Cerium-ethylenediamine ketone-type and cerium-salen-type complexes and their uses in organic electronic devices

Abstract

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

Description

Technology Field

[0001] The present invention relates to electronically doped semiconductor materials and electronic components comprising cerium-ethylenediamine ketone-type and cerium-salen-type complexes. The present invention also relates to the use of cerium-ethylenediamine ketone-type and cerium-salen-type complexes as electron acceptors, particularly as p-dopants and electron transport materials in organic-electronic components. The present invention also relates to novel cerium-ethylenediamine ketone-type and cerium-salen-type complexes. Background Technology

[0002] Organic electronics focuses on the development, characterization, and application of new materials based on small organic molecules and polymers with specific desired electronic properties for the production of electronic components. These include, for example, organic field-effect transistors (OFETs) such as organic thin-film transistors (OTFTs), organic electroluminescent devices such as organic light-emitting diodes (OLEDs), organic solar cells (OSCs), for example, exciton solar cells, dye-sensitized solar cells (DSSCs), or perovskite solar cells, and photoconductive materials in electrophotography, for example, organic photoconductors (OPCs), organic optical detectors, organic photoreceptors, light-emitting electrochemical cells (LECs), and organic laser diodes.

[0003] It is known that the electrical conductivity of organic semiconductor matrices can be significantly affected by doping. These organic semiconductor matrix materials can be formed from compounds with excellent electron conductivity (p-conductors) or compounds with excellent electron acceptor properties (n-conductors). Unlike inorganic semiconductors, organic semiconductors have very low intrinsic charge carrier concentrations. Therefore, organic semiconductor matrix materials are generally doped to achieve excellent semiconductor properties. In the case of n-doping, a strong electron donor (n-dopant) is used, which transfers electrons to the LUMO of the semiconductor matrix (n-doping), generating free electrons (SOMO) in the matrix. In the case of p-doping, a strong electron acceptor (p-dopant) is used, which removes electrons from the HOMO (p-doping) of the semiconductor matrix, generating holes. That is, in the case of p-doping, the LUMO of the dopant must be lower than the HOMO energy of the matrix. The dopant acts as an acceptor and leaves mobile holes (SOMO) in the matrix.

[0004] P-dopants known for use as electron acceptor materials include tetracyanoquinone methane (TCNQ), 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone methane (F4TCNQ), trinaphtylene (HATNA), metal oxides such as MoO3 or WO3, or electron acceptors such as radialene compounds as described in EP 2180029. Acceptor molecules generate so-called holes in a semiconductor matrix material (hole transport material) through an electron transfer process, and the conductivity of the semiconductor matrix material (hole transport material) changes somewhat depending on the number and mobility of the holes.

[0005] However, the aforementioned compounds or classes of compounds have disadvantages in terms of technical application in the manufacture of doped semiconductors or corresponding electronic components having such doped layers. The mentioned compounds or classes of compounds are, for example, too volatile, have too high an absorption coefficient, have unstable evaporation rates, or exhibit low thermal stability. Furthermore, some of these compounds have very high production costs.

[0006] Therefore, there is still a demand for compounds that are easily available or manufacturable, suitable for doping electron donor materials, and do not have the aforementioned disadvantages.

[0007] Only a few cerium ethylenediamine ketone-type complexes are known, and cerium salene-type (cerium bis(salicylidene)ethylenediamine-type) complexes are not known. Several complexes of cerium-(IV) are mentioned in the literature [J. Schl Homopleptic cerium(IV) complexes having the following ligands are described in [fer et al, Inorg. Chem, 2016, 55, 5422-5429]: N,N'-bis(4,4,4,-trifluorobut-1-en-3-one)-ethylenediamine, N,N'-bis(4,4,5,5-pentafluoropent-1-en-3-one)-ethylenediamine, N,N'-bis(4,4,5,5,6,6-heptafluorohex-1-en-3-one)-ethylenediamine, and N,N'-bis(4,4,4,-trifluorobut-1-en-3-one)-propylenediamine.

[0008] The following homopleptic cerium(IV) complex is described in the literature [DW Wester et al, Inorg, Chem. 1985, 24, 4435-4437]:

[0009]

[0010] The synthesis of rare-earth ethylenediamine bis-acetylacetone complexes is described in the literature [NK Dutt et al., Chemistry of Lanthanons-XIX Ethylenediamine bis-acetylacetone Complexes of Rare-Earths, J. Inorg. Nucl. Chem., 1968, Vol. 30, pp. 3273-3280]. Among other Ce(III) complexes, [Ce(ethylenediamine-bis-acetylacetone)Cl3] and [Ce(ethylenediamine-bis-acetylacetone)NO3] are mentioned. In these complexes, the ligand is neutral and therefore does not transfer charge. According to the present invention, the ligand becomes twice negatively charged.

[0011] The synthesis of lanthanide(III) chelate complexes is described in the literature [V. Balasubramanian et al., Synthesis and Reactivity of Quadridentate Schiff Base Chelates of Lanthanide(III) Ions, Asian Journal of Chemistry 2003, Vol. 15, No. 1, pp. 139-143). The mentioned Ce(III) complexes include [Ce(ethylenediamine-bis-acetacetone)Cl3] and [Ce(ethylenediamine-bis-acetylacetone-α-naphthylisocyanate))Cl3], where the ethylenediamine-bis-acetacetone ligand is of the keto type. In these complexes, the ligand is neutral and therefore does not transfer charge. According to the present invention, the ligand becomes negatively charged by number 2.

[0012] Template Synthesis and Crystal and Molecular Structure of Bis[1,1,1,12,12,12-hexafluoro-2, 11-bis(trifluoromethyl)-4,9-dimethyl-2,11-diolato-5,8-diazadodeca-4,8-diene(2-)]cerium(IV), CeC 28 H 28 F 24 A cerium(IV) complex is described in [O4N4, a fluorinated Schiff base complex of eight-coordinate cerium (IV), Inorg. Chem. 1980, Vol. 19, No. 12, p. 3553–3557]. The ligands of this complex differ in their atomic connectivity. That is, the ligands are not based on an acetylacetone structure.

[0013] WO 2021 / 048044 describes cerium(IV) diketonate complexes as electron acceptors, particularly p-dopants and electron transport materials, that can be used in organic electronic devices.

[0014] To date, it has not been known that cerium(IV) ethylenediamine ketone type and / or cerium(IV) salene type and / or cerium(IV) bis(salicylidene)ethylenediamine type complexes (hereinafter also referred to as cerium(IV) complexes) are used in organic semiconductor materials. In particular, it has not been described that these cerium(IV) complexes are used as p-dopants, as electron transport materials, or as electron acceptors.

[0015] Surprisingly, it has been revealed in the present invention that cerium(IV) complexes can be advantageously used as p-dopants. Furthermore, it has been revealed that cerium(IV) complexes can be used as electron transport materials (ETMs) in organic electronic components such as organic light-emitting diodes (OLEDs), photovoltaic cells, organic solar cells (OPVs), organic diodes, or organic transistors.

[0016] Furthermore, many cerium(IV) diketonates can evaporate very well under vacuum and sometimes exhibit high thermal stability. Therefore, they are suitable for both vacuum coating (vapor deposition) and solvent-based processing (solution processing), which are essentially variations of organic electronic component processing.

[0017] The first object of the present invention is an electronic component comprising at least one compound of the following formula (I):

[0018] Ce 4+ [L1L2] 4- (I),

[0019] Here, L1 and L2 are each independently tetradentate ligands selected from the ligands of the following chemical formula (I.1), and

[0020] , here

[0021] X independently represents O or S;

[0022] Z is a bridging group having two or three carbon atoms between nitrogen atoms, where each carbon atom is unsubstituted or one, two, three, four, five, or six identical or different radicals R 12 It is substituted with, where two adjacent carbon atoms can be connected to each other by a double bond, or two or three of the carbon atoms are mononuclear, 2-nuclear, or 3-nuclear C6-C 14 It is part of an aromatic or heteroaromatic ring system, wherein the heteroaromatic ring system has 4 to 13 carbon atoms and N, NR as ring elements 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aromatic or heteroaromatic ring system is unsubstituted or has 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;

[0023] A and B are independently N or CR 7 Representing;

[0024] R 1 and R 6 is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; or

[0025] R 1 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or

[0026] R 6 and B are C6-C together with the carbon atoms to which they are attached 14Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0027] R 2 and R 5 is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;

[0028] R 2 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or

[0029] R 5 and B are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0030] R 4a R 4b are independently hydrogen, C1-C6 alkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0031] R 7 Silver, hydrogen, CN, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0032] R 8 Silver hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0033] R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryl, wherein the 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;

[0034] R 10 is selected from CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl;

[0035] R 11 is selected from CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl;

[0036] R 12 is independently selected from halogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 It is replaced with.

[0037] A further object of the present invention is an electronic component comprising at least one compound of the following general formula (I):

[0038] Ce 4+ [L1L2] 4- (I),

[0039] Here, L1 and L2 are each independently selected tetradentate ligands from the ligands of the following chemical formula (II), and

[0040] , here

[0041] Group CR 3 -CR 4 between represents a single or double bond;

[0042] X independently represents O or S;

[0043] A and B are independently N or CR 7 Representing;

[0044] R 1 and R 6 Silver hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8, having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; or

[0045] R 1 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or

[0046] R 6 and B are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0047] R 3 and R 4 is hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with, or

[0048] R 3 and R 4 C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0049] R 2 and R 5 is hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;

[0050] R 4a R4b are independently hydrogen, C1-C6 alkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0051] R 7 Silver, hydrogen, CN, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0052] R 8 Silver hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0053] R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryl, wherein the 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;

[0054] R 10 It is selected from CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl.

[0055] A further object of the present invention is a doped semiconductor matrix material comprising at least one electron donor and at least one compound of formula (I), wherein L1 and L2 are each tetradentate ligands independently selected from ligands of formula (I.1) or formula (II), and wherein X, Z, A, B, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 It is as defined above and below.

[0056] A further object of the present invention is the use of a compound of formula (I), wherein L1 and L2 are each independently selected from tetradentate ligands of formula (I.1) or formula (II),

[0057] - As an organic semiconductor,

[0058] - As a doping agent for organic semiconductor matrix materials, particularly as a p-dopant in the hole transport layer,

[0059] - As a charge injector of the charge injection layer,

[0060] - As an electron transport layer,

[0061] - As a cathode material for organic batteries,

[0062] - As an electrochromic material,

[0063] - as an electron acceptor

[0064] It is the use, the purpose, where X, Z, A, B, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 It is as defined above and below.

[0065] Another object of the present invention is the use of an organic conductor, in particular as an organic conductor, electrochromic material, charge transfer complex, or ferromagnet, of a Ce(III)-complex anion obtained by the reduction of a compound (I) as defined above and below, or a charge transfer complex of compound (I) as defined above and below, together with an electron donor.

[0066] Further objects of the present invention are compounds of the following general formula (I), charge transfer complexes thereof, reduction products thereof, and mixtures thereof, and

[0067] Ce 4+ [L1L2] 4- (I),

[0068] Here, L1 and L2 are each independently selected tetradentate ligands from the ligands of the following chemical formula (I.1), and

[0069] , here

[0070] X independently represents O or S;

[0071] Z is a bridging group having two or three carbon atoms between nitrogen atoms, where each carbon atom is unsubstituted or one, two, three, four, five, or six identical or different radicals R 12 It is substituted with, where two adjacent carbon atoms can be connected to each other by a double bond, or two or three of the carbon atoms are mononuclear, 2-nuclear, or 3-nuclear C6-C 14 It is part of an aromatic or heteroaromatic ring system, wherein the heteroaromatic ring system has 4 to 13 carbon atoms and N, NR as ring elements 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aromatic or heteroaromatic ring system is unsubstituted or has 1, 2, 3, 4, or 5 identical or different radicals R9 Replaced with;

[0072] A and B are independently N or CR 7 Representing;

[0073] R 1 and R 6 is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; or

[0074] R 1 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or

[0075] R 6 and B are C6-C together with the carbon atoms to which they are attached 14Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0076] R 2 and R 5 is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;

[0077] R 2 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or

[0078] R 5 and B are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0079] R 4a R 4b are independently hydrogen, C1-C6 alkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0080] R 7 Silver, hydrogen, CN, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0081] R 8 Silver hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0082] R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryl, wherein the 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;

[0083] R 10 is selected from CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl;

[0084] R 11 is selected from CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl;

[0085] R 12 is independently selected from halogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 It is replaced with;

[0086] However, the following compounds are excluded:

[0087]

[0088] Further objects of the present invention are compounds of the following general (I), charge transfer complexes thereof, reduction products thereof and mixtures thereof, and

[0089] Ce 4+ [L1L2] 4- (I),

[0090] Here, L1 and L2 are each independently selected tetradentate ligands from the ligands of formula (II), and

[0091] , here,

[0092] Group CR 3 -CR 4 fraud represents a single or double bond;

[0093] X independently represents O or S;

[0094] A and B are independently N or CR 7 Representing;

[0095] R 1 and R 6 Silver hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8, having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; or

[0096] R 1 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or

[0097] R 6 and B are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0098] R 3 and R 4 is hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with, or

[0099] R 3 and R 4 C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0100] R 2 and R 5 is hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;

[0101] R 4a R4b are independently hydrogen, C1-C6 alkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0102] R 7 Silver, hydrogen, CN, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0103] R 8 Silver hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0104] R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryl, wherein the 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;

[0105] R 10 It is selected from CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl.

[0106] However, the following compounds of chemical formula (I) and their reaction products are excluded:

[0107] L1= L2= N,N'-bis(4,4,4,-trifluorobut-1-en-3-one)-ethylenediamine,

[0108] L1= L2= N,N'-bis(4,4,5,5,5-pentafluoropent-1-en-3-one)-ethylenediamine,

[0109] L1= L2= N,N'-bis(4,4,5,5,6,6,6-heptafluorohex-1-en-3-one)-ethylenediamine and the following compounds and their reaction products:

[0110] .

[0111] The present invention has the following advantages:

[0112] - The cerium-(IV)-complex according to the present invention has a low production cost.

[0113] - The cerium-(IV)-complex according to the present invention is advantageously suitable as an electron acceptor for use as a p-dopant and as an electron transport material for organic-electronic components.

[0114] - The cerium-(IV)-complex according to the present invention exhibits superior conductivity compared to known electron acceptors.

[0115] - The cerium-(IV)-complex according to the present invention exhibits improved thermal stability of the doped layer compared to the latest technology.

[0116] - In addition, the cerium(IV) complex according to the present invention is characterized by higher doping efficiency.

[0117] - The cerium-(IV)-complex according to the present invention exhibits only low absorption of the doped layer. Therefore, parasitic absorption and emission can be reduced or prevented.

[0118] - The cerium-(IV)-complex according to the present invention is suitable for the production of organic and hybrid opto-electronic components by both solvent treatment and vacuum reprocessing.

[0119] The terms cerium compound and cerium complex are used synonymously and are defined by chemical formula (I). Ligands without metal atoms (cerium atoms) are defined by chemical formula (II).

[0120] The term reduction product of compound (I) is an anionic complex, in particular a Ce(III) anionic complex, where the corresponding counterion is provided by the hole-conducting material (HTL) of the matrix. The semiconductor matrix material is defined below.

[0121] In the sense of the present invention, [Ce(ac2en)Cl3], [Ce(enac)2Cl3] and [Ce(enac)2(NO3)3] are not reduction products of compound (I), where ac2en and enac have the same meaning, and in particular, ac2en is bis(acetylacetone)ethylenediamine in the keto form and enac is ethylenediamine-bis-acetylacetone.

[0122] The term charge transfer complex of compound (I) refers to the ionic bonding with radical cations of the matrix material (hole transport material, HTL).

[0123] In the context of the present invention, formula (II) represents an exemplary mesomeric structure in which ligands L1 and L2 are not limited. Other mesomeric structures are selected from formulas a, b, c, and d.

[0124]

[0125] Mesome structures a, b, c, and d are similarly applied to the ligands of chemical formula (I.1).

[0126] Preferably, L1 and L2 have a mesomer structure of chemical formula a.

[0127] In the context of the present invention, the tetradentate ligand (also referred to as tetradentate) is a ligand that binds to a metal atom (cerium atom) with four atoms.

[0128] In the context of the present invention, homoleptic cerium(IV) compounds are complexes in which all ligands are identical (L1=L2).

[0129] In the context of the present invention, heteroleptic cerium (IV) compounds are complexes in which one ligand has a different meaning from the other ligand (L1 ≠ L2).

[0130] In the context of the present invention, the prefix C n -C m This indicates the number of carbon atoms that the molecule or residue designated by this may contain.

[0131] In the context of the present invention, the expression "C1-C6-alkyl" refers to an unbranched or branched saturated hydrocarbon group having 1 to 6 carbon atoms. C1-C6-alkyl is, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or There is 1-ethyl-2-methylpropyl. C1-C4-alkyl refers, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl.

[0132] In the context of the present invention, the expression "C1-C6-alkoxy" refers to an unbranched or branched saturated C1-C6-alkyl group as defined above, bonded through an oxygen atom. An alkoxy radical having 1 to 4 carbon atoms is preferred, and 1 or 2 carbon atoms are particularly preferred. The C1-C2-alkoxy is methoxy or ethoxy. The C1-C4-alkoxy is, for example, methoxy, ethoxy, n-propoxy, 1-methylethoxy (isopropoxy), butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy), or 1,1-dimethylethoxy (tert-butoxy). C1-C6-alkoxy includes the meaning given for C1-C4-alkoxy, and additionally, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexyloxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, and 3,3-dimethylbutoxy.

[0133] In the context of the present invention, the expression "C1-C6-alkylsulfanyl" refers to an unbranched or branched saturated C1-C6-alkyl group as defined above, bonded through a sulfur atom. An alkylsulfanyl radical having 1 to 4 carbon atoms is preferred, and 1 or 2 carbon atoms are particularly preferred. C1-C2-alkylsulfanyl includes methylsulfanyl or ethylsulfanyl. C1-C4-alkylsulfanyl includes, for example, methylsulfanyl, ethylsulfanyl, n-propylsulfanyl, 1-methylethylsulfanyl (isopropylsulfanyl), butylsulfanyl, 1-methylpropylsulfanyl (sec-butylsulfanyl), 2-methylpropylsulfanyl (isobutylsulfanyl), or 1,1-dimethylethylsulfanyl (tert-butylsulfanyl). C1-C6-alkylthio includes the meaning given for C1-C4-alkylsulfanyl, and additionally also, e.g., pentylsulfanyl, 1-methylbutylsulfanyl, 2-methylbutylsulfanyl, 3-methylbutylsulfanyl, 1,1-dimethylpropylsulfanyl, 1,2-dimethylpropylsulfanyl, 2,2-dimethylpropylsulfanyl, 1-ethylpropylsulfanyl, hexylsulfanyl, 1-methylpentylsulfanyl, 2-methylpentylsulfanyl, 3-methylpentylsulfanyl, 4-methylpentylsulfanyl, 1,1-dimethylbutylsulfanyl, 1,2-dimethylbutylsulfanyl, 1,3-dimethylbutylsulfanyl, 2,2-dimethylbutylsulfanyl, 2,3-dimethylbutylsulfanyl, 3,3-dimethylbutylsulfanyl, There are 1-ethylbutylsulfanil, 2-ethylbutylsulfanil, 1,1,2-trimethylpropylsulfanil, 1,2,2-trimethylpropylsulfanil, 1-ethyl-1-methylpropylsulfanil, or 1-ethyl-2-methylpropylsulfanil.

[0134] In the context of the present invention, the expressions “haloalkyl,” “holoalkoxy,” and “haloalkyl-sulfanyl” refer to partially or completely halogenated alkyl, alkoxy, or alkylsulfanyl. That is, one or more hydrogen atoms, for example, 1, 2, 3, 4, or 5 hydrogen atoms bonded to one or more carbon atoms of the alkyl, alkoxy, or alkylsulfanyl, are replaced with halogen atoms, in particular fluorine or chlorine.

[0135] In the context of the present invention, the term “cycloalkyl” refers to a carbocyclic, monocyclic radical having 3 to 7 carbons, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl; cyclopentyl, cyclohexyl, and cycloheptyl are preferred, wherein bonding to the radical of the molecule may occur through any suitable C atom. In the case of substitution, they may generally have 1, 2, 3, 4, 4, 5, or 6, preferably 1, 2, or 3, particularly preferably 1 “substituent” as defined above.

[0136] In the context of the present invention, the term "alkylene" refers to an alkanediyl group, i.e., a hydrocarbon crosslinking group having two or three carbon atoms, such as -(CH2)2-, -(CH2)3-, or -CH2-CH-CH2-. In the case of substitution, these generally consist of one, two, or three substituents R as defined above. 12 Can have.

[0137] In the context of the present invention, the term "alkenylene" refers to a single- or poly-unsaturated, particularly single-unsaturated, analogue of an alkylene group having two or three carbon atoms, such as -CH=CH-, -CH=CH-CH2-, and -CH2-CH=CH-. In the case of substitution, these generally consist of one, two, or three substituents R as defined above. 12 Can have.

[0138] In the context of the present invention, the term "1-nuclear, 2-nuclear, or 3-nuclear C6-C" 14 Part of an aromatic or heteroaromatic ring system (part of a 1-nuclear, 2-nuclear, or 3-nuclear C6-C 14 "Aromatic or heteroaromatic ring system" refers to the corresponding twice- or multiple-linked analogues of aryl or heta-aryl.

[0139] In the context of the present invention, the expression “bridging group having 2 or 3 carbon atoms between nitrogen atoms” corresponds to having 2 or 3 carbon atoms in a straight line between lateral bonds (nitrogen atoms).

[0140] The term "halogen" refers to fluorine, chlorine, bromine, or iodine in each case.

[0141] In the context of the present invention, the expression "aryl" generally comprises a mononuclear or polynuclear aromatic hydrocarbon radical having 6 to 14, preferably 6 to 10, carbon atoms. Examples of aryls include, in particular, phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, and the like, and in particular, phenyl or naphthyl.

[0142] The expression "hetaryl" in the context of the present invention comprises a mononuclear or polynuclear aromatic hydrocarbon radical having 4 to 13 carbon atoms, wherein 1, 2, or 3 carbon atoms are 1, 2, or 3 identical or different heteroatoms or N, NR 8It includes a heteroatom-containing group selected from O, S, SO, and SO2 as a ring. The heteroaryl group may be attached to the rest of the molecule through a ring carbon or ring nitrogen. Examples of 5- or 6-membered aromatic heterocyclic rings (also called heteroaromatic rings or heta-aryls) include 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,3,4-triazole-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, and There is 2-pyrazinyl. Examples of 8-, 9-, or 10-membered aromatic heterocyclic rings include one of the aforementioned 5- or 6-membered heteroaromatic rings and another aromatic carbocycle or 5- or 6-membered heterocycle fused thereto, for example, a fused benzene, thiophene-, furan-, pyrrole-, pyrazol-, imidazole-, pyridine-, or pyrimidine- ring. These bicyclic heta-arylenes include, for example, quinolinyl, isoquinolinyl, cinnolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, particularly 2-benzofuryl, benzothienyl, particularly 2-benzothienyl, benzo[b]thiazolyl, particularly 2-benzo[b]thiazolyl, benzoxazolyl, particularly 2-benzoxazolyl, benzothiazolyl, particularly 2-benzothiazolyl, benzimidazolyl, particularly 2-benzimidazolyl, imidazo[1,2-a]pyridin-2-yl, thieno[3,2-b]pyridin-5-yl, imidazo[2,1-b]-thiazol-6-yl and 1,2,4-triazolo[1,5-a]pyridin-2-yl.

[0143] The expression "CN" represents a cyano group (-C≡N).

[0144] When # appears in the chemical formula representing the preferred substructure of the compound of the present invention, it indicates a bond to the rest of the molecule.

[0145] Cerium compound of chemical formula (I)

[0146] Suitable cerium(IV) compounds in the sense of the present invention are compounds of general formula (I):

[0147] Ce 4+ [L1L2] 4- (I),

[0148] Here, L1 and L2 have one of the meanings defined above and below, where

[0149] - L1 and L2 have the same meaning,

[0150] - L1 and L2 each have different meanings,

[0151] - It is a mixture of two or more compounds of chemical formula (I).

[0152] A compound of chemical formula (I) in which L1 and L2 have the same meaning is preferred.

[0153] The homoleptic compound of formula (I) is prepared by the reaction of a ligand of formula (I.1) or formula (II) with a cerium salt. Generally, the cerium salt is dissolved in the reaction medium. Suitable salts are ammonium cerium nitrate and cerium ammonium sulfate. The ligand may be commercially available or prepared by synthesis known to those skilled in the art.

[0154] The heteroleptic compound of chemical formula (I) is

[0155] - The step of mixing two different homoleptic cerium compounds in a suitable solvent,

[0156] - A step of mixing a homoleptic cerium compound with a ligand of the cerium compound used and another ligand or its alkali / alkaline earth salt,

[0157] - Deposition of two different homoleptic cerium compounds,

[0158] - Deposition (vapor cocondensation) of a homoleptic cerium compound having a ligand different from the ligand of the cerium compound used,

[0159] It is manufactured by.

[0160] In the cerium compound of formula (I), L1 and L2 are tetradentate ligands independently selected from the ligands of formula (I.1) or formula (II):

[0161] , here

[0162] The above radicals X, Z, A, B, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 has the meanings defined above and below.

[0163] In a preferred embodiment, Z is a C2-C3 alkylene or C2-C3 alkenylene, wherein the alkylene or alkenylene is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 12 Replaced with; or

[0164] Two or three carbon atoms in the bridging group are 1-nucleus or 2-nucleus C6-C 10 It is part of an aromatic or heteroaromatic ring system, said heteroaromatic ring system having 4-13 carbon atoms, and N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2 as ring elements, wherein the aromatic or heteroaromatic ring system is unsubstituted or has 1, 2, 3, 4, or 5 identical or different radicals R 9 It is replaced with, where R 12 and R 9 is defined above and below.

[0165] A cerium compound of formula (I) is preferred, in which ligands L1 and L2 are independently selected ligands of formula (II).

[0166] R 1 , R 2 , R 5 and R 6 This independently hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b A ligand of formula (I.1) or (II) selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18 and A19 is preferred.

[0167]

[0168]

[0169] Here, # indicates a bond to a group of chemical formula (I.1) or (II), where R A , R B , R C , R D and R E is independently selected from hydrogen, CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl; or

[0170] R 1 and A are C6-C together with the carbon atoms to which they are attached 14 Forms an aryl group, where the aryl is unsubstituted or consists of 1, 2, 3, or 4 identical or different radicals R 9 Replaced with; or

[0171] R 6 and B are C6-C together with the carbon atoms to which they are attached 14 Forms an aryl group, where the aryl is unsubstituted or consists of 1, 2, 3, or 4 identical or different radicals R 9Replaced with;

[0172] R 4a , R 4b is hydrogen, C1-C6 alkyl and C6-C 14 Independently selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0173] R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryl, wherein the 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;

[0174] R 10 It is selected from CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl.

[0175] Regardless of their appearance, radical R A , R B , R C , R D and R E It is preferably selected from hydrogen, CN, fluorine, chlorine, C1-C4 alkyl, C1-C4 fluoroalkyl, and C1-C4 chloroalkyl.

[0176] Particularly desirable radical R A , R B , R C , R D and R E are independently selected from hydrogen, CN, C1-C4 fluoroalkyl, fluorine, and chlorine. In particular, radical R A , R B , R C , R D and R E They independently represent hydrogen or CF3.

[0177] In one embodiment, R in formula (I.1) or (II) 1 , R 2, R 5 and R 6 It is independently selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, and A1:

[0178]

[0179] # indicates a bond to the remaining molecule of chemical formula (II), where R A , R B , R C , R D and R E is independently selected from hydrogen, CN, fluorine, chlorine, C1-C4 alkyl, C1-C4 fluoroalkyl, and C1-C4 chloroalkyl, preferably selected from hydrogen, CN, fluorine, and chlorine; or

[0180] R 1 and A form a phenyl ring with the carbon atom to which they are attached, where phenyl is unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with; or

[0181] R 6 and B form a phenyl ring with the carbon atom to which they are attached, where phenyl is unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0182] R 9 is selected from CN, halogen, C1-C4 alkyl, C1-C4 haloalkyl and phenyl, wherein phenyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from C1-C4 alkyl or C1-C4 haloalkyl.

[0183] In another embodiment, in formula (I.1) or (II), R 1 and R 6 is selected independently from CF3 and A1, where R A , R B , R C , R Dand R E is independently selected from CN, CF3, fluoro, and chloro;

[0184] R 2 and R 5 is independently selected from hydrogen, CF3, and A1, where R A , R B , R C , RD and R E is independently selected from hydrogen, CN, CF3, fluorine, and chlorine; or

[0185] R 1 and A form a phenyl ring with the carbon atom to which they are attached, where phenyl is unsubstituted or one or two identical or different radicals R 9 Replaced with; or

[0186] R 6 and B form a phenyl ring with the carbon atom to which they are attached, where phenyl is unsubstituted or one or two identical or different radicals R 9 Replaced with;

[0187] R 9 is selected from CN, halogen, C1-C2 alkyl, and C1-C2 haloalkyl.

[0188] In certain embodiments, in formula (I.1) or (II), R 1 and R 6 is independently selected from hydrogen, CF3, and A1, where R A , R B , R C , R D and R E is independently selected from hydrogen and CF3;

[0189] R 2 and R 5 is independently selected from hydrogen, CF3, and A1, where R A , R B , R C , R D and R Eis independently selected from hydrogen and CF3;

[0190] R 1 and A form a phenyl ring with the carbon atom to which they are attached, where phenyl is unsubstituted or one or two identical or different radicals R 9 Replaced with;

[0191] R 6 and B form a phenyl ring with the carbon atom to which they are attached, where phenyl is unsubstituted or one or two identical or different radicals R 9 Replaced with;

[0192] R 9 is selected from CN, F, Cl, and CF3.

[0193] In another specific embodiment, R in formula (I.1) or (II) 2 and R 5 is independently selected from hydrogen and CF3, and R 1 and R 6 is independently selected from CF3 and A1, where R A , R B , R C , R D and R E is hydrogen or CF3, or

[0194] R 1 and A form a phenyl ring with the carbon atom to which they are attached, where phenyl is unsubstituted or also one or two identical or different radicals R 9 Replaced with; or

[0195] R 6 and B form a phenyl ring with the carbon atom to which they are attached, where phenyl is unsubstituted or also one or two identical or different radicals R 9 Replaced with;

[0196] R 9 is selected from CN, F, Cl, and CF3.

[0197] Preferably, it is a ligand of formula (II), where R in formula (II) 3 and R 4 is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, and C1-C6 haloalkoxy, or

[0198] R 3 and R 4 C6-C together with the carbon atoms to which they are attached 14 It forms an aryl group, where the aryl is unsubstituted or consists of 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0199] R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl or C6-C 14 Selected from aryl, wherein the aryl is unsubstituted or substituted with 1, 2, 3, 4, or 5 identical or different substituents selected from C1-C4 alkyl or C1-C4 haloalkyl.

[0200] Particularly desirable is a ligand of formula (II), where R of formula (II) is 3 and R 4 is independently selected from hydrogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, and phenyl, wherein phenyl is unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or

[0201] R 3 and R 4 They form a phenyl ring with the carbon atom to which they are attached, where the phenyl is unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0202] R 9is selected from CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl, or phenyl, wherein phenyl is unsubstituted or substituted with 1, 2, 3, or 4 identical or different substituents selected from C1-C4-alkyl or C1-C4-haloalkyl.

[0203] Particularly desirable is a ligand of formula (II), where R in formula (II) is a ligand of formula (II). 3 and R 4 is independently selected from hydrogen, CN, C1-C2 alkyl and CF3;

[0204] R 3 and R 4 They form a phenyl group together with the carbon atom to which they are attached, where the phenyl is unsubstituted.

[0205] A ligand of formula (I.1) or (II) is preferred, wherein in formula (II), A and B are independently radical CR 7 and R 7 It is selected from group B consisting of hydrogen, CN, nitro, halogen, and B1, B2, B3, B4, B5, B6, B7, B8, B9, B10, B11, B12, B13, B14, and B15.

[0206]

[0207]

[0208] Here, # represents the bond to the group of chemical formula (II), where R F , R G , R H , R I and R J is independently selected from hydrogen, CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl.

[0209] Regardless of their appearance, radical R F , R G , R H , R I and R Jis preferably selected from hydrogen, CN, fluorine, chlorine, C1-C4-alkyl, C1-C4-fluoroalkyl, and C1-C4-chloroalkyl. In a preferred embodiment, radical R F , R G , R H , R I and R J is independently hydrogen, CN, fluorine, or chlorine.

[0210] A ligand of formula (I.1) or (II) is preferred, wherein in formula (II), A and B are independently radical CR 7 and R 7 is selected from hydrogen, CN, nitro, halogen, C1-C2 alkyl, C1-C2 haloalkyl, and B1, wherein R F , R G , R H , R I and R J It is independently selected from hydrogen, CN, fluorine, and chlorine.

[0211] Ligands of formula (I.1) or (II) are particularly preferred, wherein in formula (II), A and B are independently radical CR 7 and R 7 It is selected from hydrogen, CN, nitro, halogen, C1-C2 alkyl, and C1-C2 haloalkyl. In particular, R 7 It is selected from hydrogen, CN, nitro, fluorine, and chlorine, in particular hydrogen, fluorine, and CN.

[0212] In one embodiment A, the ligand of formula (II) is selected from the following formula (IA).

[0213] (IA),

[0214] X is O and,

[0215] R 1is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and is substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above, and

[0216] R 2 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and is substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above, and

[0217] R 5 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4band is substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above, and

[0218] R 6 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and is substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above, and

[0219] R 7 It is selected from hydrogen, CN, nitro, halogen, C1-C2 alkyl and C1-C2 haloalkyl.

[0220] In one embodiment B, the ligand of formula (II) is selected from the following formula (IB).

[0221] (IB)

[0222] Here

[0223] X represents O;

[0224] R 1 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 3 to 6 carbon atoms, the hetaaryl consists of N and NR as ring members. 8Having 1, 2, or 3 heteroatoms or heteroatom-containing groups selected from, wherein the aryl and heteroaryl are unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0225] R 2 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above;

[0226] R 5 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above;

[0227] R 6 and B are C6-C together with the carbon atoms to which they are attached 14It forms an aryl group or a heta-aryl group having 3 to 6 carbon atoms, and the heta-aryl is a cyclic group consisting of N and NR 8 Having 1, 2, or 3 heteroatoms or heteroatom-containing groups selected from, wherein the aryl and heteroaryl are unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 It is replaced with.

[0228] In one embodiment C, the ligand of formula (II) is selected from the following formula (IC):

[0229] (IC)

[0230] Here

[0231] X represents O;

[0232] R 1 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above;

[0233] R 2 and A are C6-C together with the carbon atoms to which they are attached 14 It forms an aryl group or a heta-aryl group having 3 to 6 carbon atoms, and the heta-aryl is a cyclic group consisting of N and NR 8Having 1, 2, or 3 heteroatoms or heteroatom-containing groups selected from, wherein the aryl and heteroaryl are unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0234] R 5 and B are C6-C together with the carbon atoms to which they are attached 14 It forms an aryl group or a heta-aryl group having 3 to 6 carbon atoms, and the heta-aryl is a cyclic group consisting of N and NR 8 Having 1, 2, or 3 heteroatoms or heteroatom-containing groups selected from, wherein the aryl and heteroaryl are unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0235] R 6 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and is substituted with 1, 2, 3, 4, 5 or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18 and A19 defined above.

[0236] In embodiment D, the ligand of formula (II) is selected from the following formula (ID):

[0237] (ID)

[0238] R 1is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above;

[0239] R 2 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above;

[0240] R 3 and R 4 C6-C together with the carbon atoms to which they are attached 14 It forms an aryl group or a heta-aryl group having 3 to 6 carbon atoms, and the heta-aryl is a cyclic group consisting of N and NR 8 Having 1, 2, or 3 heteroatoms or heteroatom-containing groups selected from, wherein the aryl and heteroaryl are unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9Replaced with;

[0241] R 5 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above;

[0242] R 6 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above;

[0243] R 7 It is selected from hydrogen, CN, nitro, halogen, C1-C2 alkyl and C1-C2 haloalkyl.

[0244] In one embodiment E, the ligand of formula (II) is selected from the following formula (IE).

[0245] (IE)

[0246] Here

[0247] R 1 and A are C6-C together with the carbon atoms to which they are attached 14 It forms an aryl group or a heta-aryl group having 3 to 6 carbon atoms, and the heta-aryl is a cyclic group consisting of N and NR 8 Having 1, 2, or 3 heteroatoms or heteroatom-containing groups selected from, wherein the aryl and heteroaryl are unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0248] R 2 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above;

[0249] R 3 and R 4 C6-C together with the carbon atoms to which they are attached 14 It forms an aryl group or a heta-aryl group having 3 to 6 carbon atoms, and the heta-aryl is a cyclic group consisting of N and NR 8 Having 1, 2, or 3 heteroatoms or heteroatom-containing groups selected from, wherein the aryl and heteroaryl are unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0250] R 5is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above;

[0251] R 6 and B are C6-C together with the carbon atoms to which they are attached 14 It forms an aryl group or a heta-aryl group having 3 to 6 carbon atoms, and the heta-aryl is a cyclic group consisting of N and NR 8 Having 1, 2, or 3 heteroatoms or heteroatom-containing groups selected from, wherein the aryl and heteroaryl are unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 It is replaced with.

[0252] In one embodiment F, the ligand of formula (II) is selected from the following formula (IF):

[0253] (IF)

[0254] Here

[0255] R 1 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4band substituted with 1, 2, 3, 4, 5, or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, and A19 defined above;

[0256] R 2 and A are C6-C together with the carbon atoms to which they are attached 14 It forms an aryl group or a heta-aryl group having 3 to 6 carbon atoms, and the heta-aryl is a cyclic group consisting of N and NR 8 Having 1, 2, or 3 heteroatoms or heteroatom-containing groups selected from, wherein the aryl and heteroaryl are unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0257] R 3 and R 4 C6-C together with the carbon atoms to which they are attached 14 It forms an aryl group or a heta-aryl group having 3 to 6 carbon atoms, and the heta-aryl is a cyclic group consisting of N and NR 8 Having 1, 2, or 3 heteroatoms or heteroatom-containing groups selected from, wherein the aryl and heteroaryl are unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0258] R 5 and B are C6-C together with the carbon atoms to which they are attached 14 It forms an aryl group or a heta-aryl group having 3 to 6 carbon atoms, and the heta-aryl is a cyclic group consisting of N and NR 8 Having 1, 2, or 3 heteroatoms or heteroatom-containing groups selected from, wherein the aryl and heteroaryl are unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0259] R 6 is selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, wherein C3-C7 cycloalkyl is unsubstituted or CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and is substituted with 1, 2, 3, 4, 5 or 6 identical or different substituents selected from group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18 and A19 defined above.

[0260] In a preferred embodiment, of the compound of formula (I), the ligand of formula (II).

[0261] , here

[0262] Group CR 3 -CR 4 between means a single or double bond, and

[0263] X is O and;

[0264] A and B independently CR 7 and, here R 7 is selected from H and CN;

[0265] R 1 and R 6 is independently selected from hydrogen, CH3, CF3, C2F5, and phenyl; or

[0266] R 1 and A form [4-(trifluoro-methyl)phenyl] together with the carbon atoms to which they are attached, or

[0267] R 6 and B form [4-(trifluoro-methyl)phenyl] together with the carbon atoms to which they are attached;

[0268] R 3 and R 4 represents hydrogen, or

[0269] R 3 and R 4 They form phenyl or (3,4-difluorophenyl) together with the carbon to which they are attached;

[0270] R 2 and R 5 is independently selected from hydrogen, CH3, CF3, C2F5, phenyl, and [3-chloro-4-(trifluoromethyl)phenyl].

[0271] In particular, the compound is selected from the following:

[0272] .

[0273] Regardless of their appearance, radical R 4a and R 4b It is preferably selected from hydrogen and C1-C4 alkyl.

[0274] Regardless of their appearance, radical R 8 It is preferably selected from C1-C4 alkyl and C1-C4 haloalkyl.

[0275] Regardless of its appearance, radical R 9 It is preferably selected from CN, halogen, C1-C4 alkyl, C1-C4 haloalkyl, and phenyl, wherein the phenyl is unsubstituted or is unsubstituted or substituted by 1, 2, 3, 4, or 5 identical or different radicals selected from C1-C4 alkyl or C1-C4 haloalkyl. In particular, R 9 is selected from CN, halogen, C1-C2 alkyl and C1-C2 haloalkyl, and in particular, R 9 is selected from CN, F, Cl, and CF3.

[0276] Regardless of its appearance, radical R 12is preferably selected from halogens, CN, C1-C4 alkyl, C1-C4 haloalkyl, and phenyl, wherein phenyl is unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 It is replaced with.

[0277] part

[0278] In the context of the present invention, an electronic component is understood as an individual or integrated electrical component utilizing the properties of a compound of general formula (I) or a semiconductor matrix material containing a compound of general formula (I). In a particular embodiment, the electronic component has a layered structure particularly comprising two, three, four, five, six, seven or more layers, at least one of which contains at least one compound of formula (I). Each layer may also contain an inorganic material, or the component may also include a layer composed entirely of an inorganic material.

[0279] Preferably, the electronic components are selected from organic field-effect transistors (OFETs), organic electroluminescent devices, organic solar cells (OSCs), electrophotographic devices, organic optical detectors, organic photodetectors, organic photosensitive materials, light-emitting electrochemical cells (LECs), and organic laser diodes. The organic field-effect transistor (OFET) is preferably an organic thin-film transistor (OTFT). The organic electroluminescent device is preferably an organic light-emitting diode (OLED). The organic solar cell is preferably an exciton solar cell, a dye-sensitized solar cell (DSSC), or a perovskite solar cell. The electrophotographic device is preferably a photoconductive material of an organic photoconductor (OPC).

[0280] Preferably, the electronic component according to the present invention is an organic light-emitting diode, an organic solar cell, a photovoltaic cell, an organic sensor, an organic diode, or an organic transistor, preferably a field-effect transistor or a thin-film transistor or a perovskite solar cell.

[0281] The electronic component may preferably be in the form of an organic electroluminescent device, particularly an organic light-emitting diode (OLED). The organic electroluminescent device comprises a cathode, an anode, and at least one emitting layer. In addition to these layers, it may also comprise other layers, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers. For example, an intermediate layer having an exciton blocking function may be inserted between the two emitting layers. Not all of these layers are necessarily required.

[0282] A preferred embodiment is an electronic component, particularly in the form of an OLED, wherein the layer containing the compound of formula (I) is a hole transport layer or a hole injection layer. Generally, the hole injection layer is a layer that facilitates the injection of electrons from an anode into an organic semiconductor matrix material. The hole injection layer may be disposed directly adjacent to the anode. The hole transport layer transports holes from the anode to the light-emitting layer and is located between the hole injection layer and the light-emitting layer.

[0283] A preferred embodiment is an electronic component in the form of an organic solar cell. Generally, an organic solar cell is layered and generally comprises at least the following layers: an anode, at least one photoactive layer, and a cathode. These layers are generally applied to a substrate commonly used for this purpose. The photoactive region of the solar cell may comprise two layers, each having a homogeneous composition and forming a flat donor-acceptor heterojunction. The photoactive region may also comprise a mixed layer and form a donor-acceptor heterojunction in the form of a donor-acceptor bulk heterojunction. In addition to these layers, the organic solar cell may also comprise another layer, for example, selected from the following:

[0284] - Layer having electron transport layer characteristics (electron transport layer, ETL),

[0285] - A layer containing a hole-conducting material (hole transport layer, HTL), which must not absorb radiation,

[0286] - Exciton and hole blocking layers (e.g., EBL), these must not be absorbed, and

[0287] - Multiplier layer.

[0288] Another preferred embodiment is an electronic component in the form of an organic solar cell, wherein a layer containing a compound of formula (I) has electronic conductivity properties (electron transport layer, ETL).

[0289] A particular embodiment is an electronic component in the form of an organic solar cell, wherein a layer comprising one or more compounds of formula (I) is part of a pn junction connecting a light absorption unit to an additional light absorption unit in a tandem device or a multi-stacked device and / or a cathode or anode connecting to a light absorption unit.

[0290] Another preferred embodiment is an electronic component comprising an electron transport layer comprising at least one compound of formula (I).

[0291] semiconductor matrix materials

[0292] According to the present invention, the compound of formula (I) used according to the present invention, as well as its charge transfer complex and its reduction product, can be used as a doping agent for an organic semiconductor matrix material, in particular as a p-dopant in a hole transport layer. The doped semiconductor matrix material preferably comprises at least one electron donor and at least one compound of formula (I) as defined above.

[0293] Suitable diaminoterphenyls are described in DE 102012007795. Diaminotrimethylphenylindanes are described in WO 2018 / 206769.

[0294] In particular, electron donors are 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-spirobifluorene, 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,N'-((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-(6-((9,9-dimethyl-9H-fluoren-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-fluoren-2-amine, N-([1,1'-biphenyl]-4-yl)-N-(4-(6-([1,1'-biphenyl]-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)phenyl)-9,9-dimethyl-9H-fluoren-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-indene-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluorene-2-yl)-9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9'-spirobi[fluoren]-2-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)phenyl)-N-(9,9-di-methyl-9H-fluoren-2-yl)-9,9'-spirobi[fluoren]-2-amine, N-(4-(6-(dibenzo[b,d]furan-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)-phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-2-amine, 9-(4-(6-(9H-carbazole-9-yl)-1,3,3-trimethyl-2,3-dihydro-1H-indene-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-indene-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-indene-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-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)-phenyl)-N-(9,9-dimethyl-9H-fluoren-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[9, H A mixture of -fluorene](spiro-MeO-TPD), 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 and 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, It is selected from N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-fluorene-2-amine and mixtures thereof.

[0295] Of course, other suitable organic semiconductor matrix materials, particularly hole-conducting materials with semiconductor properties, can also be used.

[0296] doping

[0297] Doping can occur in a manner where the molar ratio of the matrix molecule to the compound of formula (I) is 10000:1 to 1:1, preferably 1000:1 to 2:1, particularly 5:1 to 100:1.

[0298] Manufacturing of doped semiconductor matrix materials

[0299] According to the present invention, doping of a specific matrix material (hereinafter also denoted as hole-conducting matrix HT) using a compound of general formula (I) used according to the present invention can be produced by one or a combination of the following processes:

[0300] a) Mixed evaporation in vacuum using a source for HT and a source for at least one compound of general formula (I).

[0301] b) Sequential deposition of HT and at least one compound of general formula (I) with subsequent internal diffusion of the doping agent by heat treatment.

[0302] c) Doping the HT layer with a solution of at least one compound of general formula (I), followed by subsequent evaporation of the solvent by heat treatment.

[0303] d) Surface doping of the HT layer by a layer of at least one compound of general formula (I) applied to one or both surfaces of the HT layer.

[0304] e) Prepare a solution of a host and at least one compound of general formula (I), and form a film from the solution by coating, casting, or printing techniques or other film manufacturing techniques known to those skilled in the art.

[0305] Another objective of the present invention is,

[0306] - As an organic semiconductor,

[0307] - As a redox doping agent for organic semiconductor matrix materials, particularly as a p-dopant in the hole transport layer,

[0308] - As an electronic transport material,

[0309] - As a charge injector of a charge injection layer,

[0310] - As a cathode material for organic batteries,

[0311] - As an electrochromic material,

[0312] The use of the compound (I) or a mixture thereof as defined above.

[0313] Another objective of the present invention is to use a Ce(III) complex anion obtained by the reduction of the compound (I) as defined above or the charge transfer complex of the compound (I) as defined above together with an electron donor as an organic semiconductor or an electrochromic material.

[0314] Further objects of the present invention are compounds of the following general formula (I), charge transfer complexes thereof, reduction products thereof, and mixtures thereof:

[0315] Ce 4+ [L1L2] 4- (I),

[0316] L1 and L2 are each independently tetradentate ligands selected from the ligands of the following chemical formula (I.1), and

[0317] , here

[0318] X independently represents O or S;

[0319] Z is a bridging group having two or three carbon atoms between nitrogen atoms, where each carbon atom is unsubstituted or one, two, three, four, five, or six identical or different radicals R 12 It is substituted with, where two adjacent carbon atoms can be connected to each other by a double bond, or two or three of the carbon atoms are mononuclear, 2-nuclear, or 3-nuclear C6-C 14 It is part of an aromatic or heteroaromatic ring system, wherein the heteroaromatic ring system has 4 to 13 carbon atoms and N, NR as ring elements 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aromatic or heteroaromatic ring system is unsubstituted or has 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;

[0320] A and B are independently N or CR 7 Representing;

[0321] R 1 and R 6 is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; or

[0322] R 1 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or

[0323] R 6 and B are C6-C together with the carbon atoms to which they are attached 14Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0324] R 2 and R 5 is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;

[0325] R 2 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or

[0326] R 5 and B are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0327] R 4a R 4b are independently hydrogen, C1-C6 alkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0328] R 7 Silver, hydrogen, CN, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0329] R 8 Silver hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0330] R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryl, wherein the 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;

[0331] R 10 is selected from CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl;

[0332] R 11 is selected from CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl;

[0333] R 12 is independently selected from halogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 It is replaced with;

[0334] However, the following compounds are excluded:

[0335] .

[0336] Further objects of the present invention are compounds of the following general formula (I), charge transfer complexes thereof, reduction products thereof, and mixtures thereof:

[0337] Ce 4+ [L1L2] 4- (I),

[0338] Here, L1 and L2 are each independently selected tetradentate ligands from the ligands of formula (II), and

[0339] , here

[0340] Group CR 3 -CR 4 between represents a single or double bond;

[0341] X independently represents O or S;

[0342] A and B are independently N or CR 7 Representing;

[0343] R 1 and R 6 Silver hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8, having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; or

[0344] R 1 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or

[0345] R 6 and B are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0346] R 3 and R 4 is hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with, or

[0347] R 3 and R 4 C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;

[0348] R 2 and R 5 is hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;

[0349] R 4a R4b are independently hydrogen, C1-C6 alkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0350] R 7 Silver, hydrogen, CN, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0351] R 8 Silver hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;

[0352] R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryl, wherein the 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;

[0353] R 10 is selected from CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl, and

[0354] However, the following compounds of chemical formula (I) and their reaction products are excluded:

[0355] L1= L2= N,N'-bis(4,4,4,-trifluorobut-1-en-3-one)-ethylenediamine,

[0356] L1= L2= N,N'-bis(4,4,5,5,5-pentafluoropent-1-en-3-one)-ethylenediamine,

[0357] L1= L2= N,N'-bis(4,4,5,5,6,6,6-heptafluorohex-1-en-3-one)-ethylenediamine and the following compounds and their reaction products:

[0358] Specific details for implementing the invention

[0359] The following examples illustrate the invention without limiting it in any way.

[0360] Examples

[0361] abbreviation:

[0362] APCI-MS Atmospheric Pressure Chemical Ionization-Mass Spectrometer

[0363] DCM dichloromethane

[0364] DEM ethylene glycol dimethyl ether

[0365] HTM Particle Transport Materials

[0366] MeCN Acetonitrile

[0367] iPrOH iso-propanol

[0368] EDTA (ethylenediaminetetraacetic acid)

[0369] Cerium isopropoxide literature[ Gradeff, PS et al., Journal of the less common metals, Vol. 126, 1986, 335-338 Manufactured according to ]

[0370] Sample preparation for conductivity measurement:

[0371] Doped thin film samples were prepared using a glass substrate with 50 nm thick patterned Au electrodes having a channel length of 100 μm. The layers were deposited by thermal evaporation or, for example, by deposition from a liquid phase via spin coating. Thermal evaporation was performed at room temperature under high vacuum (base pressure < 5x10⁻⁶). -7 It occurred at mbar. Hole transport material (HTM) and dopant were co-deposited according to a dopant concentration of 20 wt%, and the evaporation rate was controlled by two independent quartz crystal microbalances.

[0372] The liquid-treated film was spin-coated from a chlorobenzene solution of HTM and dotand at 3000 rpm. The concentration of dotand in HTM was nominally 10 wt%. The layer was then baked at 80°C for 5 minutes. The film thickness was determined by profilometry and ranged from 50 to 110 nm.

[0373] Characterization:

[0374] The lateral conductivity of the coating was determined from the slope of the current-voltage characteristic between -10 and 10 V. For the liquid-treated coating in air, measurements were performed immediately after sample preparation for the thermal evaporation coating in high vacuum.

[0375] Synthesis of 1:

[0376]

[0377] Synthesis literature [J. Schl fer, D. Graf, G. Fornalczyk, and A. Mettenb. It was performed according to [rger, S. Mathur, Inorg. Chem. 2016, 55, 5422-5429].

[0378] The following results were obtained by cyclovoltametry on 1 in dichloromethane (DCM, 200 mV / s, 0.1 M NBu4PF6): E 1 / 2 (Fc / Fc +Contrast (vs.)) = -0.51V.

[0379] Compound 1 is at an external temperature of 140℃ and a pressure of 10 -2 It is sublimated without residue in mbar.

[0380] 2's Synthesis:

[0381]

[0382] The preparation of 4,4,4-trifluoro-3-oxobutanenitrile was carried out according to WO2005 / 49033.

[0383] 4,4,4-trifluoro-3-oxobutanenitrile (1.9 g, 13.9 mmol) was dissolved in acetic anhydride (Ac2O, 5 ml) and (EtO)3CH (2.05 g, 13.9 mmol). The reaction mixture was refluxed for 1 hour. Subsequently, all volatile components were removed under vacuum. The brown residue was dissolved in dichloromethane (DCM 20 ml), and 1,2-diaminoethane (0.2 ml) was added. The white precipitate was filtered out (0.079 g, 0.22 mmol, 1.6%). The mass spectrum of the ligand was [MH] + ; appeared as 353.

[0384] The ligand (76 mg, 0.21 mmol) was added under N2 to a 0.3 M solution of Ce2(OiPr)8(HOiPr)2 (0.17 ml, 0.055 mmol) in ethylene glycol dimethyl ether / ipropanol (DME / iOrOH, 1:1 v / v). After 30 minutes, the solvent was removed. 0.078 mg of the red solid Compound 2 was obtained. The mass spectrum of Compound 2 is [MH] - ; appeared as 843.

[0385] The following results were obtained by cyclic voltammetry for 2 in acetonitrile (ACN, 200 mV / s, 0.1M NBu4PF6):

[0386] E 1 / 2 (Fc / Fc + (Comparison) = +0.40V.

[0387] Synthesis of 3:

[0388]

[0389] The synthesis of the ligand was performed according to the literature [Gurley, L.; Beloukhina, N.; Boudreau, K.; Klegeris, A.; McNeil, WS Journal of Inorganic Biochemistry 2011, 105, 6, 858 - 866].

[0390] 1 (120 mg, 0.26 mmol) was added under N2 to a 0.4 M solution of Ce2(OiPr)8(HOiPr)2 (0.33 ml, 0.131 mmol) in ethylene glycol dimethyl ether / ipropanol (DME / iPrOH) (1:1 v / v). After 30 minutes, the solvent was removed and the solid was washed with diethyl ether (Et2O). 56 mg of the red solid compound 3 was obtained. The mass spectrum of compound 3 was [MH]-; 1047.

[0391] The following results were obtained by cyclic voltammetry for 3 in acetonitrile (ACN, 200 mV / s, 0.1 M NBu4PF6): E 1 / 2 (Fc / Fc + (Comparison) = -0.36V.

[0392] Synthesis of 4:

[0393]

[0394] 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 at 90°C for 12 hours. Upon cooling to -20°C, colorless crystals were formed and filtered. After vacuum drying, 2.0 g (0.37 mmol, 24%) of the colorless solid N1,N2-bis(1-(3,5-bis(trifluoromethyl)phenyl)vinyl)ethane-1,2-diamine was obtained: APCI-MS (Positive): 537.3 [M+H] + .

[0395] N1,N2-bis(1-(3,5-bis(trifluoromethyl)phenyl)vinyl)ethane-1,2-diamine (9.72 g, 18.1 mmol) was added to DCM (50 ml) and trifluoroacetic anhydride (8.37 g, 39.8 mmol). After stirring at room temperature for 12 hours, the reaction solution was cooled to -20°C and the white solid was filtered. The solid was recrystallized from acetonitrile (50 ml) and filtered. White solid, 4.16 g (5.71 mmol, 31%): 4,4'-(ethane-1,2-diylbis(azandyl))bis(4-(3,5-bis(trifluoromethyl)phenyl)-1,1,1-trifluorobut-3-en-2-one), APCI-MS (positive): 729.4 [M+H] + .

[0396] 4,4'-(ethane-1,2-diylbis(azandyl))bis(4-(3,5-bis(trifluoromethyl)phenyl)-1,1,1-trifluorobut-3-en-2-one) (2 g, 2.74 mmol) was added to a solution of cerium(IV) isopropoxide (0.32 M in DME / iPrOH, 4.3 ml, 1.37 mmol). After stirring for 12 hours, the suspension was filtered and washed with DME. Red solid, 1.9 g (1.19 mmol, 87%), cerium bis((2Z,2'Z,4Z,4'Z)-4,4'-(ethane-1,2-diylbis(azanilylide))bis(4-(3,5-bis(trifluoromethyl)phenyl)-1,1,1-trifluorobut-2-en-2-oleate))(4), APCI-MS(positive): 1593 [M+H] + .

[0397] The metal complex (4) (538 mg) is 200°C, 4·10 -6 It was sublimated at mbar. The yield was 335 mg (62%). The metal complex (4) decomposes at 260°C.

[0398] The following results were obtained by cyclic voltammetry for 4 in acetonitrile (ACN, 200 mV / s, 0.1M NBu4PF6):

[0399] E 1 / 2 (Fc / Fc + (Comparison) = -0,12V.

[0400] When 20 wt% of dopant (4) is doped into Spiro-MeO-TAD (CAS No.: 207739-72-8), the conductivity after solvent treatment is up to 1.5·10 -6 It was measured to increase to S / cm (spin coating). The intrinsic conductivity of undoped Spiro-MeO-TAD is 2·10 -8 It was measured in S / cm.

[0401] Synthesis of 5:

[0402]

[0403] 1-(2-hydroxy-5-(trifluoromethyl)phenyl)ethane-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 hours. The solid was then filtered. A white solid, 0.63 g (1.45 mmol, 50%), 2,2'-(-(ethane-1,2-diylbis(azanylylidene))bis(ethane-1-yl-1-ylidene))bis(4-(trifluoromethyl)phenol), APCI-MS (positive): 433.3 [M+H] + .

[0404] 2,2'-(-(ethane-1,2-diylbis(azanylylidene))bis(ethane-1-yl-1-ylidene))bis(4-(trifluoromethyl)phenol) (0.59 g, 1.36 mmol) was added to a solution of cerium(IV) isopropoxide (0.32 M, 0.68 mmol, 2.12 ml in DME / iPrOH). The solvent was removed and the residue was washed with hexane. The residue was dissolved in CHCl3, filtered, precipitated with hexane, and filtered. An orange-red solid, 0.42 g (0.42 mmol, 62%), cerium bis((2,2'-((1E,1'E)-(ethane-1,2-diylbis(azanylylidene))bis(ethane-1-yl-1-ylidene))bis(4-(trifluoromethyl)phenolate))(5) was obtained. APCI-MS (positive): 1001 [M+H] + .

[0405] The metal complex (5) (350 mg) is 4·10 -6 It was sublimated at 180-200°C in mbar. The yield was 12 mg (0.3%).

[0406] The following results were obtained by cyclic voltammetry for 5 in acetonitrile (ACN, 200 mV / s, 0.1 M NBu4PF6): E 1 / 2 (Fc / Fc + Contrast) = +0,3V.

[0407] Synthesis of 6:

[0408]

[0409] Ethylenediamine (830 mg, 13.6 mmol) was added to a 50 ml solution of 2-benzoyl-3-ethoxyacrylonitrile (5.54 g, 27.6 mmol) in dichloromethane and stirred at room temperature. After 2 hours, a precipitate was formed, which was filtered and washed with dichloromethane. After vacuum drying, 2.75 g (7.43 mmol, 55%) of (2Z,2'E)-2,2'-((ethane-1,2-diylbis(azandyl))bis(methanylylidene))bis(3-oxo-3-phenylpropanenitrile) was obtained.

[0410] 2.67 g (7.2 mmol) (2Z,2'E)-2,2'-((ethane-1,2-diylbis(azandyl))bis(methanylylidene))bis(3-oxo-3-phenylpropanenitrile) was added to a solution of cerium isopropoxide (11.25 ml, 3.6 mmol). The brown solid was filtered 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 washing solution was filtered. The washing solution was concentrated by half, and hexane (100 ml) was added. The formed microcrystalline dark solid was filtered and dried under vacuum. 1.80 g (2.05 mmol, 57%) of (6) was obtained. (6) decomposed at 170°C.

[0411] The following results were obtained by cyclic voltammetry for 6 in acetonitrile (ACN, 200 mV / s, 0.1 M NBu4PF6): E 1 / 2 (Fc / Fc + (Comparison) = -0,1V.

[0412] Synthesis of 7:

[0413]

[0414] 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 in 100 ml of dichloromethane at room temperature for 2 days. After concentrating the solution by half, 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 under vacuum. 4.12 g (11.7 mmol, 78%) was isolated.

[0415] 4,4'-(1,2-phenylenebis(azanylylidene))bis(1,1,1-trifluorobut-2-en-2-ol) (2.04 g, 5.80 mmol) was added to solution cerium (IV) isopropoxide (0.32 M in DME / iPrOH, 9 ml, 2.89 mmol). The resulting red solid was filtered and washed with DME. A dark red solid (7), 1.08 g (1.39 mmol, 48%), was obtained. APCI-MS (positive): 841.1 [M+H] + .

[0416] The metal complex (7) (1.00g) is heated to 180-210℃, 3·10 -6 It was sublimated at mbar. The yield was 205 mg (20%). The metal complex (7) decomposes at 237°C.

[0417] The following results were obtained by cyclic voltammetry for 7 in acetonitrile (ACN, 200 mV / s, 0.1 M NBu4PF6): E 1 / 2 (Fc / Fc + (Comparison) = -0.09V.

[0418] Synthesis of 8:

[0419]

[0420] 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 in 500 ml of dichloromethane at room temperature for 2 days. 100 ml of dichloromethane was removed under vacuum, and 200 ml of pentane was added. The microcrystalline solid, (2Z,2'Z,4E,4'E)-4,4'-((4,5-difluoro-1,2-phenylene)bis(azanylylidene))bis(1,1,1-trifluorobut-2-en-2-ol), was filtered and dried under vacuum. 3.60 g (9.27 mmol, 62%) was isolated.

[0421] 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 (0.32 M in DME / iPrOH, 4.3 ml, 1.37 mmol). The suspension was filtered and the red solid was washed with small amounts of DME and hexane. A dark red solid, (8), 0.70 g (0.77 mmol, 12%), cerium bis((2Z,2'Z,4E,4'E)-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] + .

[0422] The metal complex (8) (700 mg) is 180°C, 3·10 -6 It was sublimated at mbar. The yield was 150 mg (22%). The metal complex (8) decomposes at 244°C.

[0423] The cyclic voltammetry for 8 in acetonitrile (ACN, 200 mV / s, 0.1 M NBu4PF6) yielded the following results: E 1 / 2 (Fc / Fc + (Comparison) = +0.08V.

[0424] When ZnPc (zinc phthalocyanine) is doped with 20 wt% of dopant (8), the conductivity after co-evaporation in vacuum is up to 7.6·10 -5 It was measured to increase up to S / cm. The intrinsic conductivity of undoped ZnPc is <1·10 -8 It is S / cm. (Tietze, ML, Pahner, P., Schmidt, K., Leo, K., & L ssem, B. (2015). Advanced Functional Materials, 25(18), 2701-2707).

[0425] When MeO-TPD (CAS No.: 122738-21-0) is doped with 20 wt% of a dopant (8), the conductivity after co-evaporation in vacuum is at most 1.10 -5 It was measured to increase up to S / cm. The intrinsic conductivity of undoped ZnPc is 7·10 -8 It is S / cm. ( Sakai, N., Warren, R., Zhang, F., Nayak, S., Liu, J., Kesava, SV, Lin, Y.-H., Biswal, H.S., Lin, (2021). Adduct-based p-doping of organic semiconductors. Nature Materials 2021 20:9 , 20 (9), 1248-1254. )

[0426] When 20 wt% of a dopant (8) is doped into Spiro-MeO-TAD (CAS No.: 207739-72-8), the conductivity is up to 2.8·10 after solvent treatment (spin coating). -6It was measured to increase up to S / cm. The intrinsic conductivity of undoped spiro-MeO-TAD is 2·10 -8 It was measured in S / cm.

[0427] Synthesis of 9:

[0428]

[0429] 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)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 and washed with a small amount of 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-pentafluoropenta-1-en-3-one, was obtained. APCI-MS (Positive): 459 [M+H] + .

[0430] 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 hours, and then the solvent was removed. The residue was dissolved in acetonitrile, and then copper(II) acetate (1.5 g) was added. Water was added to this dark green solution, and the solid was filtered. The solid was purified by column chromatography (chloroform as the eluent). The residue was treated with oxalic acid and EDTA, followed by concentrated HCl and chloroform, and the phases were separated. The organic phase was washed with saturated NaHCO3 and saturated NaCl solutions and dried (Na2SO4). 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] + .

[0431] 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 (0.32 M in DME / iPrOH, 1.63 mmol, 5.1 ml). Hexane was added, and the resulting solid was filtered and washed with hexane. The residue was dissolved in chloroform, filtered, and recrystallized with chloroform / hexane. A red solid (9), 0.41 g (0.316 mmol, 20%), was obtained. APCI-MS (positive): 1296.8 [M+H] + .

[0432] The metal complex (9) (313 mg) is 3·10 -6It was sublimated at 180-190°C in mbar. The yield was 167 mg (53%). The metal complex (9) decomposes at 244°C.

[0433] The cyclic voltammetry for 9 in acetonitrile (ACN, 200 mV / s, 0.1M NBu4PF6) yielded the following results: E 1 / 2 (Fc / Fc + Contrast) = +0,0V.

[0434] When ZnPc (zinc phthalocyanine) is doped with 20 wt% of dopant (9), the conductivity is at most 1.1·10 after co-evaporation in vacuum. -5 It was measured to increase up to S / cm. The intrinsic conductivity of undoped ZnPc is < 1·10 -8 It is S / cm. (Tietze, M.L., Pahner, P., Schmidt, K., Leo, K., & L ssem, B. (2015). Advanced Functional Materials, 25(18), 2701-2707).

[0435] When Spiro-MeO-TAD (CAS No.: 207739-72-8) is doped with 20 wt% of a dopant (9), the conductivity after solvent treatment (spin coating) is up to 5.1·10 -6 It was measured to increase up to S / cm. The intrinsic conductivity of undoped spiro-MeO-TAD is 2·10 -8 It was measured in S / cm.

Claims

Claim 1 Electronic component comprising at least one compound of chemical formula (I): Ce 4+ [L1L2] 4- (I), where L1 and L2 are each independently selected from the ligands of the following chemical formula (I.1), and ,where X represents O; Z is a bridging group having 2 or 3 carbon atoms between nitrogen atoms, where each carbon atom is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 12 It is substituted with, where two adjacent carbon atoms can be connected to each other by a double bond, or two or three of the carbon atoms are mononuclear, 2-nuclear, or 3-nuclear C6-C 14 It is part of an aromatic or heteroaromatic ring system, wherein the heteroaromatic ring system has 4 to 13 carbon atoms and N, NR as ring elements 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aromatic or heteroaromatic ring system is unsubstituted or has 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; A and B independently N or CR 7 Represents;R 1 and R 6 is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; or R 2 and R 5 is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;R 2 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or R 5 and B are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;R 4a R 4b are independently hydrogen, C1-C6 alkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 7 Silver, hydrogen, CN, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 8 Silver hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryl, wherein the 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; R 10 is selected from CN, halogen, C1-C4 alkyl, C1-C4 haloalkyl; R 11 is selected from CN, halogen, C1-C4 alkyl, C1-C4 haloalkyl; R 12 is independently selected from halogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 It is replaced with. Claim 2 In claim 1, an electronic component comprising one or more compounds of the following chemical formula (I): Ce 4+ [L1L2] 4- (I), where L1 and L2 are each independently selected from the ligands of the following chemical formula (II), and , here group CR 3 -CR 4 fraud represents a single or double bond; X independently represents O; A and B independently represent N or CR 7 Representing; R 1 and R 6 Silver hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; or R 3 and R 4 is hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with, or R 3 and R 4 C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;R 2 and R 5 is hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;R 4a R 4b are independently hydrogen, C1-C6 alkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 7 Silver, hydrogen, CN, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 8 Silver hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryl, wherein the 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; R 10 It is selected from CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl. Claim 3 In claim 1 or 2, in the above formula (I.1) or formula (II), R 1 , R 2 , R 5 and R 6 This hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b and electronic components independently selected from group A consisting of the following A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18 and A19: Here, # represents a bond to the group of chemical formula (I), where R A , R B , R C , R D and R E is independently selected from hydrogen, CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl; or R 4a , R 4b is hydrogen, C1-C6 alkyl and C6-C 14 Independently selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or substituted with 1, 2, 3, 4, or 5 identical or different radicals selected from C1-C4 alkyls and C1-C4 halos and kill;R 10 It is selected from CN, halogen, C1-C4 alkyl and C1-C4 haloalkyl. Claim 4 In claim 1 or 2, in the above formula (II), R 3 and R 4 ga is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy and C1-C6 haloalkoxy and phenyl, wherein phenyl is unsubstituted or 1, 2, 3 or 4 identical or different radicals R 9 Replaced with, or R 3 and R 4 They form a phenyl ring with the carbon atom to which they are attached, where the phenyl is unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;R 9 a CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl or C6-C 14 An electronic component selected from aryl, wherein the aryl is unsubstituted or substituted with 1, 2, 3, 4, or 5 identical or different substituents selected from C1-C4 alkyl or C1-C4 haloalkyl. Claim 5 In claim 1 or 2, in the above formula (I.1) or formula (II), A and B are independently radical CR 7 Selected from, R 7 Electronic component selected from group B consisting of hydrogen CN, nitro, halogen and the following B1, B2, B3, B4, B5, B6, B7, B8, B9, B10, B11, B12, B13, B14 and B15: Here, # indicates a bond to the group of chemical formula (II), where R F , R G , R H , R I and R J is independently selected from hydrogen, CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl. Claim 6 In claim 1 or 2, in the above formula (I.1) or formula (II), R 1 , R 2 , R 5 and R 6 Electronic component independently selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, and A1: Here, # represents a bond to the remaining molecule of formula (I.1) or formula (II), where R A , R B , R C , R D and R E is independently selected from hydrogen, CN, fluorine, chlorine, C1-C4 alkyl, C1-C4 fluoroalkyl, and C1-C4 chloroalkyl; or R 9 is selected from CN, halogen, C1-C4 alkyl, C1-C4 haloalkyl and phenyl, wherein phenyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from C1-C4 alkyl or C1-C4 haloalkyl. Claim 7 In claim 1 or 2, in the above formula (I.1) or formula (II), independently radical CR 7 and R 7 Electronic component selected from hydrogen, CN, nitro, halogen, C1-C2 alkyl and C1-C2 haloalkyl. Claim 8 In paragraph 1 or 2, R 3 and R 4 are independently selected from hydrogen, CN, C1-C4-alkyl, C1-C4-haloalkyl, or R 3 and R 4 They form a phenyl ring with the carbon atom to which they are attached, where the phenyl is unsubstituted or 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;R 9 An electronic component selected from CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl, or phenyl, wherein phenyl is unsubstituted or substituted with 1, 2, 3, or 4 identical or different substituents selected from C1-C4-alkyl or C1-C4-haloalkyl. Claim 9 An electronic component according to claim 1 or 2, wherein L1 and L2 have the same definition. Claim 10 An electronic component 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 in claim 1 or 2. Claim 11 An electronic component having a layered structure comprising 2, 3, 4, 5, 6, 7 or more layers according to claim 1 or 2. Claim 12 An electronic component comprising, in claim 1 or 2, a hole transport layer and / or a hole injection layer comprising at least a compound of formula (I). Claim 13 An electronic component comprising an electron transport layer, comprising at least a compound of formula (I) in claim 1 or 2. Claim 14 A doped semiconductor matrix material comprising at least one electron donor and at least one compound of formula (I) as defined in either claim 1 or 2, wherein the electron donor is 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,N'-((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-(6-((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-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9'-spirobi[fluoren]-2-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)phenyl)-N-(9,9-di-methyl-9H-fluoren-2-yl)-9,9'-spirobi[fluoren]-2-amine, N-(4-(6-(dibenzo[b,d]furan-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)-phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-2-amine, 9-(4-(6-(9H-carbazole-9-yl)-1,3,3-trimethyl-2,3-dihydro-1H-indene-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-indene-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-indene-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-fluoren-2-yl)-[1,1'-biphenyl]-4,4'-diamine(TDMFB), N-([1,1'-biphenyl]-2-yl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi[fluoren]-2-amine, (2,7-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobi[9, H A mixture of -fluorene](spiro-MeO-TPD), 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 and 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, A doped semiconductor matrix material selected from N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-fluorene-2-amine and mixtures thereof. Claim 15 A compound of formula (I) as defined in claim 1 or 2, which is used as an organic semiconductor, as a doping agent for an organic semiconductor matrix material, as a p-dopant for a hole transport layer, as a charge injector for a charge injection layer, as an electron transport layer, as a cathode material for an organic battery, as an electrochromic material, or as an electron acceptor. Claim 16 A mixture of compounds of formula (I) as defined in claim 1 or 2, which is used as: - as an organic semiconductor; - as a doping agent for an organic semiconductor matrix material; - as a p-dopant for a hole transport layer; - as a charge injector for a charge injection layer; - as an electron transport layer; - as a cathode material for an organic battery; - as an electrochromic material; - as an electron acceptor. Claim 17 A Ce(III) complex anion obtained by the reduction of a compound of formula (I) as defined in claim 1 or 2 together with an electron donor, or a charge transfer complex of a compound of formula (I) as defined in claim 1 or 2, which is used as an organic semiconductor, electrochromic material or ferromagnetic material. Claim 18 Compounds of the following general formula (I), their charge transfer complexes, their reduction products, and mixtures thereof: Ce 4+ [L1L2] 4- (I), where L1 and L2 are each independently selected from the ligands of the following chemical formula (I.1), and , where X independently represents O; Z is a bridging group having 2 or 3 carbon atoms between nitrogen atoms, where each carbon atom is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 12 It is substituted with, where two adjacent carbon atoms can be connected to each other by a double bond, or two or three of the carbon atoms are mononuclear, 2-nuclear, or 3-nuclear C6-C 14 It is part of an aromatic or heteroaromatic ring system, wherein the heteroaromatic ring system has 4 to 13 carbon atoms and N, NR as ring elements 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aromatic or heteroaromatic ring system is unsubstituted or has 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; A and B independently N or CR 7 Represents;R 1 and R 6 is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; or R 2 and R 5 is independently selected from hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;R 2 and A are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with, or R 5 and B are C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a hetaaryl group having 4 to 13 carbon atoms, wherein the hetaaryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;R 4a R 4b are independently hydrogen, C1-C6 alkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 7 Silver, hydrogen, CN, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 8 Silver hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryl, wherein the 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; R 10 is selected from CN, halogen, C1-C4 alkyl, C1-C4 haloalkyl; R 11 is selected from CN, halogen, C1-C4 alkyl, C1-C4 haloalkyl; R 12 is independently selected from halogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3-C7 cycloalkyl, wherein the C3-C7 cycloalkyl is unsubstituted or 1, 2, 3, 4, 5, or 6 identical or different radicals R 11 , C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 It is substituted with an aryl and a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 It is substituted with; provided that the following compounds are excluded: . Claim 19 In paragraph 18, as compounds of the following general formula (I), charge transfer complexes thereof, reduction products thereof, and mixtures thereof, Ce 4+ [L1L2] 4- Compounds, charge transfer complexes thereof, reduction products thereof, and mixtures thereof, wherein (I), L1 and L2 are each independently selected from tetradentate ligands of the ligands of the following formula (II): , here group CR 3 -CR 4 between represents a single or double bond; X independently represents O; A and B independently represent N or CR 7 Representing; R 1 and R 6 Silver hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with; or R 3 and R 4 is hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with, or R 3 and R 4 C6-C together with the carbon atoms to which they are attached 14 Forming an aryl group or a heta-aryl having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic group consisting of N, NR 8 Having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from , O, S, SO, and SO2, and the aryl and heteroaryl are unsubstituted or have 1, 2, 3, or 4 identical or different radicals R 9 Replaced with;R 2 and R 5 is hydrogen, CN, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Independently selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 9 Replaced with;R 4a R 4b are independently hydrogen, C1-C6 alkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 7 Silver, hydrogen, CN, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfanyl, C1-C6 haloalkylsulfanyl, NR 4a R 4b , C6-C 14 Selected from aryls and heta-aryls having 4 to 13 carbon atoms, wherein the heta-aryl is a cyclic element N, NR 8 , having 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups selected from O, S, SO, and SO2, wherein the aryl and heteroaryl are unsubstituted or have 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 8 Silver hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryls, wherein the aryl is unsubstituted or 1, 2, 3, 4, or 5 identical or different radicals R 10 Replaced with;R 9 is CN, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C6-C 14 Selected from aryl, wherein the 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; R 10 is selected from CN, halogen, C1-C4 alkyl, and C1-C4 haloalkyl, provided that the following compounds of formula (I) and their reaction products are excluded: L1= L2= N,N'-bis(4,4,4,-trifluorobut-1-en-3-one)-ethylenediamine, L1= L2= N,N'-bis(4,4,5,5,5-pentafluoropent-1-en-3-one)-ethylenediamine, L1= L2= N,N'-bis(4,4,5,5,6,6,6-heptafluorohex-1-en-3-one)-ethylenediamine and the following compounds and their reaction products: .

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