CERIUM-ETHYLENEDIAMINE KETONE-TYPE AND CERIUM-SALEN-TYPE COMPLEXES AND USE THEREOF IN ORGANIC ELECTRONICS

Abstract

The present invention relates to an electronically doped semiconductor material and to an electronic component comprising cerium-ethylenediamine ketone-type and cerium-salen-type complexes. The invention also relates to the use of the cerium-ethylenediamine ketone-type and cerium-salen-type complexes as electron acceptors, especially as p-dopants and electron transport materials in organic-electronic components. The invention further relates to novel cerium-ethylenediamine ketone-type and cerium-salen-type complexes.

Claims

1. A electronic component comprising at least one compound of general formula (I)
Ce.sup.4+[L.sub.1L.sub.2].sup.4(I), wherein L.sub.1 and L.sub.2 are each a tetradentate ligand independently selected from ligands of formula (I.1) ##STR00045## 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 R.sup.12, 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 C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2 and wherein the aromatic or heteroaromatic ring system is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R.sup.9; A and B independently from each other represent N or CR.sup.7; R.sup.1 and R.sup.6 are independently selected from hydrogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.3-C.sub.7 cycloalkyl, wherein C.sub.3-C.sub.7 cycloalkyl is unsubstituted or substituted by 1, 2, 3, 4, 5 or 6 identical or different radicals R.sup.11, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9; or R.sup.1 and A together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9, or R.sup.6 und B together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9; R.sup.2 und R.sup.5 are independently selected from hydrogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.3-C.sub.7 cycloalkyl, wherein C.sub.3-C.sub.7 cycloalkyl is unsubstituted or substituted by 1, 2, 3, 4, 5 or 6 identical or different radicals R.sup.11, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9; R.sup.2 and A together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9, or R.sup.5 and B together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9; R.sup.4aR.sup.4b are independently from each other selected from hydrogen, C.sub.1-C.sub.6 alkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.10; R.sup.7 is selected from hydrogen, CN, nitro, halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl are unsubstituted or substituted with 1, 2, 3, 4 or identical or different radicals R.sup.10; R.sup.8 is selected from hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.10; R.sup.9 is selected from CN, halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals selected from C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl; R.sup.10 is selected from CN, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl; R.sup.11 is selected from CN, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl; R.sup.12 independently selected from halogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.3-C.sub.7 cycloalkyl, where C.sub.3-C.sub.7 cycloalkyl is unsubstituted or substituted by 1, 2, 3, 4, 5 or 6 identical or different radicals R.sup.11, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9.

2. The electronic component according to claim 1 comprising at least one compound of general formula (I)
Ce.sup.4+[L.sub.1L.sub.2].sup.4(I), wherein L.sub.1 and L.sub.2 are each a tetradentate ligand independently selected from ligands of formula (II) ##STR00046## wherein between the group CR.sup.3-CR.sup.4 represents a single or double bond; X independently from each other represents O or S; A and B independently from each other represent N or CR.sup.7; R.sup.1 and R.sup.6 are independently selected from hydrogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9; or R.sup.1 and A together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9, or R.sup.6 and B together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9; R.sup.3 and R.sup.4 are independently selected from hydrogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9, or R.sup.3 and R.sup.4 together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different R.sup.9 radicals; R.sup.2 and R.sup.5 are independently selected from hydrogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9; R.sup.4aR.sup.4b are independently from each other selected from hydrogen, C.sub.1-C.sub.6 alkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.10; R.sup.7 is selected from hydrogen, CN, nitro, halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.10; R.sup.8 is selected from hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.10; R.sup.9 is selected from CN, halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals selected from C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl; R.sup.10 is selected from CN, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl.

3. The electronic component according to claim 1 or 2, wherein in formula (I.1) wherein R.sup.1, R.sup.2, R.sup.5 and R.sup.6 are independently selected from hydrogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b and group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18 and A19 ##STR00047## ##STR00048## ##STR00049## wherein # denotes the bond to the group of formula (I) wherein R.sup.A, R.sup.B, R.sup.C, R.sup.D and R.sup.E are independently selected from hydrogen, CN, halogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl; or R.sup.1 and A together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 aryl group, wherein aryl is unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9; or R.sup.6 and B together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 aryl group, wherein aryl is unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9; R.sup.4a, R.sup.4b are independently selected from hydrogen, C.sub.1-C.sub.6 alkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.10; R.sup.9 is selected from CN, halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals selected from C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl; and R.sup.10 is selected from CN, halogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl.

4. The electronic component according to claim 1, wherein in formula (II) R.sup.3 and R.sup.4 are independently selected from hydrogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy and C.sub.1-C.sub.6 haloalkoxy and phenyl, wherein phenyl is unsubstituted or substituted by 1, 2, 3 or 4 identical or different radicals R.sup.9, or R.sup.3 and R.sup.4 together with the carbon atoms to which they are attached form a C.sub.6-C.sub.14 aryl group wherein aryl is unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9; R.sup.9 is selected from CN, halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl or C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 haloalkyl.

5. The electronic component according to claim 1, wherein in formula (I.1) A and B are independently a radical CR.sup.7 and R.sup.7 is selected from hydrogen, CN, nitro, halogen and group B consisting of B1, B2, B3, B4, B5, B6, B7, B8, B9, B10, B11, B12, B13, B14 and B15 ##STR00050## ##STR00051## wherein # denotes the bond to the group of formula (I.1), and wherein R.sup.F, R.sup.G, R.sup.H, R.sup.I and R.sup.J are independently selected from hydrogen, CN, halogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl.

6. The electronic component according to claim 1, wherein in R.sup.1, R.sup.2, R.sup.5 and R.sup.6, in formula (I.1), are independently selected from hydrogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, and A1 ##STR00052## # denotes the bond to the remaining molecule of formula (I.1) or formula (II), and wherein R.sup.A, R.sup.B, R.sup.C, R.sup.D and R.sup.E are independently selected from hydrogen, CN, fluorine, chlorine, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 fluoroalkyl and C.sub.1-C.sub.4 chloroalkyl, preferably selected from hydrogen, CN, fluorine and chlorine; or R.sup.1 and A together with the carbon atom to which they are attached form a phenyl ring, wherein phenyl is unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9; or R.sup.6 and B together with the carbon atom to which they are attached form a phenyl ring, wherein phenyl is unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9; R.sup.9 is selected from CN, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl and phenyl, wherein phenyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 haloalkyl.

7. The electronic component according claim 1, wherein in formula (I.1) are independently a radical CR.sup.7 and R.sup.7 is selected from hydrogen, CN, nitro, halogen, C.sub.1-C.sub.2 alkyl and C.sub.1-C.sub.2 haloalkyl.

8. The electronic component according to claim 1, wherein R.sup.3 and R.sup.4 are selected independently of one another from hydrogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, or R.sup.3 and R.sup.4 together with the carbon atoms to which they are attached form a phenyl ring, wherein phenyl is unsubstituted or substituted by 1, 2, 3 or 4 identical or different radicals R.sup.9; R.sup.9 is selected from CN, halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl or phenyl, where phenyl is unsubstituted or substituted by 1, 2, 3 or 4 identical or different substituents selected from C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-haloalky.

9. The electronic component according to claim 1, wherein L.sub.1 and L.sub.2 have the same meanings.

10. The electronic component according to claim 1, in the form of an organic light-emitting diode, an organic solar cell, a photovoltaic cell, an organic sensor, an organic diode or an organic field-effect transistor, preferably in form of a thin-film transistor.

11. The electronic component according to claim 1, having a layer structure, which comprises 2, 3, 4, 5, 6, 7 or more layers.

12. The electronic component according to claim 1, comprising an hole transport layer and/or a hole injection layer, which comprises at least of the compound of formula (I).

13. The electronic component according to claim 1, comprising an electron transport layer, which comprises at least of the compound of formula (I).

14. Doped semiconductor matrix material comprising at least one electron donor and at least one compound of the formula (I) as defined in claim 1, wherein the electron donor is preferably selected from 4,4,4-tris(N-(2-naphthyl)-N-phenyl-amino)triphenylamine (2-TNATA), 4,4,4-tris(N-3-methylphenyl-N-phenyl-amino)triphenylamine (m-MTDATA), N,N,N,N-tetrakis(4-methoxy-phenyl)benzidine (MeO-TPD), (2,2,7,7-tetrakis-(N,N-diphenylamino)-9,9-spirobifluorene (spiro-TTB), N,N-bis(naphthalene-1-yl)-N,N-bis(phenyl)-benzidine, N,N-bis(naphthalene-1-yl)-N,N-bis(phenyl)-9,9-spiro-bifluorene, 9,9-bis[4-(N,N-bis-biphenyl-4-yl-amino)phenyl]-9H-fluorene, 2,2-bis[N,N-bis(biphenyl-4-yl)amino]-9,9-spiro-bifluorene, N,N4(9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(N-([1,1-biphenyl]-4-yl)-[1,1-biphenyl]-4-amine) (BPAPF), N,N-bis(phenanthrene-9-yl)-N,N-bis(phenyl)-benzidine, 1,3,5-tris{4-[bis(9,9-dimethyl-fluorene-2-yl)amino]phenyl}benzene, tri(terphenyl-4-yl)amine, N-(4-(64(9,9-dimethyl-9H-fluorene-2-yl)(6-methoxy-[1,1-biphenyl]-3-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)phenyl)-N-(6-methoxy-[1,1-biphenyl]-3-yl)-9,9-dimethyl-9H-fluorene-2-amine, N-([1,1-biphenyl]-4-yl)-N-(4-(6-([1,1-biphenyl]-4-yl(9,9-dimethyl-9H-fluorene-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)phenyl)-9,9-dimethyl-9H-fluorene-2-amine, N,N-di([1,1-biphenyl]-4-yl)-3-(4-(di([1,1-biphenyl]-4-yl)amino)phenyl)-1,1,3-trimethyl-2,3-dihydro-1H-indene-5-amine, N-(4-(6-(bis(9,9-dimethyl-9H-fluorene-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluorene-2-yl)-9,9-dimethyl-9H-fluorene-2-amine, N-(4-(6-(9,9-spirobi[fluorene]-2-yl(9,9-dimethyl-9H-fluorene-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-spirobi[fluorene]-2-amine, N-(4-(6-(dibenzo[b,d]furane-2-yl(9,9-dimethyl-9H-fluorene-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluorene-2-yl)dibenzo[b,d]furan-2-amine, 9-(4-(6-(9H-carbazol-9-yl)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-9H-carbazole, N-([1,1-biphenyl]-4-yl)-3-(4-([1,1-biphenyl]-4-yl(4-methoxyphenyl)amino)phenyl)-N-(4-methoxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1H-inden-5-amine, 3-(4-(bis(6-methoxy-[1,1-biphenyl]-3-yl)amino)phenyl)-N,N-bis(6-methoxy-[1,1-biphenyl]-3-yl)-1,1,3-trimethyl-2,3-dihydro-1H-indene-5-amine, N1-([1,1-biphenyl]-4-yl)-N1-(4-(6-([1,1-biphenyl]-4-yl(4-(diphenylamino)phenyl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, N,N-di([1,1-biphenyl]-4-yl)-4-(6-(4-(di([1,1-biphenyl]-4-yl)amino)phenyl)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)-[1,1-biphenyl]-4-amine, N-(4-(5-(bis(9,9-dimethyl-9H-fluorene-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluorene-2-yl)-9,9-dimethyl-9H-fluorene-2-amine, N-(4-(6-(bis(9,9-dimethyl-9H-fluorene-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluorene-2-yl)-9,9-dimethyl-9H-fluorene-2-amine, N,N-bis(9,9-dimethyl-fluorene-2-yl)-N,N-diphenyl-benzidine (BF-DPB), N,N-((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(N-([1,1-biphenyl]-4-yl)-[1,1-biphenyl]-4-amine) (BPAPF), N4,N4,N4,N4-tetrakis(9,9-dimethyl-9H-fluorene-2-yl)-[1,1-biphenyl]-4,4-diamine (TDMFB), N-([1,1-biphenyl]-2-yl)-N-(9,9-dimethyl-9H-fluorene-2-yl)-9,9-spirobi[fluorene]-2-amine, (2,7-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobi[9H-fluorene] (spiro-MeO-TPD), a mixture of N-(4-(5-(bis(9,9-dimethyl-9H-fluorene-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluorene-2-yl)-9,9-dimethyl-9H-fluorene-2-amine and N-(4-(6-(bis(9,9-dimethyl-9H-fluorene-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluorene-2-yl)-9,9-dimethyl-9H-fluorene-2-amine, N-([1,1-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine and mixtures thereof.

15. A method for the production of an organic semiconductor, doping agent in organic semiconductor matrix materials, especially as p-dopant in hole transport layers, a charge injector in a charge injection layer, an electron transport layer, a cathode material in organic batteries, an electrochromic material an electron acceptor, wherein a compound of formula (I) or mixtures thereof, as defined in claim 1 is employed.

16. (canceled)

17. A compound of general formula (I)
Ce.sup.4+[L.sub.1L.sub.2].sup.4(I), their charge transfer complexes, their reduction products and mixtures thereof, wherein L.sub.1 and L.sub.2 are each a tetradentate ligand independently selected from ligands of formula (I.1) ##STR00053## 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 R.sup.12, 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 C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2 and wherein the aromatic or heteroaromatic ring system is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R.sup.9; A and B independently from each other represent N or CR.sup.7; R.sup.1 and R.sup.6 are independently selected from hydrogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.3-C.sub.7 cycloalkyl, wherein C.sub.3-C.sub.7-cycloalkyl is unsubstituted or substituted by 1, 2, 3, 4, 5 or 6 identical or different radicals R.sup.11, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9; or R.sup.1 and A together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9, or R.sup.6 and B together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9; R.sup.2 and R.sup.5 are independently selected from hydrogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.3-C.sub.7 cycloalkyl, wherein C.sub.3-C.sub.7 cycloalkyl is unsubstituted or substituted by 1, 2, 3, 4, 5 or 6 identical or different radicals R.sup.11, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9; R.sup.2 and A together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9, or R.sup.5 and B together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9; R.sup.4aR.sup.4b are independently from each other selected from hydrogen, C.sub.1-C.sub.6 alkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.10; R.sup.7 is selected from hydrogen, CN, nitro, halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl are unsubstituted or substituted with 1, 2, 3, 4 or identical or different radicals R.sup.10; R.sup.8 is selected from hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.10; R.sup.9 is selected from CN, halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals selected from C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl; R.sup.19 is selected from CN, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl; R.sup.11 is selected from CN, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl; R.sup.12 independently selected from halogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.3-C.sub.7 cycloalkyl, where C.sub.3-C.sub.7 cycloalkyl is unsubstituted or substituted by 1, 2, 3, 4, 5 or 6 identical or different radicals R.sup.11, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9; with the proviso that the following compounds are excluded: ##STR00054## ##STR00055## ##STR00056##

18. The compounds of general formula (I) according to claim 17
Ce.sup.4+[L.sub.1L.sub.2].sup.4(I), their charge transfer complexes, their reduction products and mixtures thereof, wherein L.sub.1 and L.sub.2 are each a tetradentate ligand independently selected from ligands of formula (II) ##STR00057## wherein between the group CR.sup.3-CR.sup.4 represents a single or double bond; X independently from each other represents O or S; A and B independently from each other represent N or CR.sup.7; R.sup.1 and R.sup.6 are independently selected from hydrogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9; or R.sup.1 and A together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9, or R.sup.6 and B together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different radicals R.sup.9; R.sup.3 and R.sup.4 are independently selected from hydrogen, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9, or R.sup.3 and R.sup.4 together with the carbon atom to which they are attached form a C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, aryl and hetaryl being unsubstituted or substituted with 1, 2, 3 or 4 identical or different R.sup.9 radicals; R.sup.2 and R.sup.5 are independently selected from hydrogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkylsulfanyl, C.sub.1-C.sub.6-haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl being unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.9; R.sup.4aR.sup.4b are independently from each other selected from hydrogen, C.sub.1-C.sub.6 alkyl and C.sub.6 C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.10; R.sup.7 is selected from hydrogen, CN, nitro, halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 haloalkylsulfanyl, NR.sup.4aR.sup.4b, C.sub.6-C.sub.14 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, NR.sup.8, O, S, SO and SO.sub.2, wherein aryl and hetaryl are unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.10; R.sup.8 is selected from hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R.sup.10; R.sup.9 is selected from CN, halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and C.sub.6-C.sub.14 aryl, wherein aryl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals selected from C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 haloalkyl; R.sup.10 is selected from CN, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, with the proviso that the following compounds and their reaction products of formula (I) are excluded: L.sub.1=L.sub.2=N,N-bis(4,4,4,-trifluorobut-1-en-3-one)-ethylendiamine, L.sub.1=L.sub.2=N,N-bis(4,4,5,5,5-pentafluoropent-1-en-3-one)-ethylendiamine, L.sub.1=L.sub.2=N,N-bis(4,4,5,5,6,6,6-heptafluorohex-1-en-3-one)-ethylendiamine and the following compounds and their reaction products: ##STR00058## ##STR00059##

Description

EXAMPLES

Abbreviation

[0347] APCI-MS atmospheric pressure chemical ionization-Mass spectrometer [0348] DCM Dichloromethane [0349] DEM Ethylene glycol dimethyl ether [0350] HTM Hole transport material [0351] MeCN Acetonitrile [0352] iPrOH Iso-Propanol [0353] EDTA Ethylenediaminetetraacetic acid

[0354] Cerium isopropoxide was prepared according to Gradeff, P. S. et al., Journal of the less common metals, Vol. 126, 1986, 335-338.

[0355] Sample Preparation for Conductivity Measurement:

[0356] Glass substrates with 50 nm thick patterned Au electrodes with channel length 100 m were used to prepare the doped thin film samples. The layers were deposited either by thermal evaporation or by deposition from the liquid phase, e.g., with spin coating. Thermal evaporation took place at room temperature in high vacuum (base pressure <510.sup.7 mbar). Hole transport material (HTM) and dopant were co-evaporated according to a dopant concentration of 20 wt %, with evaporation rates controlled by two independent quartz crystal microbalances.

[0357] The liquid-processed films were spin-coated from a chlorobenzene solution of HTM and dotand at 3000 rpm. The concentration of dotand in the HTM was nominally 10 wt %. The layers were then baked at 80 C. for 5 min. The film thickness was checked by profilometry and ranged from 50 to 110 nm.

[0358] Characterization:

[0359] The lateral conductivity of the coatings was determined from the slope of the current-voltage characteristics between 10 and 10V. The measurement took place directly after sample preparation for thermal evaporated coatings in-situ in high vacuum, for liquid processed coatings in air.

[0360] Synthesis of 1:

##STR00036##

[0361] The synthesis was performed according to the literature J. Schlfer, D. Graf, G. Fornalczyk, A. Mettenbrger, S. Mathur, Inorg. Chem. 2016, 55, 5422-5429.

[0362] Cyclovoltametry of 1 in dichloromethane (DCM, 200 mV/s, 0.1M NBu.sub.4PF.sub.6) resulted in the following: E.sub.1/2 (vs. Fc/Fc.sup.+)=0.51V.

[0363] Compound 1 sublimates without residue at an external temperature of 140 C. and a pressure of 10-2 mbar.

[0364] Synthesis of 2:

##STR00037##

[0365] The preparation of 4,4,4-trifluoro-3-oxobutanenitrile was carried out according to WO2005/49033.

[0366] 4,4,4-Trifluoro-3-oxobutanenitrile (1.9 g, 13.9 mmol) was dissolved in acetic anhydride (Ac.sub.2O, 5 ml) and (EtO).sub.3CH (2.05 g, 13.9 mmol). The reaction mixture was refluxed for one hour. Subsequently, all volatile components were removed in vacuo. The brown residue was dissolved in dichloromethane (DCM 20 ml) and 1,2-diaminoethane (0.2 ml) was added. The white precipitate was filtered off (0.079 g, 0.22 mmol, 1.6%). The mass spectrum of the ligand shows [MH].sup.+; 353.

[0367] To a 0.3M solution of Ce.sub.2(OiPr).sub.8(HOiPr).sub.2 (0.17 ml, 0.055 mmol) in ethylene glycol dimethyl ether/ipropanol (DME/iOrOH, 1:1 v/v) was added the ligand (76 mg, 0.21 mmol) under N.sub.2. After 30 min, the solvent was removed. 0.078 mg of red solid of compound 2 was obtained. The mass spectrum of compound 2 shows [MH].sup.; 843.

[0368] Cyclic voltametry of 2 in acetonitrile (ACN, 200 mV/s, 0.1M NBu.sub.4PF.sub.6) resulted in the following:

E.sub.1/2(vs. Fc/Fc.sup.+)=+0.40V.

[0369] Synthesis of 3:

##STR00038##

[0370] The synthesis of the ligand was performed according to the literature Gurley, L.; Beloukhina, N.; Boudreau, K.; Klegeris, A.; McNeil, W. S. Journal of Inorganic Biochemistry 2011, 105, 6, 858-866.

[0371] To a 0.4M solution of Ce.sub.2(OiPr).sub.8(HOiPr).sub.2 (0.33 ml, 0.131 mmol) in ethylene glycol dimethyl ether/ipropanol (DME/iPrOH) (1:1 v/v) was added 1 (120 mg, 0.26 mmol) under N.sub.2. After 30 min, the solvent was removed and the solid was washed with diethyl ether (Et.sub.2O). 56 mg of red solid of compound 3 was obtained. The mass spectrum of compound 3 shows [MH].sup.; 1047.

[0372] Cyclic voltammetry of 3 in acetonitrile (ACN, 200 mV/s, 0.1M NBu.sub.4PF.sub.6) resulted in the following: E.sub.1/2 (vs. Fc/Fc.sup.+)=0.36V.

[0373] Synthesis of 4:

##STR00039##

[0374] 3,5-Bistrifluoromethylacetophenone (8 g, 31.3 mmol) was dissolved in ethanol (40 ml), and acetic acid (0.1 ml) was added. Then 1,2-diaminoethane (0.94 g, 15.6 mmol) was added, and the solution was heated in a pressure tube for 12 h at 90 C. Upon cooling to 20 C., colorless crystals were formed, which were filtered off. After drying in vacuo, 2.0 g (0.37 mmol, 24%) of a colorless solid, N1,N2-bis(1-(3,5-bis(trifluoromethyl)phenyl)vinyl)ethane-1,2-diamine, APCI-MS (positive): 537.3 [M+H].sup.+, was obtained.

[0375] N1,N2-Bis(1-(3,5-bis(trifluoromethyl)phenyl)vinyl)ethane-1,2-diamine (9.72 g, 18.1 mmol) was suspended in DCM (50 ml) and trifluoroacetic anhydride (8.37 g, 39.8 mmol) were added. After stirring at room temperature for 12 h, the reaction solution was cooled to 20 C. and the white solid was filtered off. The solid was recrystallized from acetonitrile (50 ml) and filtered off. White solid, 4.16 g (5.71 mmol, 31%): 4,4-(ethane-1,2-diylbis(azanediyl))bis(4-(3,5-bis(trifluoromethyl)phenyl)-1,1,1-trifluorobut-3-en-2-one), APCI-MS (positive): 729.4 [M+H].sup.+.

[0376] 4,4-(ethane-1,2-diylbis(azanediyl))bis(4-(3,5-bis(trifluoromethyl)phenyl)-1,1,1-trifluorobut-3-en-2-one) (2 g, 2.74 mmol) were added to a solution of cerium(IV) isopropoxide (0.32M in DME/iPrOH, 4.3 ml, 1.37 mmol). After stirring for 12 h, the suspension was filtered and washed with DME. Red solid, 1.9 g (1.19 mmol, 87%),cerium bis((2Z,2Z,4Z,4Z)-4,4-(ethane-1,2-diylbis(azanylylide))bis(4-(3,5-bis(trifluoromethyl)phenyl)-1,1,1-trifluorobut-2-ene-2-olate)) (4), APCI-MS (positive): 1593 [M+H].sup.+.

[0377] The metal complex (4) (538 mg) was sublimed at 200 C. at 4.Math.10.sup.6 mbar. The yield was 335 mg (62%). The metal complex (4) decomposes at 260 C.

[0378] Cyclic voltammetry of 4 in acetonitrile (ACN, 200 mV/s, 0.1M NBu.sub.4PF.sub.6) resulted in the following:

E.sub.1/2(vs. Fc/Fc.sup.+)=0.12V.

[0379] When spiro-MeO-TAD (CAS No.: 207739-72-8) was doped with 20 wt % of the dopant (4), an increase in conductivity up to 1.5.Math.10.sup.6 S/cm was measured after solvent processing (spin coating). The intrinsic conductivity of the spiro-MeO-TAD without doping was measured to be 2.Math.10.sup.8 S/cm.

[0380] Synthesis of 5:

##STR00040##

[0381] 1-(2-hydroxy-5-(trifluoromethyl)phenyl)ethan-1-one (1.19 g, 0.583 mmol) and 1,2-diaminoethane (0.18 g, 0.29 mmol) were dissolved in DCM and stirred for 12 h. The solid was then filtered off. A white solid, 0.63 g (1.45 mmol, 50%), 2,2+(ethane-1,2-diylbis(azaneylylidene))bis(ethan-1-yl-1-ylidene))bis(4-(trifluoromethyl)phenol) was obtained, APCI-MS (positive): 433.3 [M+H].sup.+.

[0382] 2,2-(-(ethane-1,2-diylbis(azaneylylidene))bis(ethan-1-yl-1-ylidene))bis(4-(trifluoromethyl)phenol) (0.59 g, 1.36 mmol) were added to a solution of cerium(IV) isopropoxide (0.32M in DME/iPrOH, 0.68 mmol, 2.12 ml). The solvent was removed and the residue was washed with hexane. The residue was dissolved in CHCl.sub.3, filtered, and precipitated with hexane and filtered off. An orange-red solid, 0.42 g (0.42 mmol, 62%), cerium bis((2,2-((1E,1E)-(ethane-1,2-diylbis(azanylylidene))bis(ethan-1-yl-1-ylidene))bis(4-(trifluoromethyl)phenolate)) (5) was obtained. APCI-MS (positive): 1001 [M+H].sup.+.

[0383] The metal complex (5) (350 mg) was sublimed at 180-200 C. at 4.Math.10.sup.6 mbar. The yield was 12 mg (0.3%).

[0384] Cyclic voltammetry of 5 in acetonitrile (ACN, 200 mV/s, 0.1M NBu.sub.4PF.sub.6) resulted in the following: E.sub.1/2 (vs. Fc/Fc.sup.+)=+0.3V.

[0385] Synthesis of 6:

##STR00041##

[0386] Ethylenediamine (830 mg, 13.6 mmol) was added to a solution of 2-benzoyl-3-ethoxyacrylonitrile (5.54 g, 27.6 mmol) in 50 ml dichloromethane and allowed to stir at room temperature. After 2 h, a precipitate had formed, which was filtered off and washed with dichloromethane. After drying in vacuo, 2.75 g (7.43 mmol, 55%) of (2Z,2E)-2,2-((ethane-1,2-diylbis(azanediyl))bis(methanylylidene))bis(3-oxo-3-phenylpropanenitrile) was obtained.

[0387] To a solution of cerium isopropoxide (11.25 ml, 3.6 mmol) was added 2.67 g (7.2 mmol) (2Z,2E)-2,2-((ethane-1,2-diylbis(azanediyl))bis(methanylylidene))bis(3-oxo-3-phenylpropanenitrile). The brown solid was filtered off and washed with DME (15 ml) and hexane (20 ml). The solid was then washed three times with a total of 200 ml of dichloromethane and the wash solution was filtered. The wash solution was concentrated to half and hexane (100 ml) was added. The microcrystalline dark solid formed was filtered and dried in vacuo. 1.80 g (2.05 mmol, 57%) was obtained of (6). (6) decomposed at 170 C.

[0388] Cyclic voltammetry of 6 in acetonitrile (ACN, 200 mV/s, 0.1M NBu.sub.4PF.sub.6) resulted in the following: E.sub.1/2 (vs. Fc/Fc.sup.+)=0.1V.

[0389] Synthesis of 7:

##STR00042##

[0390] Phenylenediamine (1.62 g, 15 mmol) and (E)-4-ethoxy-1,1,1-trifluorobut-3-en-2-one (5 g, 30 mmol) were added together and stirred for 2 d at room temperature in 100 ml dichloromethane. The solution was concentrated by half then 100 ml of pentane was added. The microcrystalline solid, 4,4-(1,2-phenylenebis(azanylylidene))bis(1,1,1-trifluorobut-2-en-2-ol) (2.04 g, 5.80 mmol), was filtered and dried in vacuo. 4.12 g (11.7 mmol, 78%) was isolated.

[0391] 4,4-(1,2-Phenylenebis(azanylylidene))bis(1,1,1-trifluorobut-2-en-2-ol) (2.04 g, 5.80 mmol) was added to a solution cerium(IV) isopropoxide (0.32M in DME/iPrOH, 9 ml, 2.89 mmol) against. The directly resulting red solid was filtered off and washed with DME. Dark red solid (7) was obtained, 1.08 g (1.39 mmol, 48%). APCI-MS (positive): 841.1 [M+H].sup.+.

[0392] The metal complex (7) (1.00 g) was sublimed at 180-210 C. at 3.Math.10.sup.6 mbar. The yield was 205 mg (20%). The metal complex (7) decomposes at 237 C.

[0393] Cyclic voltammetry of 7 in acetonitrile (ACN, 200 mV/s, 0.1M NBu.sub.4PF.sub.6) resulted in the following: E.sub.1/2 (vs. Fc/Fc.sup.+)=0.09V.

[0394] Synthesis of 8:

##STR00043##

[0395] 4,5-difluorobenzene-1,2-diamine (2.14 g, 15 mmol) and (E)-4-ethoxy-1,1,1-trifluorobut-3-en-2-one (5 g, 30 mmol) were combined and stirred for 2 d at room temperature in 500 ml of dichloromethane. 100 ml of the dichloromethane was removed in vacuo and 200 ml of pentane was added. The microcrystalline solid, (2Z,2Z,4E,4E)-4,4-((4,5-difluoro-1,2-phenylene)bis(azanylylidene))bis(1,1,1-trifluorobut-2-en-2-ol), was filtered and dried in vacuo. 3.60 g (9.27 mmol, 62%) was isolated.

[0396] 4,4-((4,5-Difluoro-1,2-phenylene)bis(azanylylidene))bis(1,1,1-trifluorobut-2-en-2-ol) (2.50 g, 6.44 mmol) was added to a solution of cerium(IV) isopropoxide (0.32M in DME/iPrOH, 4.3 ml, 1.37 mmol). The suspension was filtered and the red solid was washed with a little DME and hexane. A dark red solid, (8), 0.70 g (0.77 mmol, 12%), cerium bis((2Z,2Z,4E,4E)-4,4-((4,5-difluoro-1,2-phenylene)bis(azanylylidene))bis(1,1,1-trifluorobut-2-en-2-olate)) was obtained, APCI-MS (positive): 913 [M+H].sup.+.

[0397] The metal complex (8) (700 mg) was sublimed at 180 C. at 3.10-6 mbar. The yield was 150 mg (22%). The metal complex (8) decomposes at 244 C.

[0398] Cyclic voltammetry of 8 in acetonitrile (ACN, 200 mV/s, 0.1M NBu.sub.4PF.sub.6) resulted in the following: E.sub.1/2 (vs. Fc/Fc.sup.+)=+0.08V.

[0399] When ZnPc (zinc phthalocyanine) was doped with 20 wt % of the dopant (8), an increase in conductivity up to 7.6.Math.10.sup.5 S/cm was measured after co-evaporation in vacuum. The intrinsic conductivity of ZnPc without doping is <1.Math.10.sup.8 S/cm. (Tietze, M. L., Pahner, P., Schmidt, K., Leo, K., & Lssem, B. (2015). Advanced Functional Materials, 25(18), 2701-2707).

[0400] When MeO-TPD (CAS No.: 122738-21-0) was doped with 20 wt % of the dopant (8), an increase in conductivity up to 1.10-5 S/cm was measured after co-evaporation in vacuum. The intrinsic conductivity of ZnPc without doping is 7.Math.10.sup.8 S/cm. (Sakai, N., Warren, R., Zhang, F., Nayak, S., Liu, J., Kesava, S. V., Lin, Y.-H., Biswal, H. S., Lin, X., Grovenor, C., Malinauskas, T., Basu, A., Anthopoulos, T. D., Getautis, V., Kahn, A., Riede, M., Nayak, P. K., & Snaith, H. J. (2021). Adduct-based p-doping of organic semiconductors. Nature Materials 2021 20:9, 20(9), 1248-1254.)

[0401] When spiro-MeO-TAD (CAS No.: 207739-72-8) was doped with 20 wt % of dopant (8), an increase in conductivity up to 2.8.10-6 S/cm was measured after solvent processing (spin coating). The intrinsic conductivity of the spiro-MeO-TAD without doping was measured to be 2.Math.10.sup.8 S/cm.

[0402] Synthesis of 9:

##STR00044##

[0403] 1-(3-Chloro-4-(trifluoromethyl)phenyl)-4,4,5,5-pentafluoropentane-1,3-dione (3.00 g, 8.13 mmol) was suspended in B(nBuO).sub.3 (9.35 g, 40.7 mmol) and 1,2-diaminophenylene (0.88 g, 8.13 mmol) was added. After 15 minutes, the white solid was filtered off and washed with little hexane. A white solid, 2.2 g (4.79 mmol, 59%), 1-((2-aminophenyl)amino)-1-(3-chloro-4-(trifluoromethyl)phenyl)-4,4,5,5-pentafluoropent-1-en-3-one, was obtained. APCI-MS (positive): 459 [M+H].sup.+.

[0404] 4-Ethoxy-1,1,1-trifluorobut-3-en-2-one (0.73 g, 4.37 mmol) was dissolved in DCM and 1-((2-aminophenyl)amino)-1-(3-chloro-4-(trifluoromethyl)phenyl)-4,4,5,5-pentafluoropent-1-en-3-one (2.0 g, 4.37 mmol) was added. The reaction mixture was stirred for 12 h and then the solvent was removed. The residue was dissolved in acetonitrile and subsequently copper(II) acetate (1.5 g) was added. Water was added to this dark green solution and the solid was filtered off. The solid was purified by column chromatography (chloroform as eluent). The residue was treated with oxalic acid and EDTA, then conc. HCl and chloroform, and the phases were separated. The organic phase was washed with saturated NaHCO.sub.3 and saturated NaCl solution and dried (Na.sub.2SO.sub.4). The solvent was removed. A white solid, 2.0 g (3.44 mmol, 79%), 1-(3-chloro-4-(trifluoromethyl)phenyl)-4,4,5,5-pentafluoro-1-((2-((-4,4,4-trifluoro-3-oxobut-1-en-1-yl)amino)phenyl)amino)pent-1-en-3-one was obtained. APCI-MS (positive): 581.8 [M+H].sup.+.

[0405] 1-(3-Chloro-4-(trifluoromethyl)phenyl)-4,4,5,5-pentafluoro-1-((2-((-4,4,4-trifluoro-3-oxobut-1-en-1-yl)amino)phenyl)amino)pent-1-en-3-one (1.9 g, 3.2 mmol) was added to a solution of cerium(IV) isopropoxide (0.32M in DME/iPrOH, 1.63 mmol, 5.1 ml). Hexane was added and the resulting solid was filtered off and washed with hexane. The residue was dissolved in chloroform, filtered, and recrystallized from chloroform/hexane. A red solid (9), 0.41 g (0.316 mmol, 20%) was obtained. APCI-MS (positive): 1296.8 [M+H].sup.+.

[0406] The metal complex (9) (313 mg) was sublimed at 180-190 C. at 3.Math.10.sup.6 mbar. The yield was 167 mg (53%). The metal complex (9) decomposes at 244 C.

[0407] Cyclic voltammetry of 9 in acetonitrile (ACN, 200 mV/s, 0.1M NBu.sub.4PF.sub.6) resulted in the following: E.sub.1/2 (vs. Fc/Fc.sup.+)=+0.0V.

[0408] When ZnPc (zinc phthalocyanine) was doped with 20 wt % of the dopant (9), an increase in conductivity up to 1.1.Math.10.sup.5 S/cm was measured after co-evaporation in vacuum. The intrinsic conductivity of ZnPc without doping is <1.Math.10.sup.8 S/cm. (Tietze, M. L., Pahner, P., Schmidt, K., Leo, K., & Lssem, B. (2015). Advanced Functional Materials, 25(18), 2701-2707).

[0409] When spiro-MeO-TAD (CAS No.: 207739-72-8) was doped with 20 wt % of dopant (9), an increase in conductivity up to 5.1.10-6 S/cm was measured after solvent processing (spin coating). The intrinsic conductivity of the spiro-MeO-TAD without doping was measured to be 2.Math.10.sup.8 S/cm.