PERI-CONDENSED HETEROCYCLIC COMPOUNDS AS MATERIALS FOR ELECTRONIC DEVICES

Abstract

The present application relates to compounds of a formula (I), to processes for preparing the compounds, and to electronic devices comprising one or more of the compounds.

Claims

1.-24. (canceled)

25. A compound of a formula (I) ##STR00876## where A is C═O, C═S, C═NR.sup.0, P(═O)R.sup.0, SO or SO.sub.2; Y is the same or different at each instance and is selected from N and CR.sup.1; Ar.sup.1 is an aromatic ring system which has 6 to 40 aromatic ring atoms and is substituted by R.sup.2 radicals, and which is fused onto the rest of the formula (I) via the three carbon atoms shown in formula (I), or a heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is substituted by R.sup.2 radicals, and which is fused onto the rest of the formula (I) via the three carbon atoms shown in formula (I); Z is the same or different at each instance and is selected from CR.sup.4 and N, or the Z—Z unit represents a unit of formula (Ar.sup.2) ##STR00877## where Ar.sup.2 is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals, and which include the C—C unit, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals, and which include the C—C unit, and where the dotted lines are the bonds of the Z—Z unit to the rest of the formula; R.sup.0 is the same or different at each instance and is selected from straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.1 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.2 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals selected from R.sup.2, R.sup.3 and R.sup.4 may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.3 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals selected from R.sup.2, R.sup.3 and R.sup.4 may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.4 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.2, R.sup.3 and R.sup.4 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.5 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(═O)(R.sup.6).sub.2, OR.sup.6, S(═O)R.sup.6, S(═O).sub.2R.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.5 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.6 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, NR.sup.6, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2; R.sup.6 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.6 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by one or more radicals selected from F and CN; where, when the two Y groups in formula (I) are CR.sup.1, either a) at least one group selected from the R.sup.1, R.sup.2, R.sup.3 and R.sup.4 groups is selected from aromatic ring systems which have 7 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals; and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals; or b) at least two groups selected from the R.sup.1, R.sup.2, R.sup.3 and R.sup.4 groups are selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals; and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals.

26. The compound according to claim 25, wherein A is C═O.

27. The compound according to claim 25, wherein Ar.sup.1 is selected from benzene, pyridine, pyrimidine, pyridazine, naphthalene, quinoline, quinazoline, phenanthrene, anthracene, triphenylene, fluorene, carbazole, dibenzofuran and dibenzothiophene.

28. The compound according to claim 25, wherein the Z—Z unit is a unit of the formula (Ar.sup.2) ##STR00878## where Ar.sup.2 is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals, and which include the C—C unit, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals, and which include the C—C unit, and where the dotted lines are the bonds of the Z—Z unit to the rest of the formula.

29. The compound according to claim 25, wherein Ar.sup.2 is selected from benzene, pyridine, pyrimidine, pyridazine, pyrazine, naphthalene, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, benzothiophene, benzofuran, indole and indane, each of which is substituted by R.sup.3 radicals, and which include the C—C unit in formula (Ar.sup.2).

30. The compound according to claim 25, wherein formula (I) includes at least one R.sup.1 group selected from N(R.sup.5).sub.2, aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.5 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.5 radicals.

31. The compound according to claim 25, wherein formula (I) includes at least one R.sup.1 group selected from the R-1 to R-82 groups ##STR00879## ##STR00880## ##STR00881## ##STR00882## ##STR00883## ##STR00884## ##STR00885## ##STR00886## ##STR00887## ##STR00888## ##STR00889## ##STR00890## ##STR00891## ##STR00892## ##STR00893## where the dotted bond represents the bond to the base skeleton of the formula (I), and in addition: Ar.sup.3 is the same or different at each instance and is a bivalent aromatic or heteroaromatic ring system which has 6 to 12 aromatic ring atoms and is substituted in each case by R.sup.5 radicals; Ar.sup.5 is the same or different at each instance and is an aromatic ring system which has 6 to 40 aromatic ring atoms and is substituted by R.sup.6 radicals, or a heteroaromatic ring system which has 6 to 40 aromatic ring atoms and is substituted by R.sup.6 radicals; A.sup.1 is the same or different at each instance and is C(R.sup.5).sub.2, NR.sup.5, O or S; k is 0 or 1, where k=0 means that no A.sup.3 group is bonded at this position and R.sup.5 radicals are bonded to the corresponding carbon atoms instead; m is 0 or 1, where m=0 means that the Ar.sup.3 group is absent and that the corresponding aromatic or heteroaromatic group is bonded directly to the base skeleton of the formula (I).

32. The compound according to claim 25, wherein formula (I) includes at least one R.sup.2 group selected from N(R.sup.5).sub.2, aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.5 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.5 radicals.

33. The compound according to claim 25, wherein formula (I) includes at least one R.sup.2 group selected from the R-1 to R-82 groups ##STR00894## ##STR00895## ##STR00896## ##STR00897## ##STR00898## ##STR00899## ##STR00900## ##STR00901## ##STR00902## ##STR00903## ##STR00904## ##STR00905## ##STR00906## ##STR00907## ##STR00908## ##STR00909##

34. The compound according to claim 25, wherein formula (I) includes at least one R.sup.3 group selected from N(R.sup.5).sub.2, aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.5 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.5 radicals.

35. The compound according to claim 25, wherein formula (I) includes at least one R.sup.3 group selected from the R-1 to R-82 groups ##STR00910## ##STR00911## ##STR00912## ##STR00913## ##STR00914## ##STR00915## ##STR00916## ##STR00917## ##STR00918## ##STR00919## ##STR00920## ##STR00921## ##STR00922## ##STR00923## ##STR00924## ##STR00925##

36. The compound according to claim 25, wherein formula (I) includes at least one group selected from the R.sup.1, R.sup.2, and R.sup.3 groups which is selected from aromatic ring systems which have 7 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals.

37. Compound according to claim 25, wherein formula (I) includes at least one group selected from the R.sup.2, and R.sup.3 groups which is selected from the R-1 to R-81 groups ##STR00926## ##STR00927## ##STR00928## ##STR00929## ##STR00930## ##STR00931## ##STR00932## ##STR00933## ##STR00934##

38. The compound according to claim 25, wherein the compound has one of the formulae (I-A-1) to (I-A-3) ##STR00935## where R.sup.1-1, R.sup.2-1 and R.sup.3-1 are selected from aromatic ring systems which have 7 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals; and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals.

39. The compound according to claim 25, wherein the compound conforms to one of the following formulae: ##STR00936## ##STR00937## ##STR00938## where the variables are as defined in claim 25, and where, when Y is CR.sup.1, either a) at least one group selected from the R.sup.1, R.sup.2, R.sup.3 and R.sup.4 groups is selected from aromatic ring systems which have 7 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals; and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals; or b) at least two groups selected from the R.sup.1, R.sup.2, R.sup.3 and R.sup.4 groups are selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals; and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals.

40. The compound according to claim 39, wherein the formulae each include at least one group selected from the R.sup.1, R.sup.2 and R.sup.3 groups which is selected from aromatic ring systems which have 7 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are each substituted by R.sup.5 radicals.

41. A compound of one of the following structural formulae HT-1 to HT-13: ##STR00939## ##STR00940## ##STR00941## ##STR00942## ##STR00943##

42. A process for preparing the compound according to claim 25, comprising i) reacting an imidazole or benzimidazole derivative with an aryl or heteroaryl compound having a halogen in a benzyl position, and ii) conducting a ring closure reaction under Pd catalysis, and iii) oxidating a methylene group in the ring formed to a carbonyl group; or iv) reacting an imidazole or benzimidazole derivative with an aryl or heteroaryl compound having a carbonyl halide group, and v) conducting a ring closure reaction.

43. A formulation comprising at least one compound according to claim 25, and at least one further compound and/or at least one solvent.

44. A method comprising providing a compound of the formula (I) ##STR00944## where the variables that occur are as follows: A is C═O, C═S, C═NR.sup.0, P(═O)R.sup.0, SO or SO.sub.2; Y is the same or different at each instance and is selected from N and CR.sup.1; Ar.sup.1 is an aromatic ring system which has 6 to 40 aromatic ring atoms and is substituted by R.sup.2 radicals, and which is fused onto the rest of the formula (I) via the three carbon atoms shown in formula (I), or a heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is substituted by R.sup.2 radicals, and which is fused onto the rest of the formula (I) via the three carbon atoms shown in formula (I); Z is the same or different at each instance and is selected from CR.sup.4 and N, or the Z—Z unit represents a unit of formula (Ar.sup.2) ##STR00945## where Ar.sup.2 is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals, and which include the C—C unit, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals, and which include the C—C unit, and where the dotted lines are the bonds of the Z—Z unit to the rest of the formula; R.sup.0 is the same or different at each instance and is selected from straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.1 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.2 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals selected from R.sup.2, R.sup.3 and R.sup.4 may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.3 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals selected from R.sup.2, R.sup.3 and R.sup.4 may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.4 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.2, R.sup.3 and R.sup.4 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.5 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(═O)(R.sup.6).sub.2, OR.sup.6, S(═O)R.sup.6, S(═O).sub.2R.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.5 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.6 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, NR.sup.6, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2; R.sup.6 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.6 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by one or more radicals selected from F and CN; and incorporating the compound in an electronic device.

45. An electronic device comprising at least one compound as defined in claim 41.

46. The electronic device according to claim 45, wherein it is an organic electroluminescent device, and wherein the compound is used in an emitting layer as matrix material for phosphorescent emitters or for emitters that exhibit TADF (thermally activated delayed fluorescence), or in an electron transport layer and/or in a hole blocker layer and/or in a hole transport layer and/or in an electron blocker layer.

47. A material comprising at least one compound as defined in claim 43 and at least one further compound selected from the group of the biscarbazoles, the bridged carbazoles, the triarylamines, the dibenzofuranyl-carbazole derivatives, the dibenzofuranyl-amine derivatives, and the carbazoleamines.

48. An organic electroluminescent device comprising the material according to claim 47 in a layer.

Description

EXAMPLES

A) Synthesis of Compounds of the Formula (I)

a) 9-Phenyl-3-(2-phenyl-1H-benzimidazol-5-yl)carbazole

[0156] ##STR00539##

[0157] 31.5 g (110.0 mmol) of phenylcarbazole-3-boronic acid, 30 g (110.0 mmol) of 6-bromo-2-phenyl-1H-benzimidazole and 44.6 g (210.0 mmol) of tripotassium phosphate are suspended in 500 ml of toluene, 500 ml of dioxane and 500 ml of water. To this suspension are added 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate, 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 each time of water and then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane/iso-propanol. The yield is 39.6 g (91 mmol), corresponding to 83% of theory.

[0158] The following compounds can be obtained analogously:

TABLE-US-00005 Ex. Reactant 1 Reactant 2 Product Yield  1a [00540] [00541] [00542] 74%  2a [00543] [00544] [00545] 72%  3a [00546] [00547] [00548] 66%  4a [00549] [00550] [00551] 76%  5a [00552] [00553] [00554] 65%  6a [00555] [00556] [00557] 60%  7a [00558] [00559] [00560] 59%  8a [00561] [00562] [00563] 62%  9a [00564] [00565] [00566] 67% 10a [00567] [00568] [00569] 80% 11a [00570] [00571] [00572] 82% 12a [00573] [00574] [00575] 80% 13a [00576] [00577] [00578] 85% 14a [00579] [00580] [00581] 81% 15a [00582] [00583] [00584] 80% 16a [00585] [00586] [00587] 83% 17a [00588] [00589] [00590] 80% 18a [00591] [00592] [00593] 82% 19a [00594] [00595] [00596] 79% 20a [00597] [00598] [00599] 78% 21a [00600] [00601] [00602] 79% 22a [00603] [00604] [00605] 70%

b)1-[(2-bromophenyl)methyl]-2-phenylbenzimidazole

[0159] ##STR00606##

[0160] 13.3 g (334 mmol) of 60% NaH in mineral oil is dissolved in 1000 ml of dimethylformamide under protective atmosphere. 50 g (257 mmol) of 2-phenylbenzimidazole is dissolved in 500 ml of DMF and added dropwise to the reaction mixture. After 1 h at room temperature, a solution of 70 g (283 mmol) of 2-bromobenzyl bromide in 500 ml of DMF is added dropwise. The reaction mixture is then stirred at room temperature for 1 h. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and concentrated. The residue is subjected to hot extraction with toluene and recrystallized from toluene/n-heptane.

[0161] Yield: 75 g (207 mmol), 80%.

[0162] The following compounds can be obtained analogously:

TABLE-US-00006 Ex. Reactant 1 Reactant 2 Product Yield  1b [00607] [00608] [00609] 78%  2b [00610] [00611] [00612] 80%  3b [00613] [00614] [00615] 83%  4b [00616] [00617] [00618] 83%  5b [00619] [00620] [00621] 84%  6b [00622] [00623] [00624] 79%  7b [00625] [00626] [00627] 80%  8b [00628] [00629] [00630] 77%  9b [00631] [00632] [00633] 79% 10b [00634] [00635] [00636] 81% 11b [00637] [00638] [00639] 85% 12b [00640] [00641] [00642] 78% 13b [00643] [00644] [00645] 82% 14b [00646] [00647] [00648] 80% 15b [00649] [00650] [00651] 87% 16b [00652] [00653] [00654] 88% 17b [00655] [00656] [00657] 86% 18b [00658] [00659] [00660] 83% 19b [00661] [00662] [00663] 84% 20b [00664] [00665] [00666] 80% 21b [00667] [00668] [00669] 76% 22b [00670] [00671] [00672] 78% 23b [00673] [00674] [00675] 70% 24b [00676] [00677] [00678] 77% 25b [00679] [00680] [00681] 80% 26b [00682] [00683] [00684] 78% 27b [00685] [00686] [00687] 81% 28b [00688] [00689] [00690] 80% 29b [00691] [00692] [00693] 77% 30b [00694] [00695] [00696] 87% 31b [00697] [00698] [00699] 80%

c) 5-Phenyl-1H-imidazo[4,5,1-de]phenanthridine

[0163] ##STR00700##

[0164] 68 g (187 mol) of 1-[(2-bromophenyl)methyl]-2-phenylbenzimidazole is dissolved in 500 ml of dimethylformamide under protective atmosphere. 38 g (394 mmol) of potassium acetate is added to this solution, which is stirred for 30 min, and then 21 g (18.7 mmol) of Pd(PPh.sub.3).sub.4 is added, and stirring of the mixture is continued at 110° C. for 5 days. After this time, the reaction mixture is cooled to room temperature and extracted with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and concentrated. The residue is recrystallized from acetone. Yield: 42 g (151 mmol), 81%.

[0165] The following compounds can be obtained analogously:

TABLE-US-00007 Ex. Reactant 1 Product Yield  1c [00701] [00702] 80%  2c [00703] [00704] 84%  3c [00705] [00706] 85%  4c [00707] [00708] 81%  5c [00709] [00710] 83%  6c [00711] [00712] 79%  7c [00713] [00714] 77%  8c [00715] [00716] 76%  9c [00717] [00718] 81% 10c [00719] [00720] 68% 11c [00721] [00722] 60% 12c [00723] [00724] 69% 13c [00725] [00726] 71% 14c [00727] [00728] 71% 15c [00729] [00730] 76% 16c [00731] [00732] 83% 17c [00733] [00734] 85% 18c [00735] [00736] 69% 19c [00737] [00738] 61% 20c [00739] [00740] 72% 21c [00741] [00742] 76% 22c [00743] [00744] 76% 33c [00745] [00746] 74% 24c [00747] [00748] 81% 25c [00749] [00750] 66% 26c [00751] [00752] 76% 27c [00753] [00754] 77% 28c [00755] [00756] 69% 29c [00757] [00758] 71% 30c [00759] [00760] 76% 31c [00761] [00762] 77%

d) 5-Phenyl-1H-imidazo[4,5,1-de]phenanthridin-7-one

[0166] ##STR00763##

[0167] 34 g (120 mmol) of 5-phenyl-1H-imidazo[4,5,1-de]phenanthridine is dissolved in 600 ml of dichloromethane and 600 ml of water. 13 g (120 mmol) of 18-crown-16 and 28 g (181 mmol) of potassium permanganate are added to this solution in portions, and the mixture is stirred at room temperature for two days. After this time, the rest of the potassium permanganate is filtered off, and the solution is concentrated and purified by chromatography (eluent: heptane/dichloromethane, 5:1). The residue is recrystallized from toluene and from dichloromethane and finally sublimed under high vacuum; purity is 99.9%.

[0168] Yield: 121 g (71 mmol), 59%.

[0169] The following compounds can be obtained analogously:

TABLE-US-00008 Ex. Reactant 1 Product Yield  1d [00764] [00765] 83%  2b [00766] [00767] 76%  3d [00768] [00769] 86%  4d [00770] [00771] 66%  5d [00772] [00773] 82%  6d [00774] [00775] 92%  7d [00776] [00777] 66%  8d [00778] [00779] 69%  9d [00780] [00781] 71% 10d [00782] [00783] 78% 11d [00784] [00785] 72% 12d [00786] [00787] 79% 13d [00788] [00789] 76% 14d [00790] [00791] 72% 15d [00792] [00793] 83% 16d [00794] [00795] 75% 17d [00796] [00797] 75% 18d [00798] [00799] 76% 19d [00800] [00801] 74% 20d [00802] [00803] 81% 21d [00804] [00805] 79% 22d [00806] [00807] 69% 23d [00808] [00809] 73% 24d [00810] [00811] 86% 25d [00812] [00813] 77% 26d [00814] [00815] 76% 27d [00816] [00817] 78% 28d [00818] [00819] 80% 29d [00820] [00821] 83% 30d [00822] [00823] 78%

e) 1-[2-(5-Bromo-2-phenyl-3H-benzimidazol-4-yl)phenyl]ethanone

[0170] ##STR00824##

[0171] 6.5 g (22 mmol) of 5-phenyl-1H-imidazo[4,5,1-de]phenanthridin-7-one is initially charged in 160 ml of DMF. Subsequently, a solution of 4 g (22.5 mmol) of NBS in 100 ml of DMF is added dropwise in the dark at room temperature, the mixture is allowed to come to room temperature and stirring is continued at this temperature for 4 h. Subsequently, 150 ml of water are added to the mixture and extraction is effected with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4 and the solvents are removed under reduced pressure. The product is subjected to extractive stirring with hot hexane and filtered off with suction. Yield: 5 g (13 mmol), 61% of theory, purity by .sup.1H NMR about 98%.

[0172] The following compounds are obtained in an analogous manner:

TABLE-US-00009 Ex. Reactant 1 Product Yield 1e [00825] [00826] 65% 2e [00827] [00828] 62% 3e [00829] [00830] 71% 4e [00831] [00832] 79%

f) 3-[9-(1H-benzimidazol-2-yl)carbazol-3-yl]-9-phenylcarbazole

[0173] ##STR00833##

[0174] 16.3 g (40 mmol) of 3-(9H-carbazol-3-yl)-9-phenylcarbazole and 11 g (45 mmol) of 2-iodo-1H-benzimidazole and 44.7 g (320 mmol) of potassium carbonate, 3 g (16 mmol) of copper(I) iodide and 3.6 g (16 mmol) of 1,3-di(pyridin-2-yl)propane-1,3-dione are stirred in 100 ml of DMF at 150° C. for h. The solution is diluted with water and extracted twice with ethyl acetate, and the combined organic phases are dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. The residue is purified by chromatography (EtOAc/hexane: ⅔). The purity is 99.9%.

[0175] The yield is 13 g (25 mmol), 63% of theory.

[0176] The following compounds can be prepared analogously:

TABLE-US-00010 Reactant 1 Reactant 2 Product Yield 1f [00834] [00835] [00836] 66%

g) 9-Phenyl-3-[9-(2-phenyl-1H-benzimidazol-5-yl)carbazol-3-yl]carbazole

[0177] ##STR00837##

[0178] 27 g (66 mmol) of 3-(9H-carbazol-3-yl)-9-phenylcarbazole, 19.11 g (70 mmol) of 5-bromo-2-phenyl-1H-benzimidazole and 19 g of NaOtBu are suspended in 1 I of p-xylene. To this suspension are added 0.3 g (1.33 mmol) of Pd(OAc).sub.2 and 1.0 ml of a 1M tri-tert-butylphosphine solution. The reaction mixture is heated under reflux for 16 h. After cooling, methylene chloride is added, and the organic phase is removed and washed three times with 200 ml of water and then concentrated to dryness. The residue is subjected to hot extraction with toluene and recrystallized from toluene; purity is 99.9% by HPLC. The yield is 29 g (49 mmol; 75%).

[0179] The following compounds can be prepared analogously:

TABLE-US-00011 Reactant 1 Reactant 2 Product Yield 1g [00838] [00839] [00840] 79% 2g [00841] [00842] [00843] 80% 3g [00844] [00845] [00846] 85% 4g [00847] [00848] [00849] 80% 5g [00850] [00851] [00852] 77%

B) Device Examples

[0180] Examples E1 to E14 which follow (see table 1) present the use of the materials of the invention in OLEDs.

[0181] Glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plates form the substrates to which the OLEDs are applied.

[0182] The OLEDs basically have the following layer structure: substrate/optional interlayer (IL)/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 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 2. The data of the OLEDs are listed in tables 3 and 4.

[0183] 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 IC1:EG1:TEG1 (45%:45%:10%) mean here that the material IC1 is present in the layer in a proportion by volume of 45%, EG1 in a proportion of 45% and TEG1 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0184] The OLEDs are characterized in a standard manner. For this purpose, electroluminescence spectra, current efficiency (CE, measured in cd/A) and external quantum efficiency (EQE, measured in %) are determined as a function of luminance, calculated from current-voltage-luminance characteristics assuming Lambertian emission characteristics. Electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and these are used to calculate the CIE 1931 x and y colour coordinates. The results thus obtained can be found in tables 3 and 4.

[0185] Use of Compounds of the Formula (I) as Matrix Materials in the Emitting Layer

[0186] The inventive compounds EG1 to EG7 are used in examples E1 to E9 as matrix material in the emission layer of phosphorescent green OLEDs (table 3). Low voltage and good efficiency occur here.

[0187] The inventive compounds EG8, EG9 and EG10 are used in examples E10 to E13 as matrix material in the emission layer of phosphorescent red OLEDs (table 3). Low voltage and good efficiency occur here.

[0188] Use of Compounds of the Formula (I) as Electron Transport Materials in the Emitting Layer

[0189] When the inventive compound EG5 is used as electron transport material in example E14, low voltage and good efficiency are obtained (table 4).

TABLE-US-00012 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. IL thickness thickness thickness thickness thickness thickness thickness E1  HATCN SpMAl SpMA2 EG1:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (88%:12%) 40 nm  5 nm (50%:50%) 30 nm 1 nm E2  HATCN SpMAl SpMA2 EG2:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (88%:12%) 40 nm  5 nm (50%:50%) 30 nm 1 nm E3  HATCN SpMAl SpMA2 EG3:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (88%:12%) 40 nm  5 nm (50%:50%) 30 nm 1 nm E4  HATCN SpMAl SpMA2 EG1:IC1:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (49%:44%:7%) 40 nm  5 nm (50%:50%) 30 nm 1 nm E5  HATCN SpMAl SpMA2 EG3:IC2:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (44%:44%:12%) 40 nm  5 nm (50%:50%) 30 nm 1 nm E6  HATCN SpMAl SpMA2 EG4:IC3:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (49%:44%:7%) 40 nm  5 nm (50%:50%) 30 nm 1 nm E7  HATCN SpMAl SpMA2 EG5:IC4:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (49%:44%:7%) 40 nm  5 nm (50%:50%) 30 nm 1 nm E8  HATCN SpMAl SpMA2 EG6:IC1:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (49%:44%:7%) 40 nm  5 nm (50%:50%) 30 nm 1 nm E9  HATCN SpMAl SpMA2 EG7:IC1:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (49%:44%:7%) 40 nm  5 nm (50%:50%) 30 nm 1 nm E10 HATCN SpMAl SpMA2 EG8:TER5 ST2 ST2:LiQ LiQ 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm 1 nm E11 HATCN SpMAl SpMA2 EG9:TER5 ST2 ST2:LiQ LiQ 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm 1 nm E12 HATCN SpMAl SpMA2 EG10:TER5 ST2 ST2:LiQ LiQ 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm 1 nm E13 HATCN SpMAl SpMA2 EG8:IC5:TER5 ST2 ST2:LiQ LiQ 5 nm 125 nm 10 nm (72%:25%:3%) 35 nm 10 nm (50%:50%) 30 nm 1 nm E14 SpAl HATCN SpMAl IC1:TEG1 — EG5:LiQ 70 nm  5 nm 90 nm (90%:10%) 30 nm (50%:50%) 40 nm

TABLE-US-00013 TABLE 2 Structural formulae of the materials for the OLEDs [00853] [00854] HATCN SpMA1 [00855] [00856] SpMA2 TEG1 [00857] [00858] TER5 IC1 [00859] [00860] IC2 IC3 [00861] [00862] IC4 IC5 [00863] [00864] ST2 LiQ [00865] [00866] SpA1 EG1 (5g) [00867] [00868] EG2 (15d) EG3 (26d) [00869] [00870] EG4 (29d) EG5 (31d) [00871] [00872] EG6 (17a) EG7 (19a) [00873] [00874] EG8 (21d) EG9 (27d) [00875] EG 10 (22a)

TABLE-US-00014 TABLE 3 Data of the OLEDs U1000 SE1000 EQE 1000 CIE x/y at Ex. (V) (cd/A) (%) 1000 cd/m.sup.2 E1 4.2 66 15.5 0.33/0.62 E2 4.4 67 15 0.34/0.62 E3 4.6 58 16 0.34/0.61 E4 3.3 62 17 0.35/0.60 E5 3.5 64 17 0.34/0.63 E6 3.1 67 18 0.35/0.61 E7 3.2 72 19 0.33/0.62 E8 3.1 67 18 0.34/0.61 E9 3.1 68 18 0.33/0.62 E10 3.9 23 19.5 0.67/0.33 E11 3.8 24 20 0.66/0.34 E12 3.2 23 21 0.67/0.33 E13 3.5 23 18.2 0.67/0.33

TABLE-US-00015 TABLE 4 Data of the OLEDs U1000 SE1000 EQE 1000 CIE x/y at Ex. (V) (cd/A) (%) 1000 cd/m.sup.2 E14 3.8 65 16 0.31/0.64