of formula (II): ##STR00396## wherein X is the same or different in each instance and is N or CR.sup.1, with the proviso that not more than two X in one cycle are N; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.2).sub.2, CHO, C(═O)R.sup.2, CR.sup.2═C(R.sup.2).sub.2, CN, C(═O)OR.sup.2, C(═O)N(R.sup.2).sub.2, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, NO.sub.2, P(═O)(R.sup.2).sub.2, OSO.sub.2R.sup.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, 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 is optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally 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 having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 radicals, or a combination of these systems; and wherein two or more R.sup.1 substituents together optionally define a ring system: R.sup.2 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.3).sub.2, CHO, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, CN, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, 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 is optionally substituted by one or more R.sup.3 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Si(R.sup.2).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S′C═Se′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 wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.3 radicals, or a combination of these systems; and wherein two or more R.sup.2 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; R.sup.3 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein hydrogen atoms are optionally replaced by F; and wherein two or more R.sup.3 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; and L.sup.1 is a bond or an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.1 radicals, and at least one further compound is selected from the group consisting of fluorescent emitters, phosphorescent emitters, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials, and hole blocker materials.

6. A composition comprising at least one compound of the structure of formula (Ia): ##STR00397## wherein R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.2).sub.2, CHO, C(═O)R.sup.2, CR.sup.2═C(R.sup.2).sub.2, CN, C(═O)OR.sup.2, C(═O)N(R.sup.2).sub.2, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, NO.sub.2, P(═O)(R.sup.2).sub.2, OSO.sub.2R.sup.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, 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 is optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally 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.2P(═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 having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 radicals, or a combination of these systems; and wherein two or more R.sup.1 substituents together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, Cl, Br, I, B(OR.sup.3).sub.2, CHO, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, CN, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, 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 is optionally substituted by one or more R.sup.3 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Si(R.sup.2).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S C═Se C═NR.sup.3—C(═O)O—C(═O)NR.sup.3—NR.sup.3P(═O)(R.sup.3)—O—S—SO, or SO.sub.2 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.3 radicals, or a combination of these systems; and wherein two or more R.sup.2 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; R.sup.3 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein hydrogen atoms are optionally replaced by F; and wherein two or more R.sup.3 substituents together optionally define a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system; and L.sup.1 is a bond or an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.1 radicals; l is 0,1,2, 3,4, or 5; and m is 0, 1, 2, 3, or 4, and at least one further compound is selected from the group consisting of fluorescent emitters, phosphorescent emitters, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials, and hole blocker materials.

Description

EXAMPLES

(1) Synthesis Scheme:

(2) ##STR00280## ##STR00281##

1. Preparation of 2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-5H-phenanthridin-6-one (3)

(3) In a four-neck flask, 20.0 g (73.0 mmol, 1.00 eq) of 2-bromo-5H-phenanthridin-6-one [27353-48-6] 1 together with 22.2 g (87.6 mmol, 1.20 eq) of bis(pinacolato)diborane [73183-34-3] 2 and 21.5 g (219 mmol, 3.00 eq) of potassium acetate are dissolved in 800 ml of dioxane and inertized with argon. Subsequently, 1.79 g (2.19 mmol, 0.03 eq) of 1,1-bis(diphenylphosphino)ferrocene-dichloropalladium(II) complex [95464-05-4] are added and the reaction mixture is stirred at bath temperature 115° C. overnight. After the reaction has ended, the mixture is cooled down to room temperature and the solvent is removed by rotary evaporator. The residue is taken up in 250 ml of dichloromethane and extracted by shaking with 250 ml of water. The aqueous phase is extracted three times with 250 ml of dichloromethane, the combined organic phases are dried over sodium sulfate and the solvent is removed on a rotary evaporator. The resulting solids are washed with ethanol at 60° C. After drying, 20.6 g (64.0 mmol, 88%) of the desired product 3 are obtained.

(4) The following compounds can be prepared in an analogous manner:

(5) TABLE-US-00002 Yield Compound Reactant Product [%] 3b 82 3c 97 3d 66 3e 45 3f 0 78 3g 47 3h 33 3i 93 3j 68 3k 00 01 27 3l 02 03 95 3m 04 05 74

2. Preparation of 2-(10-phenylanthracen-9-yl)-5H-phenanthridin-6-one (5)

(6) A four-neck flask is initially charged with 14.4 g (44.9 mmol, 1.00 eq) of intermediate 3, 15.7 g (47.1 mmol, 1.05 eq) of 9-bromo-10-phenylanthracene [23674-20-6] and 4.80 g (44.9 mmol, 1.00 eq) of sodium carbonate in 185 ml of toluene, 375 ml of 1,4-dioxane and 375 ml of water, and the mixture is degassed with argon. Subsequently, 1.03 g (0.891 mmol, 0.02 eq) of tetrakis(triphenylphosphine)-palladium(0) [14221-01-3] are added and the mixture is stirred at 120° C. overnight. After the reaction has ended, the precipitated solids are washed with water and ethanol and dried in a vacuum drying cabinet. 11.9 g (26.7 mmol, 59%) of the desired target compound 5 are obtained.

(7) The following compounds can be prepared in an analogous manner:

(8) TABLE-US-00003 Yield Compd. Reactant Reactant Product [%] 5b 06 07 08 43% 5c 09 0 47% 5d 53% 5e 37% 5f 0 42% 5g 51% 5h 53% 5i 47% 5j 0 59% 5k 57% 5l 53% 5m 0 37%

3. Preparation of 5-biphenyl-3-yl-2-(10-phenylanthracen-9-yl)-5H-phenanthridin-6-one (7)

(9) 11.1 g (24.8 mmol, 1.00 eq) of 2-(10-phenylanthracen-9-yl)-5H-phenanthridin-6-one 5, 21.3 ml (128 mmol, 5.2 eq) of 3-bromobiphenyl [2113-57-7] and 7.20 g of potassium carbonate (52.1 mmol, 2.10 eq) are initially charged in 220 ml of dried DMF and inertized with argon. Subsequently, 0.62 g (2.7 mmol, 0.11 eq) of 1,3-di(2-pyridyl)propane-1,3-dione and 0.52 g (2.7 mmol, 0.11 eq) of copper(l) iodide are added and the mixture is heated at 14000 for three days. After the reaction has ended, the mixture is concentrated cautiously on a rotary evaporator, and the precipitated solids are filtered off with suction and washed with water and ethanol. The crude product is purified twice by means of a hot extractor (toluene/heptane 1:1), and the solids obtained are recrystallized from toluene. After sublimation, 5.3 g (8.8 mmol, 36%) of the desired target compound 7 are obtained.

(10) The following compounds can be prepared in an analogous manner:

(11) TABLE-US-00004 Yield Compd. Reactant Reactant Product [%] 7b 42% 7c 47% 7d 0 53% 7e 51% 7f 47% 7g 49% 7h 0 59% 7i 42% 7j 59% 7k 0 52% 7l 41% 7m 40%

(12) Preparation of the Comparative Compound (COMP)

(13) ##STR00378##

(14) 20 g (86 mmol) of E2, 11.4 g (94 mmol) of E1, 23.6 g (171 mmol) of potassium carbonate, 1.72 g (20 mmol) of N,N′-dimethylethylenediamine, 1.62 g (9 mmol) of CuI are initially charged in 200 ml of anhydrous toluene and refluxed for 5 days. On completion of reaction, the reaction mixture is cooled down to room temperature and filtered through a short silica gel bed and washed through with dichloromethane. The solvents are removed under reduced pressure and the residue is washed with ethanol. Yield: 22.4 g (82 mmol; 95%)

(15) Final Step to the Comparative Compound (COMP):

(16) ##STR00379##

(17) Synthesis was effected analogously to compound 7. Yield 33%

(18) Production of the OLEDs

(19) In examples C1 and I2 to I6 which follow (see tables 1 and 2), the data of various OLEDs are presented.

(20) Pretreatment for examples C1 and I2-I6: Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm, for improved processing, are 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). These coated glass plaques form the substrates to which the OLEDs are applied.

(21) The OLEDs basically have the following layer structure: substrate/hole transport layer (HTL)/optional interlayer (IL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in Table 1. The materials required for production of the OLEDs are shown in Table 3.

(22) All materials are applied by thermal vapour 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 H:SEB(95%:5%) mean here that the material H is present in the layer in a proportion by volume of 95% and SEB in a proportion of 5%. Analogously, the electron transport layer may also consist of a mixture of two materials.

(23) 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 determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter U1000 in Table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. CE1000 and PE1000 respectively refer to the current and power efficiencies which are achieved at 1000 cd/m.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2.

(24) The data for the various OLEDs are collated in Table 2. Example C1 serves as a comparative example; examples 12 to 16 show data of OLEDs of the invention.

(25) Some of the examples are elucidated in detail hereinafter, in order to illustrate the advantages of the OLEDs of the invention.

(26) Use of Materials of the Invention as Electron Transport Material in OLEDs

(27) The materials of the invention, when used as electron transport material (ETL) in OLEDs, give a significant improvement in power efficiency over the prior art. Through use of inventive compound 7 in Example 12, it is possible to observe an increase in power efficiency by 50% compared to the comparative compound (COMP) in example C1.

(28) TABLE-US-00005 TABLE 1 Structure of the OLEDs HTL IL EBL EML ETL Ex. thickness thickness thickness thickness thickness C1 SpA HATCN SpMA H:SEB COMP:LiQ 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm I2 SpA HATCN SpMA H:SEB 7:LiQ 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm I3 SpA HATCN SpMA H:SEB 7g:LiQ 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm I4 SpA HATCN SpMA H:SEB 7j:LiQ 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm I5 SpA HATCN SpMA H:SEB 7d:LiQ 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm I6 SpA HATCN SpMA H:SEB 7l:LiQ 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm

(29) TABLE-US-00006 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE1000 CIE x/y at Ex. (V) (cd/A) (lm/W) ([%]) 1000 cd/m.sup.2 C1 5.5 5.2 3.0 4.5 0.14/0.15 I2 5.0 7.5 4.6 6.5 0.13/0.14 I3 5.1 7.2 4.5 6.0 0.14/0.15 I4 5.2 6.5 3.9 5.6 0.14/0.15 I5 5.2 6.9 4.2 5.9 0.13/0.14 I6 5.3 6.6 3.9 5.7 0.14/0.15

(30) TABLE-US-00007 TABLE 3 Structural formulae of the materials for the OLEDs 0 0