Hexacyclic heteroaromatic compounds for electronic devices

Abstract

The invention relates to heteroaromatic compounds, particularly for use in electronic devices. The invention further relates to a method for producing the compounds according to the invention and to electronic devices containing same.

Claims

1. A compound comprising at least one structure of the formula (I) ##STR00359## where the symbols used are as follows: Y is the same or different at each instance and is a bond or NR.sup.1, NAr, O, S, C(R.sup.1).sub.2, CArR.sup.1, C(Ar).sub.2, Si(Ar).sub.2, SiArR.sup.1 or Si(R.sup.1).sub.2, where at least one Y group is selected from NR.sup.1, NAr, O, S, C(R.sup.1).sub.2, CArR.sup.1, C(Ar).sub.2, Si(Ar).sub.2, SiArR.sup.1 or Si(R.sup.1).sub.2; X is the same or different at each instance and is N or CR.sup.1, 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, two Ar radicals bonded to the same carbon atom or silicon atom may also 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, OR.sup.2, 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 and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 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 radicals may form a ring system with one another; 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.1).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 substituents may also form a ring system with one another; 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 which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, it is also possible for two or more substituents to form a ring system with one another.

2. The compound as claimed in claim 1, comprising at least one structure of the formula (IIa) or (IIb) ##STR00360## where the symbols Y and X used have the definition given in claim 1.

3. The compound as claimed in claim 1, comprising at least one structure of the formula (IIIa), (IIIb), (IVa), (IVb), (Va) or (Vb) ##STR00361## ##STR00362## where the symbols R.sup.1, Y and X have the definition given in claim 1, in is 0, 1, 2, 3 or 4, and n is, 0, 1, 2 or 3.

4. The compound as claimed in claim 1, comprising at least one structure of the formula (VIa) or (VIb) ##STR00363## where the symbols R.sup.1 and Y have the definition given in claim 1, m is the same or different at each instance and is 0, 1, 2, 3 or 4, and n is 0, 1, 2 or 3.

5. The compound as claimed in claim 1, characterized in that the compound comprises a hole transport group.

6. The compound as claimed in claim 5, characterized in that the hole transport group comprises a group selected from the formulae (H-1) to (H-3) ##STR00364## where the dotted bond marks the position of attachment and in addition: Ar.sup.2, Ar.sup.3, Ar.sup.4 is in each case independently an aromatic ring system having 6 to 40 carbon atoms or a heteroaromatic ring system having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.1 radicals, p is 0 or 1, Z is C(R.sup.1).sub.2, Si(R.sup.1).sub.2, C═O, N—Ar.sup.1, BR.sup.1, PR.sup.1, POR.sup.1, SO, SOL, Se, O or S, where the symbols Ar.sup.1 and R.sup.1 have the definition given in claim 1, where the presence of an N—N bond is ruled out, such that, in the case that Y═NAr, the index p=1.

7. The compound as claimed in claim 5, characterized in that the hole transport group comprises a group selected from the formulae (H-4) to (H-26) ##STR00365## ##STR00366## ##STR00367## ##STR00368## where Y.sup.1 represents O, S, C(R.sup.1).sub.2 or NAr.sup.1, the dotted bond marks the position of attachment, e is 0, 1 or 2, j is 0, 1, 2 or 3, h is 0, 1, 2, 3 or 4, p is 0 or 1, R.sup.1 is the same or different at each instance and is H, D, OH, OR.sup.2, 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 and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 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 radicals may form a ring system with one another; 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.2.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 substituents may also form a ring system with one another; 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 which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, it is also possible for two or more substituents to form a ring system with one another, and Ar.sup.2 is in each case independently an aromatic ring system having 6 to 40 carbon atoms or a heteroaromatic ring system having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.1 radicals: where the presence of an N—N bond is ruled out, such that, in the case that Y═NAr in the formulae (H-5), (H-6), (H-9), (H-12), (H-15), (H-18), (H-21), (H-24), (H-25) and (H-26), the index p=1.

8. The compound as claimed in claim 1, characterized in that the compound comprises an electron transport group.

9. A compound as claimed in claim 8, characterized in that the Ar group present in a Y group, or an R.sup.1 group bonded to the base skeleton, is a group representable by the formula (QL) ##STR00369## in which L.sup.1 represents a bond or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals, and Q is an electron transport group, where R.sup.1 is the same or different at each instance and is H, D, OH, OR.sup.2, 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, Ce(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 and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 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 radicals may form a ring system with one another; 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 group 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 substituents may also form a ring system with one another; 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 which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, it is also possible for two or more substituents to form a ring system with one another.

10. The compound as claimed in claim 9, characterized in that the electron transport group is selected from structures of the formulae (Q-1), (Q-2), (Q-3), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9) and/or (Q-10) ##STR00370## where the dotted bond marks the position of attachment, Q′ is the same or different at each instance and is CR.sup.1 or N, where at least one Q′ is N; Q″ is NR.sup.1, O or S, and R.sup.1 is as defined in claim 9.

11. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 1, wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

12. A composition comprising at least one compound as claimed in claim 1 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

13. A formulation comprising at least one compound as claimed in claim 1 and at least one solvent.

14. A process for preparing the compound as claimed in claim 1, characterized in that, in a coupling reaction, a compound comprising at least one nitrogen-containing heterocyclic group is joined to a compound comprising at least one aromatic or heteroaromatic group.

15. An electronic device comprising at least one compound as claimed in claim 1.

16. The electronic device as claimed in claim 15 which is an organic electroluminescent device, characterized in that the compound is present as matrix material in an emitting layer, as hole transport material or as electron transport material.

17. The compound as claimed in claim 1, wherein Y is the same or different at each instance and is NR.sup.1 or NAr; R.sup.1 is the same or different at each instance and is H, D, OH, OR.sup.2, 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—, 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 and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 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 may form a ring system with one another; 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 R.sup.2 substituents may also form a ring system with one another and 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 which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, it is also possible for two or more adjacent R.sup.3 substituents to form a ring system with one another.

18. The compound as claimed in claim 1, characterized in that the compound comprises a hole transport group, and the Ar group present in the Y group, or an R.sup.1 group bonded to the base skeleton comprises and represents the hole transport group.

19. The compound as claimed in claim 1, characterized in that the Ar group present in a Y group comprises and represents an electron transport group.

Description

EXAMPLES

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. For the compounds known from the literature, the corresponding CAS numbers are also reported in each case.

Synthesis Examples

a) Indolizino[3,4,5-ab]isoindole-2-boronic Acid

(2) ##STR00242##

(3) 197 g (729 mmol) of 2-bromoindolizino[3,4,5-ab]isoindole are dissolved in 1500 ml of dry THF and cooled to −78° C. At this temperature, 305 ml (764 mmol/2.5 M in hexane) of n-butyllithium are added within about 5 min, and then the mixture is stirred at −78° C. for a further 2.5 h. At this temperature, 150 g (1455 mmol) of trimethyl borate are added very rapidly and the reaction is allowed to come gradually to room temperature (about 18 h). The reaction solution is washed with water and the precipitated solids and the organic phase are subjected to azeotropic drying with toluene. The crude product is extracted while stirring from toluene/methylene chloride at about 40° C. and filtered off with suction. Yield: 148 g (529 mmol), 81% of theory.

b) (2-Chlorophenyl)indolizino[3,4,5-ab]isoindol-2-ylamine

(4) ##STR00243##

(5) 37 g (137 mmol) of 2-bromoindolizino[3,4,5-ab]isoindole, 17.5 g (137 mmol) of 2-chloroaniline, 68.2 g (710 mmol) of sodium tert-butoxide, 613 mg (3 mmol) of palladium(II) acetate and 3.03 g (5 mmol) of 1,1′-bis(diphenylphosphino)ferrocene (dppf) are dissolved in 1.3 l of toluene and stirred under reflux for 5 h. The reaction mixture is cooled down to room temperature, extended with toluene and filtered through Celite. The filtrate is concentrated under reduced pressure and the residue is crystallized from toluene/heptane. The product is isolated as a colorless solid. Yield: 34 g (107 mmol), 80% of theory.

(6) In an analogous manner, it is possible to prepare the following compound:

(7) TABLE-US-00003 Reactant 1 Reactant 2 Product Yield 1b 80%

c) Cyclization (Method A)

(8) ##STR00247##

(9) 31.6 g (100 mmol) of (2-chlorophenyl)indolizino[3,4,5-ab]isoindol-2-yl-amine, 56 g (409 mmol) of potassium carbonate, 4.5 g (12 mmol) of tricyclohexylphosphine tetrafluoroborate and 1.38 g (6 mmol) of palladium(II) acetate are suspended in 500 ml of dimethylacetamide and stirred under reflux for 6 h. After cooling, the reaction mixture is extended with 300 ml of water and 400 ml of CH.sub.2Cl.sub.2. The mixture is stirred for a further 30 min, the organic phase is separated off and filtered through a short Celite bed, and then the solvent is removed under reduced pressure.

(10) The crude product is subjected to hot extraction with toluene and recrystallized from toluene. The product is isolated as a beige solid. Yield: 19 g (68 mmol), 68% of theory.

(11) In an analogous manner, it is possible to prepare the following compound:

(12) TABLE-US-00004 Reactant Product Yield 1c 65%

d) 2-(2-Nitrophenyl)indolizino[3,4,5-ab]isoindole

(13) ##STR00250##

(14) To a well-stirred, degassed suspension of 30 g (184 mmol) of B-(2-nitrophenyl)boronic acid, 49 g (180 mmol) of 2-bromoindolizino[3,4,5-ab]isoindole and 66.5 g (212.7 mmol) of potassium carbonate in a mixture of 250 ml of water and 250 ml of THE are added 1.7 g (1.49 mmol) of Pd(PPh.sub.3).sub.4, and the mixture is heated under reflux for 17 h. After cooling, the organic phase is removed, washed three times with 200 ml of water and once with 200 ml of saturated aqueous sodium chloride solution, dried over magnesium sulfate and concentrated to dryness by rotary evaporation. The gray residue is recrystallized from hexane. The precipitated crystals are filtered off with suction, washed with a little MeOH and dried under reduced pressure; yield: 47 g (150 mmol), 82% of theory.

e) Cyclization (Method B)

(15) ##STR00251##

(16) A mixture of 75 g (240 mmol) of 2-(2-nitrophenyl)indolizino[3,4,5-ab]isoindole and 290.3 ml (1669 mmol) of triethyl phosphite is heated under reflux for 12 h. Subsequently, the rest of the triethyl phosphite is distilled off (72-76° C./9 mmHg). Water/MeOH (1:1) is added to the residue, and the solids are filtered off and recrystallized from toluene. Yield: 47 g (167 mmol), 70% of theory.

f) Nucleophilic Substitution

(17) ##STR00252##

(18) 4.2 g of NaH (106 mmol, 60% in mineral oil), are dissolved in 300 ml of dimethylformamide under a protective atmosphere. 29 g (106 mmol) of compound (c) are dissolved in 250 ml of DMF and added dropwise to the reaction mixture. After 1 h at room temperature, a solution of 2-chloro-4,6-diphenyl-[1,3,5]-triazine (34.5 g, 0.122 mol) in 200 ml of THF is added dropwise. The reaction mixture is stirred at room temperature for 12 h and then poured onto ice. After warming to room temperature, the solids that precipitate out are filtered and washed with ethanol and heptane. The residue is subjected to hot extraction with toluene, recrystallized from toluene/n-heptane and finally sublimed under high vacuum. The purity is 99.9%. The yield is 32 g (63 mmol; 60% of theory).

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

(20) TABLE-US-00005 Reactant 1 Reactant 2 1f 2f 3f 4f 0 5f 6f 7f 8f 9f 0 Product Yield 1f 61% 2f 60% 3f 57% 4f 61% 5f 55% 6f 58% 7f 54% 8f 62% 9f 60%

g) Buchwald Coupling

(21) ##STR00280##

(22) 15.1 g (50 mmol) of compound (e) and 8.4 g (54 mmol) of bromobenzene are dissolved in 400 ml of toluene under an argon atmosphere. 1.0 g (5 mmol) of tri-tert-butylphosphine is added and the mixture is stirred under an argon atmosphere. 0.6 g (2 mmol) of Pd(OAc).sub.2 is added and the mixture is stirred under an argon atmosphere, and then 9.5 g (99 mmol) of sodium tert-butoxide are added. The reaction mixture is stirred under reflux for 24 h. After cooling, the organic phase is separated, washed three times with 200 ml of water, dried over MgSO.sub.4 and filtered, and the solvent is removed under reduced pressure. The residue is purified by column chromatography using silica gel (eluent: DCM/heptane (1:3)). The residue is subjected to hot extraction with toluene, recrystallized from toluene/n-heptane and finally sublimed under high vacuum. The yield is 16.9 g (47 mmol), 88% of theory.

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

(24) TABLE-US-00006 Reactant 1 Reactant 2 1g 2g 3g 4g 5g 0 6g 7g Product Yield 1g 71% 2g 75% 3g 74% 4g 72% 5g 78% 6g 00 70% 7g 01 71%

h) Bromination

(25) ##STR00302##

(26) 67 g (187 mmol) of compound g are suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulfuric acid (95-98%). 34 g (190 mmol) of NBS are added to this suspension in portions and the mixture is stirred in the dark for 2 h. Thereafter, water/ice is added and the solids are removed and washed with ethanol. The isomeric compounds ha and hb are separated by recrystallization. The yield is 51 g (117 mmol), 62% (ha), and 25 g (58 mmol), 31% (hb), corresponding to 93% of theory.

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

(28) TABLE-US-00007 Reactant 1 Product 1 1h 03 04 2h 05 06 Yield Product 2 (ratio 1:2) 1h 07 68%:24% 2h 08 70%:20%

j) Suzuki Coupling

(29) ##STR00309##

(30) 67 g (155 mmol) of compound (ha), 50 g (172 mmol) of N-phenylcarbazole-3-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 ml of ethylene glycol dimethyl ether and 280 ml of water. 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)palladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The yield is 56 g (94 mmol), 61% of theory.

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

(32) TABLE-US-00008 Reactant 1 Reactant 2 1j 0 2j 3j 4j 5j 6j 0 7j 8j 9j 10j 11j 0 12j Product Yield 1j 57% 2j 60% 3j 64% 4j 59% 5j 79% 6j 56% 7j 0 72% 8j 69% 9j 65% 10j 61% 11j 57% 12j 61%
Production of the OLEDs

(33) Examples 11 to 17 which follow (see Table 1) present the use of the materials of the invention in OLEDs.

(34) Pretreatment for Examples 11 to 17: Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating, first with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plaques form the substrates to which the OLEDs are applied.

(35) The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/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 aluminum 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 2.

(36) All 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 IC1:IC2:TER1 (50%:45%:5%) mean here that the material IC1 is present in the layer in a proportion by volume of 50%, IC2 in a proportion by volume of 45% and TER1 in a proportion by volume of 5%. Analogously, the electron transport layer may also consist of a mixture of two materials. The OLEDs are characterized in a standard manner. 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.

(37) Use of Mixtures of the Invention in OLEDs

(38) The materials of the invention can be used in the emission layer in phosphorescent red OLEDs. The inventive compounds 1f to 12j are used in Examples 11 to 17 as matrix material in the emission layer. The color coordinates of the electroluminescence spectra of the OLEDs are CIEx=0.67 and CIEy=0.33. These examples show that the materials of the invention are suitable for use in the emission layer of red OLEDs.

(39) In addition, the materials of the invention can be used successfully in the electron blocker layer (EBL). This is shown in Example 15. Here too, the color coordinates of the spectrum of each of the OLEDs are CIEx=0.67 and CIEy=0.33.

(40) TABLE-US-00009 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness I1 HATCN SpMA1 SpMA2 1f:TER1 — ST1:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I2 HATCN SpMA1 SpMA2 7f:TER1 — ST1:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I3 HATCN SpMA1 SpMA2 7g:TER1 — ST1:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I4 HATCN SpMA1 SpMA2 IC1:2g:TER1 — ST1:LiQ — 5 nm 125 nm 10 nm (50%:45%:5%) (50%:50%) 40 nm 35 nm I5 HATCN SpMA1 2 g IC1:2g:TER1 — ST1:LiQ — 5 nm 125 nm 10 nm (50%:45%:5%) (50%:50%) 40 nm 35 nm I6 HATCN SpMA1 SpMA2 12j:TER1 — ST1:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I7 HATCN SpMA1 SpMA2 IC2:12j:TER1 — ST1:LiQ — 5 nm 125 nm 10 nm (50%:45%:5%) (50%:50%) 40 nm 35 nm

(41) TABLE-US-00010 TABLE 2 Structural formulae of the materials for the OLEDs HATCN SpMA1 SpMA2 ST1 0 TER1 LiQ IC1 IC2 1f 7f 7g 2g 12j