Cerium-ethylenediamine ketone-type and cerium-salen-type complexes and use thereof in organic electronics

A compound of general formula (I)

• Ce4+[L1L2]4− (I),
• their charge transfer complexes, their reduction products and mixtures thereof, wherein L1 and L2 are each a tetradentate ligand independently selected from ligands of formula (I.1)
• wherein
• X independently from each other represents O or S;
• Z is a bridging group, which has 2 or 3 carbon atoms between the nitrogen atoms, wherein the carbon atoms each being unsubstituted or substituted by 1, 2, 3, 4, 5 or 6 identical or different radicals R12, wherein two adjacent carbon atoms may be linked to one another by a double bond, or 2 or 3 of the carbon atoms are part of a mononuclear, 2-nuclear or 3-nuclear C6-C14 aromatic or heteroaromatic ring system, wherein the heteroaromatic ring system has 4 to 13 carbon atoms and has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members selected from N, NR8, O, S, SO and SO2 and wherein the aromatic or heteroaromatic ring system is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R9;
• A and B independently from each other represent N or CR7;
• R1 and R6 are independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C7 cycloalkyl, wherein C3-C7-cycloalkyl is unsubstituted or substituted by 1, 2, 3, 4, 5 or 6 identical or different radicals R11, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR4aR4b, C6-C14 aryl and hetaryl having 4 to 13 carbon atoms, wherein hetaryl having 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members selected from N, NR8, O, S, SO and SO2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R9;
• or
• R1 and A together with the carbon atom to which they are attached form a C6-C14 aryl group or hetaryl group having 4 to 13 carbon atoms, wherein hetaryl having 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members selected from N, NR8, O, S, SO and SO2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R9, or
• R6 and B together with the carbon atom to which they are attached form a C6-C14 aryl group or hetaryl group having 4 to 13 carbon atoms, wherein hetaryl having 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members selected from N, NR8, O, S, SO and SO2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R9;
• R2 and R5 are independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or substituted by 1, 2, 3, 4, 5 or 6 identical or different radicals R11, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR4aR4b, C6-C14 aryl and hetaryl having 4 to 13 carbon atoms, wherein hetaryl having 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members selected from N, NR8, O, S, SO and SO2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R9;
• R2 and A together with the carbon atom to which they are attached form a C6-C14 aryl group or hetaryl group having 4 to 13 carbon atoms, wherein hetaryl having 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members selected from N, NR8, O, S, SO and SO2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R9, or
• R5 and B together with the carbon atom to which they are attached form a C6-C14 aryl group or hetaryl group having 4 to 13 carbon atoms, wherein hetaryl having 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members selected from N, NR8, O, S, SO and SO2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R9;
• R4aR4b are independently from each other selected from hydrogen, C1-C6 alkyl and C6-C14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R10;
• R7 is selected from hydrogen, CN, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR4aR4b, C6-C14 aryl and hetaryl having 4 to 13 carbon atoms, wherein hetaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members selected from N, NR8, O, S, SO and SO2, wherein aryl and hetaryl are unsubstituted or substituted with 1, 2, 3, 4 or identical or different radicals R10;
• R8 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R10;
• R9 is selected from CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals selected from C1-C4 alkyl and C1-C4 haloalkyl;
• R19 is selected from CN, halogen, C1-C4 alkyl, C1-C4 haloalkyl;
• R11 is selected from CN, halogen, C1-C4 alkyl, C1-C4 haloalkyl;
• R12 independently selected from halogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C7 cycloalkyl, where C3-C7 cycloalkyl is unsubstituted or substituted by 1, 2, 3, 4, 5 or 6 identical or different radicals R11, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR4aR4b, C6-C14 aryl and hetaryl having 4 to 13 carbon atoms, wherein hetaryl having 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members selected from N, NR8, O, S, SO and SO2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R9;
• with the proviso that the following compounds are excluded: