Novel cerium(iv) complexes and their use in organic electronics

Abstract

The present invention relates to novel cerium(IV) complexes. Furthermore, the present invention relates to electron-doped semiconductor materials and electronic components comprising the cerium(IV) complexes. A further object of the present invention is the use of the cerium(IV) complexes as electron acceptors, in particular as p-dopants and electron transport materials in organic electronic components.

Description

[0001] This invention relates to novel cerium(IV) complexes. Furthermore, this invention relates to electron-doped semiconductor materials and electronic components comprising cerium(IV) complexes. Another object of this invention is the use of cerium(IV) complexes as electron acceptors, particularly as p-type dopants and electron transport materials in organic electronic components. Background of the Invention

[0003] Organic electronics focuses on the development, characterization, and application of novel organic small molecules and polymers with certain 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) (such as exciton solar cells, dye-sensitized solar cells (DSSCs), or perovskite solar cells), electron photography (such as photoconductive materials in organic photoconductors (OPCs)), organic optical detectors, organic photoreceptors, light-emitting electrochemical cells (LECs), and organic laser diodes.

[0004] It is known that the conductivity of organic semiconductor matrices can be greatly affected by doping. Such organic semiconductor matrix materials can be formed from compounds with good electron donor properties (p-conductors) or compounds with good electron acceptor properties (n-conductors). Compared to inorganic semiconductors, organic semiconductors have very low intrinsic charge carrier concentrations. Organic semiconductor matrix materials are therefore often doped to achieve good semiconductor properties. For n-type doping, a strong electron donor (n-type dopant) is used, which transfers electrons to the LUMO of the semiconductor matrix (n-type doping), resulting in free electrons in the matrix (SOMO). For p-type doping, a strong electron acceptor (p-type dopant) is used, which removes electrons from the HOMO of the semiconductor matrix (p-type doping), resulting in holes. In other words, for p-type doping, the LUMO of the dopant must be lower than the HOMO energy of the matrix. The dopant acts as an acceptor and leaves active holes in the matrix (SOMO).

[0005] Known p-type dopants used for electron donor materials are electron acceptors, such as tetracyanoquinone methane (TCNQ), 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone methane (F4TCNQ), thiamethoxam (HATNA), metal oxides such as MoO3 or WO3, or radialene compounds as described, for example, in EP 2180029. Acceptor molecules generate so-called holes in the semiconductor matrix material (hole transport material) through an electron transfer process, and the conductivity of the semiconductor matrix material (hole transport material) varies more or less depending on the number and mobility of holes.

[0006] However, the previously described compounds or classes of compounds have disadvantages for their technical applications in the production 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, exhibit unstable evaporation rates, and / or demonstrate low thermal stability. Furthermore, some of these compounds have very high production costs.

[0007] Therefore, there is still a need for compounds that are readily available or producible, suitable for use as doped electron donor materials, and do not have the aforementioned drawbacks.

[0008] Only a few diketone cerium(IV) complexes are known. Several β-diketone cerium(IV) complexes have been described in the literature. M. Ciampolini et al., JCS Dalton, 1977, 1325; T. J. Pinnaviaia et al., Contribution from the department of Chemistry, Cornell University, Ithaca, New York, 1965, 233; I. Baxter et al., J. Chem. Cryst, Vol. 28, No. 4, 1998, 267; N. Apiro et al., Coord. Chem. Review, 260, 2014, 21; M. Delarosa et al., J. Coord. Chem., 55(7), 2002, 781; Jahr et al., Zeitschrift für Chemie, Bd. 15, 1975, S280-281; ​​Snezhko et al., Material Science and Engineering, Vol. 18, 1993, S230-231; Brill et al., Liebigs Annalen derChemie, 1979, pp. 803-810 and WO02 / 018394 describe cerium(IV) complexes.

[0009] WO 02 / 018394 relates to precursor source reagents with a metal-organic composition. It describes the formation of cerium-doped (Ca,Sr)Ga₂S₂ films using a sulfur-containing solvent system and their deposition in the presence of hydrogen sulfide gas.

[0010] Kunkely et al., Journal of Photochemistry and Photobiology A, Vol 146, No. 1-2, pp. 63-66, describe the cerium(IV)₂, 2,6,6-tetramethyl-3,5-heptane-diketoic acid anion. They further describe that this complex possesses luminescent and photosensitive properties. These properties are independent of p-type dopants or redox doping pairs in the transport layer.

[0011] US2010 / 0038632 describes a variety of complexes, including cerium(IV) complexes. However, no specific cerium(IV) complex according to the invention is mentioned.

[0012] WO 2021 / 048044 relates to cerium(IV) complexes and their uses in organic electronics. However, the compounds disclosed in this document differ from those according to the present invention.

[0013] US 4,511,515 discloses a method for synthesizing a specific cerium(IV) complex, namely [Ce(fod)4], wherein fod is β-diketone 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione. US 4,511,515 does not even mention the use of this compound in organic electronics.

[0014] WO 00 / 32719 relates to metal complexes that form films or layers on a substrate. The general formula for defining metal complexes is very broad. Therefore, the compounds according to the invention differ from those disclosed in WO 00 / 32719.

[0015] On the other hand, the large band gap in the cerium complexes mentioned in the literature is not relevant to p-type dopants.

[0016] The use of cerium(IV) complexes in organic semiconductor materials is unknown to date. In particular, the use of cerium(IV) complexes as p-type dopants, as electron transport materials, or as electron acceptors has not been described.

[0017] Surprisingly, it has now been discovered that cerium(IV) complexes can be advantageously used as p-type dopants. Furthermore, cerium(IV) complexes have been found to be suitable 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.

[0018] Furthermore, many cerium diketoates (IV) can evaporate very well under vacuum and occasionally exhibit high thermal stability. Therefore, they are essentially suitable for both approaches in the fabrication of organic electronic components: vacuum coating (vapor deposition) and solvent-based processing (solution fabrication). Summary of the Invention

[0019] The first objective of this invention is a compound of general formula (I).

[0020] Ce 4+ (L1L2L3L4) 4- (I),

[0021] in

[0022] L1, L2, L3, and L4 are independently selected from bidentate ligands having the general formula (II).

[0023] in

[0024] Y represents N or CR 3 ;

[0025] R 1 Represents CFR a R b tert-butyl, adamantyl, C2F5, n-C3F7, C3-C7-cycloalkyl, phenyl, naphthyl, pyridinyl, pyrimidinyl, triazine, among which

[0026] The cycloalkyl group is either unsubstituted or substituted with 1 to 13 groups selected from fluorine and CF3.

[0027] The phenyl group is substituted with at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2.

[0028] The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from CN, NO2, F, Cl, Br, C1-C4-haloalkyl, OCF3, SCF3, SO2CF3, N=C(CF3)2, SF5, and N(SO2CF3)2.

[0029] The pyridyl, pyrimidinyl, and triazine groups are substituted by at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2, and N(SO2CF3)2; or

[0030] R 1Together with Y and the CO- group to which they are bonded (especially the carbon atom of the CO- group), they form a 5- to 7-membered ring that may have a C=O or C(CH3)2 group as a ring member, and said 5- to 7-membered ring is fused with a phenyl group, wherein the fused phenyl group is unsubstituted or substituented by 1, 2, 3 or 4 R groups. 4 replace;

[0031] R 2 Represents CFR a R b tert-butyl, adamantyl, C2F5, n-C3F7, C3-C7-cycloalkyl, phenyl, naphthyl, pyridyl, pyrimidinyl, triazine, among which

[0032] The cycloalkyl group is either unsubstituted or substituted with 1 to 13 groups selected from fluorine and CF3.

[0033] The phenyl group is substituted with at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2.

[0034] The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from CN, NO2, F, Cl, Br, C1-C4-haloalkyl, OCF3, SCF3, SO2CF3, N=C(CF3)2, SF5, and N(SO2CF3)2.

[0035] The pyridyl, pyrimidinyl, and triazine groups are substituted by at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2, and N(SO2CF3)2; or

[0036] R 2 Together with Y and the CO- group to which they are bonded (especially the carbon atom of the CO- group), they form a 5- to 7-membered ring that may have a C=O or C(CH3)2 group as a ring member, and said 5- to 7-membered ring is fused with a phenyl group, wherein the fused phenyl group is unsubstituted or substituented by 1, 2, 3 or 4 R groups. 4 replace;

[0037] R a and R b Each of these elements independently represents halogen, CF3, CN, and C6-C. 14 -aryl, which is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from halogens, C1-C4-haloalkyl, C1-C4-haloalkoxy, SCF3, SO2CF3, NO2, N=C(CF3)2, SF5, N(SO2CF3)2 and CN; R 3Represents hydrogen, F, Cl, CN, CF3, OCF3, SCF3, methyl, ethyl, tert-butyl, adamantyl, phenyl, or a heteroaryl group having 4 to 5 carbon atoms, wherein the heteroaryl group has 1, 2, or 3 nitrogen atoms as ring members, and wherein the phenyl and heteroaryl groups are unsubstituted or surrounded by 1 or 2 identical or different groups R. 5 replace;

[0038] R 4 Represents CN, NO2, SF5, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-haloalkylsulfanyl, C1-C4-haloalkylsulfonyl, N=C(CF3)2 and N(SO2CF3)2;

[0039] R 5 It represents CN, F, Cl, CF3, OCF3, SCF3, SO2CF3, NO2, N=C(CF3)2, SF5 and N(SO2CF3)2.

[0040] Another object of the present invention is an electronic component comprising at least one compound of general formula (I).

[0041] Ce 4+ (L1L2L3L4) 4- (I), where

[0042] in

[0043] L1, L2, L3, and L4 are independently selected from bidentate ligands having the general formula (II).

[0044] in

[0045] Y represents N or CR 3 ;

[0046] R 1 Represents CFR a R b tert-butyl, adamantyl, C2F5, n-C3F7, C3-C7-cycloalkyl, phenyl, naphthyl, pyridyl, pyrimidinyl, triazine, among which

[0047] The cycloalkyl group is either unsubstituted or substituted with 1 to 13 groups selected from fluorine and CF3.

[0048] The phenyl group is substituted with at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2.

[0049] The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from CN, NO2, F, Cl, Br, C1-C4-haloalkyl, OCF3, SCF3, SO2CF3, N=C(CF3)2, SF5, and N(SO2CF3)2.

[0050] The pyridyl, pyrimidinyl, and triazine groups are substituted by at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2, and N(SO2CF3)2; or

[0051] R 1 Together with Y and the CO- group to which they are bonded (especially the carbon atom of the CO- group), they form a 5- to 7-membered ring that may have a C=O or C(CH3)2 group as a ring member, and said 5- to 7-membered ring is fused with a phenyl group, wherein the fused phenyl group is unsubstituted or substituented by 1, 2, 3 or 4 R groups. 4 replace;

[0052] R 2 Represents CFR a R b tert-butyl, adamantyl, C2F5, n-C3F7, C3-C7-cycloalkyl, phenyl, naphthyl, pyridyl, pyrimidinyl, triazine, among which

[0053] The cycloalkyl group is either unsubstituted or substituted with 1 to 13 groups selected from fluorine and CF3.

[0054] The phenyl group is substituted with at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2.

[0055] The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from CN, NO2, F, Cl, Br, C1-C4-haloalkyl, OCF3, SCF3, SO2CF3, N=C(CF3)2, SF5, and N(SO2CF3)2.

[0056] The pyridyl, pyrimidinyl, and triazine groups are substituted by at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2, and N(SO2CF3)2; or

[0057] R 2Together with Y and the CO- group to which they are bonded (especially the carbon atom of the CO- group), they form a 5- to 7-membered ring that may have a C=O or C(CH3)2 group as a ring member, and said 5- to 7-membered ring is fused with a phenyl group, wherein the fused phenyl group is unsubstituted or substituented by 1, 2, 3 or 4 R groups. 4 replace;

[0058] R a and R b Each of these elements independently represents halogen, CF3, CN, and C6-C. 14 -aryl, which is unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4-haloalkyl, C1-C4-haloalkoxy, SCF3, SO2CF3, NO2, N=C(CF3)2, SF5, N(SO2CF3)2 and CN;

[0059] R 3 Represents hydrogen, F, Cl, CN, CF3, OCF3, SCF3, methyl, ethyl, tert-butyl, adamantyl, phenyl, or a heteroaryl group having 4 to 5 carbon atoms, wherein the heteroaryl group has 1, 2, or 3 nitrogen atoms as ring members, and wherein the phenyl and heteroaryl groups are unsubstituted or surrounded by 1 or 2 identical or different groups R. 5 replace;

[0060] R 4 Represents CN, NO2, SF5, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio, C1-C4-haloalkylsulfonyl, N=C(CF3)2 and N(SO2CF3)2;

[0061] R 5 It represents CN, F, Cl, CF3, OCF3, SCF3, SO2CF3, NO2, N=C(CF3)2, SF5 and N(SO2CF3)2.

[0062] Another 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 the groups Y, R 1 and R 2 It has the meaning given above and defined below.

[0063] Another object of the present invention is the use of compound (I) or mixtures thereof, wherein groups Y, R 1 and R 2 It has the meanings defined above and below.

[0064] -As an organic semiconductor

[0065] - As a dopant in organic semiconductor matrix materials, especially as a p-type dopant in hole transport layers.

[0066] - As a charge injector in the charge injection layer

[0067] - As a cathode material in organic battery packs.

[0068] - As an electrochromic material.

[0069] Another object of the present invention is the use of Ce(III)-complex anions obtained by reducing the compound (I) as defined above and below or the charge-transfer complex of the compound (I) as defined above and below, together with an electron donor, as organic conductors, as electrochromic materials or as ferrimagnets. Detailed Implementation

[0071] The present invention has the following advantages:

[0072] - The cerium(IV) complex according to the present invention has only low production cost.

[0073] - The cerium(IV) complex according to the invention is advantageously suited as an electron acceptor for use as a p-type dopant and electron transport material in organic electronic components.

[0074] - The cerium(IV) complex according to the invention exhibits better conductivity compared to known electron acceptors.

[0075] - The cerium(IV) complex according to the present invention exhibits improved thermal stability of the doped layer compared with the prior art.

[0076] - Furthermore, the cerium(IV) complex according to the invention is characterized by high doping efficiency.

[0077] - The cerium(IV) complexes and corresponding reduced cerium(III) compounds according to the invention exhibit only low absorption of the doped layer. Therefore, parasitic absorption and emission can be reduced or even prevented.

[0078] - The cerium(IV) complexes according to the invention are suitable for producing organic and hybrid optoelectronic components by solvent processing and by vacuum reprocessing.

[0079] In this invention, a bidentate ligand (also called a didentate ligand) is a ligand in which two atoms are bonded to a metal atom (cerium atom).

[0080] In this invention, homogamic cerium(IV) compounds are complexes in which all ligands are identical.

[0081] In this invention, a heterojunction cerium(IV) compound is a complex in which at least one ligand has a different meaning than the other ligands.

[0082] In this invention, the prefix C n -C m This indicates the number of carbon atoms that the molecule or residue may contain.

[0083] In this invention, the term C1-C6-alkyl refers to an unbranched or branched saturated hydrocarbon group having 1 to 6 carbon atoms. C1-C6-alkyl groups are, 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 1-ethyl-2-methylpropyl. C1-C4-alkyl refers to, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl.

[0084] In this invention, the term C1-C6-alkoxy refers to an unbranched or branched saturated C1-C6-alkyl group as defined above, bonded via an oxygen atom. Alkoxy groups having 1 to 4 carbon atoms are preferred, and particularly preferred are those with 1 or 2 carbon atoms. C1-C2-alkoxy groups are methoxy or ethoxy groups. C1-C4-alkoxy groups are, 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, as well as other examples such as pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 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.

[0085] In this invention, the term C1-C6-alkylthio group refers to an unbranched or branched saturated C1-C6-alkyl group as defined above, bonded via a sulfur atom. Alkylthio groups having 1 to 4 carbon atoms are preferred, and particularly preferred are those with 1 or 2 carbon atoms. C1-C2-alkylthio groups are methylthio or ethylthio. C1-C4-alkylthio groups are, for example, methylthio, ethylthio, n-propylthio, 1-methylethylthio (isopropylthio), butylthio, 1-methylpropylthio (sec-butylthio), 2-methylpropylthio (isobutylthio), or 1,1-dimethylethylthio (tert-butylthio). C1-C6-alkylthio includes the meaning given for C1-C4-alkylthio, and also includes, for example, pentylthio, 1-methylbutyryl, 2-methylbutyryl, 3-methylbutyryl, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutyryl, 1,2-dimethylbutyryl, 1,3-dimethylbutyryl, 2,2-dimethylbutyryl, 2,3-dimethylbutyryl, 3,3-dimethylbutyryl, 1-ethylbutyryl, 2-ethylbutyryl, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio, or 1-ethyl-2-methylpropylthio.

[0086] In this invention, the terms haloalkyl, haloalkoxy, and haloalkylthio are used to describe partially or fully halogenated alkyl, alkoxy, or alkylthio groups. In other words, one or more hydrogen atoms, such as 1, 2, 3, 4, or 5 hydrogen atoms, bonded to one or more carbon atoms of the alkyl, alkoxy, or alkylthio group are replaced by halogen atoms, particularly by fluorine or chlorine.

[0087] The term "halogen" in each case refers to fluorine, chlorine, bromine, or iodine.

[0088] The expression "CN" represents cyano group (-C≡N).

[0089] The term "aryl" in this invention includes monocyclic or polycyclic aromatic hydrocarbon groups having typically 6 to 14, particularly preferably 6 to 10, carbon atoms. Examples of aryl groups include, in particular, phenyl, naphthyl, indene, fluorenyl, anthracene, phenanthryl, and naphthacenyl. Groups such as phenyl, pyrene, etc., especially phenyl or naphthyl.

[0090] The term "heteroaryl" in this invention includes a monocyclic aromatic hydrocarbon group having 4 to 5 carbon atoms, wherein 1, 2, or 3 carbon atoms are replaced by 1, 2, or 3 nitrogen atoms as ring members. The heteroaryl group may be attached to the rest of the molecule via a ring carbon or via a ring nitrogen. Examples of 5- or 6-membered aromatic heterocycles (also called heteroaromatic rings or heteroaryl groups) are 2-pyrrole, 3-pyrrole, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1,3,4-triazol-2-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, and 2-pyrazinyl.

[0091] In this invention, the term "C5-C7-cycloalkyl" as used herein refers to a monocyclic saturated alicyclic group, such as cyclopentyl, cyclohexyl, or cycloheptyl. The term "C5-C7-halocycloalkyl," as used herein, also means "partially or fully halogenated cycloalkyl," refers to a C5-C7-cycloalkyl group as described above in which some or all of its hydrogen atoms are replaced by halogen atoms, particularly fluorine, as described above.

[0092] When ~ appears in a formula showing a preferred substructure of the compound of the present invention, it represents a bond that connects to the rest of the molecule.

[0093] Cerium compounds of formula (I)

[0094] Formula (I)

[0095] Ce 4+ (L1L2L3L4) 4- (I), where

[0096] L1, L2, L3, and L4 are defined above and below.

[0097] Including the following compounds, wherein

[0098] - All four ligands L1, L2, L3, and L4 have the same meaning.

[0099] Three of the four ligands have the same meaning.

[0100] Two of the four ligands have the same meaning.

[0101] - All four ligands, L1, L2, L3, and L4, have different meanings.

[0102] Preferably, the compound of formula (I) in which L1, L2, L3 and L4 have the same meaning is preferred.

[0103] In the cerium compounds of formula (I), L1, L2, L3, and L4 are independently selected from bidentate ligands having general formula (II). In the following, preferred embodiments of compound (I) are defined directly by preferred embodiments of its bidentate ligand (II).

[0104] In the first implementation scheme, R 1 and R 2 Preferably, they have different meanings. Preferably, R 1 and R 2 Selected independently from CFR a R b tert-butyl, adamantyl, C2F5, n-C3F7, C3-C7-cycloalkyl, phenyl, naphthyl, pyridyl, pyrimidinyl, triazineyl

[0105] in

[0106] The cycloalkyl group is unsubstituted or substituted with 1 to 13 groups selected from fluorine and CF3, and the phenyl group is substituted with at least one group selected from NO2, CN, F, Cl, Br, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2.

[0107] The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from CN, NO2, F, Cl, Br, C1-C4-haloalkyl, OCF3, SCF3, SO2CF3, N=C(CF3)2, SF5, and N(SO2CF3)2.

[0108] The pyridyl, pyrimidinyl, and triazine groups are substituted by at least one group selected from NO2, CN, F, Cl, Br, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2, and N(SO2CF3)2.

[0109] Preferably, R 1 Selected from CFR a R b tert-butyl, adamantyl, C2F5, n-C3F7, and C3-C7-cycloalkyl, wherein the cycloalkyl group is unsubstituted or substituted by 1 to 13 groups selected from F and CF3.

[0110] and

[0111] R 2 Selected from CFR a R b , phenyl, naphthyl, pyridyl and pyrimidinyl, among which

[0112] The phenyl group is substituted with at least one group selected from NO2, CN, F, Cl, Br, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2.

[0113] The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from CN, NO2, F, Cl, Br, C1-C4-haloalkyl, OCF3, SCF3, SO2CF3, N=C(CF3)2, SF5, and N(SO2CF3)2.

[0114] The pyridyl and pyrimidinyl groups are substituted by at least one group selected from NO2, CN, F, Cl, Br, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2.

[0115] In particular, R 1 Selected from CFR a R b tert-butyl, adamantyl, C2F5, n-C3F7 and C5-C6 cycloalkyl, especially CFR a R b tert-butyl, adamantyl, C2F5, n-C3F7, 2,2,3,3,4,4,5,5-octafluoro-1-(trifluoromethyl)cyclopentyl, nonafluorocyclopentyl, 2,2,3,3,4,4,5,5,6,6-decafluoro-1-(trifluoromethyl)cyclohexyl and 1,2,2,3,3,4,4,5,5,6,6-undecanofluorocyclohexyl.

[0116] In particular, R 2 Selected from CFR a R b , phenyl, naphthyl, pyridyl and pyrimidinyl, among which

[0117] The phenyl group is substituted with at least one group selected from CN, F, Cl, and CF3.

[0118] The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from F, Cl, and CF3.

[0119] The pyridyl and pyrimidinyl groups are substituted by at least one group selected from F, Cl and CF3.

[0120] In the second implementation scheme, R 1 and R 2 They have the same meaning. Preferably, R 1 and R 2 Selected from CFR a R bAnd phenyl, wherein the phenyl group is substituted with at least one group selected from F, Cl, Br, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2,

[0121] R a The preferred choice is F, and R b Preferred selection is from C6-C 14 -aryl, which is unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4-haloalkyl, C1-C4-haloalkoxy, SCF3, SO2CF3, NO2, N=C(CF3)2, SF5, N(SO2CF3)2 and CN.

[0122] In the third implementation scheme, R 1 Together with the CO- groups to which they are bonded, they form 5- to 7-membered rings that may have C=O or C(CH3)2 groups as ring members, and said 5- to 7-membered rings are fused with phenyl groups, wherein the fused phenyl groups are unsubstituted or substituents R of 1, 2, 3 or 4. 4 Replace, and

[0123] R 2 Selected from CFR a R b tert-butyl, adamantyl, C2F5, n-C3F7 and C3-C7-cycloalkyl, wherein the cycloalkyl group is unsubstituted or substituted by 1 to 13 groups selected from F and CF3.

[0124] Wherever it appears, R 3 Preferably selected from H, CN, tert-butyl, adamantyl, 3,5-trifluoromethyl-phenyl, CF3, OCF3 and SCF3, especially selected from H, CN, tert-butyl, adamantyl, 3,5-trifluoromethyl-phenyl.

[0125] Wherever it appears, R 4 Preferably selected from CN, NO2, SF5, halogens, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, N=C(CF3)2 and N(SO2CF3)2, especially F, CF3, trifluoromethylthio, trifluoromethylsulfonyl, N=C(CF3)2, N(SO2CF3)2, especially F and CF3.

[0126] Wherever it appears, R 5 The preferred components are F, Cl, and CF3.

[0127] Wherever it appears, Ra and R b The groups A selected independently from F, CF3 and A1 to A32

[0128]

[0129] The ~ refers to the bonds that connect to the rest of the molecule.

[0130] In particular, R a It is F, and R b It is group A or R as defined above. a and R b It's CF3.

[0131] Preferably, in the implementation schemes L1, L2, L3, and L4, L4 has the same meaning.

[0132] In another specific implementation, L1, L2, L3, and L4 have different meanings.

[0133] The compounds of formula (I) in which L1, L2, L3, and L4 have the same meaning are selected from...

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158] Ad is adamantyl alkyl group.

[0159] R 3 It contains CN, F, Cl, CF3, Ar, tert-butyl, and adamantyl.

[0160] R 1 It is CF(CF3)2, n-C3F7, 2,2,3,3,4,4,5,5-octafluoro-1-(trifluoromethyl)cyclopentyl and 1,2,2,3,3,4,4,5,5,6,6-undecylfluorocyclohexyl.

[0161] X is N(SO2CF3)2, SF5, OCF3, SCF3, CF(CF3)2,

[0162] Z represents F, Cl, CF3, CN,

[0163]

[0164] Ar is selected from A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A1 7. A18, A19, A20, A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31 and A32

[0165]

[0166] Ar1 is

[0167]

[0168] The homogamic compounds of formula (I) are produced by reacting a β-diketone ligand with a cerium salt. Typically, the cerium salt is soluble in the reaction medium. Suitable salts are cerium ammonium nitrate and cerium ammonium sulfate. β-diketone ligands are commercially available, or they can be prepared by synthesis known to those skilled in the art.

[0169] The heterogamic compound of formula (I) is produced as follows:

[0170] - Mix two different homogeneous cerium compounds in a suitable solvent.

[0171] - Mix homogeneous cerium compounds with ligands that are different from the ligands of the compound or their alkali metal / alkaline earth metal salts.

[0172] - Two different homogeneous cerium compounds were deposited in the vapor phase.

[0173] - Vapor deposition (vapor co-condensation) of homogeneous cerium compounds with ligands different from those of the compound.

[0174] This invention does not include compounds of formula (Ia).

[0175] Ce 4+ [(R 1 -C(-O)=C(R 3 )-C(=O)-R 2 (R) 1’ -C(-O)=C(R 3' )-C(=O)-R 2' (R) 1” -C(-O)=C(R 3” )-C(=O)-R 2” (R) 1”' -C(-O)=C(R 3”' )-C(=O)-R 2”' )] 4- (Ia), where

[0176] (R 1 R 2 R 3 ), (R 1' R 2' R 3' ), (R 1” R 2” R 3” ) and (R 1”' R 2”' R 3”' Each is selected from the definition given in one row of Table 1 below:

[0177] Table 1

[0178]

[0179]

[0180]

[0181]

[0182] Another object of the present invention is an electronic component comprising at least one compound of general formula (I).

[0183] Ce 4+ (L1L2L3L4) 4- (I), where

[0184] in

[0185] L1, L2, L3, and L4 are independently selected from bidentate ligands having the general formula (II).

[0186] in

[0187] Y represents N or CR 3 ;

[0188] R 1 Represents CFR a R b tert-butyl, adamantyl, C2F5, n-C3F7, C3-C7-cycloalkyl, phenyl, naphthyl, pyridinyl, pyrimidinyl, triazine, among which

[0189] The cycloalkyl group is either unsubstituted or substituted with 1 to 13 groups selected from fluorine and CF3.

[0190] The phenyl group is substituted with at least one group selected from NO2, CN, F, Cl, Br, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2.

[0191] The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from CN, NO2, F, Cl, Br, C1-C4-haloalkyl, OCF3, SCF3, SO2CF3, N=C(CF3)2, SF5, and N(SO2CF3)2.

[0192] The pyridyl, pyrimidinyl, and triazine groups are substituted by at least one group selected from NO2, CN, F, Cl, Br, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2, and N(SO2CF3)2; or

[0193] R 1Together with Y and the CO- group to which they are bonded (especially the carbon atom of the CO- group), they form a 5- to 7-membered ring that may have a C=O or C(CH3)2 group as a ring member, and said 5- to 7-membered ring is fused with a phenyl group, wherein the fused phenyl group is unsubstituted or substituented by 1, 2, 3 or 4 R groups. 4 replace;

[0194] R 2 Represents CFR a R b tert-butyl, adamantyl, C2F5, n-C3F7, C3-C7-cycloalkyl, phenyl, naphthyl, pyridyl, pyrimidinyl, triazine, among which

[0195] The cycloalkyl group is either unsubstituted or substituted with 1 to 13 groups selected from fluorine and CF3.

[0196] The phenyl group is substituted with at least one group selected from NO2, CN, F, Cl, Br, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2.

[0197] The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from CN, NO2, F, Cl, Br, C1-C4-haloalkyl, OCF3, SCF3, SO2CF3, N=C(CF3)2, SF5, and N(SO2CF3)2.

[0198] The pyridyl, pyrimidinyl, and triazine groups are substituted by at least one group selected from NO2, CN, F, Cl, Br, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2, and N(SO2CF3)2; or

[0199] R 2 Together with Y and the CO- group to which they are bonded (especially the carbon atom of the CO- group), they form a 5- to 7-membered ring that may have a C=O or C(CH3)2 group as a ring member, and said 5- to 7-membered ring is fused with a phenyl group, wherein the fused phenyl group is unsubstituted or substituented by 1, 2, 3 or 4 R groups. 4 replace;

[0200] R a and R b Each of these elements independently represents halogen, CF3, CN, and C6-C. 14 -aryl, which is unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4-haloalkyl, C1-C4-haloalkoxy, SCF3, SO2CF3, NO2, N=C(CF3)2, SF5, N(SO2CF3)2 and CN;

[0201] R 3 Represents hydrogen, F, Cl, CN, CF3, OCF3, SCF3, methyl, ethyl, tert-butyl, adamantyl, phenyl, or a heteroaryl group having 4 to 5 carbon atoms, wherein the heteroaryl group has 1, 2, or 3 nitrogen atoms as ring members, and wherein the phenyl and heteroaryl groups are unsubstituted or surrounded by 1 or 2 identical or different groups R. 5 replace;

[0202] R 4 Represents CN, NO2, SF5, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio, C1-C4-haloalkylsulfonyl, N=C(CF3)2 and N(SO2CF3)2;

[0203] R 5 Representing CN, F, Cl, CF3, OCF3, SCF3, SO2CF3, NO2, N=C(CF3)2, SF5, and N(SO2CF3)2.

[0204] The condition is that it does not include the electronic components of compounds containing formula (Ia), Ce 4+ [(R 1 -C(-O)=C(R 3 )-C(=O)-R 2 (R) 1' -C(-O)=C(R 3’ )-C(=O)-R 2’ (R) 1” -C(-O)=C(R 3” )-C(=O)-R 2” (R) 1”’ C(-O)=C(R 3”’ )-C(=O)-R 2”’ )] 4 -(Ia), where

[0205] (R 1 R 2 R 3 ), (R 1’ R 2’ R 3’ ), (R 1” R 2” R 3” ) and (R 1”’ R 2”’ R 3”’ () is defined in Table 1 above.

[0206] part

[0207] In this invention, electronic components are understood as discrete or integrated electronic components that utilize the properties of compounds of general formula (I) or semiconductor matrix materials containing compounds of general formula (I). In one specific embodiment, the electronic component has a layer structure comprising 2, 3, 4, 5, 6, 7 or more layers, wherein at least one layer contains at least one compound of general formula (I). Each layer may also contain inorganic materials, or the component may also comprise layers composed entirely of inorganic materials.

[0208] 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 photoreceptors, light-emitting electrochemical cells (LECs), and organic laser diodes. Organic field-effect transistors (OFETs) are preferably organic thin-film transistors (OTFTs). Organic electroluminescent devices are preferably organic light-emitting diodes (OLEDs). Organic solar cells are preferably exciton solar cells, dye-sensitized solar cells (DSSCs), or perovskite solar cells. Electrophotographic devices are preferably photoconductive materials in organic photoconductors (OPCs).

[0209] Preferably, the electronic component according to the invention is an organic light-emitting diode, an organic photodetector, an organic solar cell, a photovoltaic cell, an organic diode, or an organic transistor, preferably in the form of a field-effect transistor, a thin-film transistor, or a perovskite solar cell.

[0210] The electronic component is preferably in the form of an organic light-emitting device, particularly an organic light-emitting diode (OLED). An organic light-emitting device comprises a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also include other layers, such as 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. An intermediate layer having, for example, exciton blocking functionality may also be interposed between two light-emitting layers. Not all of these layers are necessary.

[0211] A preferred embodiment is an electronic component, particularly in the form of an OLED, wherein the layer comprising the compound of formula (I) is a hole transport layer or a hole injection layer. In particular, electronic components, especially in the form of OLEDs, wherein the layer comprising the compound of formula (I) is a hole transport layer, a hole injection layer, or an electron blocking layer. Typically, the hole injection layer is a layer that facilitates the injection of electrons from the anode into the 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.

[0212] A preferred embodiment is an electronic component in the form of an organic photodetector unit. Typically, an organic photodetector is layered and generally comprises at least the following layers: a filter, an anode, at least one photoactive layer, and a cathode. These layers are typically applied to a substrate commonly used for this purpose. The photoactive region of the photodetector may comprise two layers, each having a uniform composition and forming a flat donor-acceptor heterojunction. The photoactive region may also comprise a hybrid layer and form a donor-acceptor heterojunction in the form of a donor-acceptor bulk heterojunction. In addition to these layers, the organic photodetector unit may also comprise other layers, such as those selected from...

[0213] - A layer with electron transport layer properties (electron transport layer, ETL).

[0214] - Layers containing hole-conducting materials (hole transport layers, HTLs) that do not need to absorb radiation.

[0215] A preferred embodiment is an electronic component in the form of an organic solar cell. Typically, 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 typically applied to a substrate commonly used for this purpose. The photoactive region of the solar cell may comprise two layers, each having a uniform 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 bulk donor-acceptor heterojunction. In addition to these layers, the organic solar cell may also comprise other layers, such as those selected from...

[0216] - A layer with electron transport layer properties (electron transport layer, ETL).

[0217] - Layers containing hole-conducting materials (hole transport layers, HTLs) that do not need to absorb radiation.

[0218] Another preferred embodiment is an electronic component in the form of an organic solar cell, wherein the layer of the compound of formula (I) has electronic conductivity properties (electron transport layer, ETL).

[0219] One specific embodiment is an electronic component, particularly in the form of an organic solar cell, wherein a layer comprising at least one compound of formula (I) is part of a pn-junction connecting a light-absorbing unit to another light-absorbing unit in a series device or a multi-stack device and / or part of a pn-junction connecting a cathode or anode to a light-absorbing unit.

[0220] Semiconductor matrix materials

[0221] The compounds of formula (I) according to the present invention, as well as their charge-transfer complexes and their reduction products, can be used as dopants in organic semiconductor matrix materials, particularly as p-type dopants in hole transport layers. The doped semiconductor matrix material preferably comprises at least one electron donor and at least one compound of formula (I) as defined above. The electron donor is preferably selected from…

[0222] 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′-Tetra(4-methoxy-phenyl)benzidine (MeO-TPD), (2,2′,7,7′-Tetra-(N,N-diphenylamino)-9,9′-spirodifluorene (spiro-TTB), N,N′-bis(naphth-1-yl)-N,N′-bis(phenyl)benzidine, N,N′-bis(naphth-1-yl)- N,N′-bis(phenyl)-9,9-spirodifluorene, 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-spirodifluorene, 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 ...-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene]-[4,1-phenylene] ,9-Dimethyl-fluorene-2-yl)amino]phenyl}benzene, tris(terphenyl-4-yl)amine, diaminotriphenylene, diaminotrimethylphenylindane, 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′-tetra(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′-spirobis[fluorene]-2-amine, (2,7-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobis[9H-fluorene](spiro-MeO-TPD), 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.

[0223] The appropriate description of diaminoterphenyl is in DE 102012007795.

[0224] Diaminotrimethylphenylindene is described in WO 2018 / 206769.

[0225] Di-, tri-, and tetraphenylindanamine derivatives are described in WO2020094847.

[0226] Specifically, the electron donor is selected from 4,4',4″-tris(N-(2-naphthyl)-N-phenyl-amino)triphenylamine (2-TNATA), 4,4',4″-tris(N-3-methylphenyl-N-phenyl-amino)triphenylamine (m-MTDATA), N,N,N',N'-tetra(4-methoxy-phenyl)benzidine (MeO-TPD), (2,2',7,7'-tetra-(N,N-diphenylamino)-9,9'-spirodifluorene (spiro-TTB), N,N'-bis(naphth-1-yl)-N,N'-bis(phenyl)benzidine, N,N'-bis(naphth-1-yl)-N,N'-bis(phenyl)-9,9-spirodifluorene, 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-spirodifluorene, 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, tris(triphenyl-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′-spirobis[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-Dimethyl-9H-fluorene-2-yl)-9,9′-spirobis[fluorene]-2-amine, N-(4-(6-(dibenzo[b,d]furan-2-yl(9,9-dimethyl-9H-fluorene-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluorene-2-yl)dibenzo[b,d]furan-2-amine, 9-(4-(6-(9H-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-methoxy) 3-(4-(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-diphenylphenyl-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-inden-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-inden-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) (9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluoren-2-amine, N,N'-bis(9,9-dimethyl-fluoren-2-yl)-N,N'-diphenyl-benzidine (BF-DPB), N,N'-((9H-fluoren-9,9-diyl)bis(4,1-phenylene))bis(N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4-amine)(BPAPF), N4,N4,N4',N4'-tetra(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-fluorene-2-yl)-9,9′-spirobis[fluorene]-2-amine, (2,7-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobis[9H-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-di A mixture of methyl-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, N-([1,1′-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine, and mixtures thereof.

[0227] Of course, other suitable organic semiconductor matrix materials can also be used, especially hole-conducting materials with semiconductor properties.

[0228] Doping

[0229] Doping can be carried out, particularly in such a way that the molar ratio of the matrix molecules to the compound of formula (I) is 10000:1 to 1:1, preferably 1000:1 to 2:1, especially 5:1 to 100:1.

[0230] Preparation of doped semiconductor matrix materials

[0231] Doping a specific matrix material (hereinafter also referred to as the hole-conducting matrix HT) with a compound of general formula (I) according to the present invention can be carried out by one or a combination of the following methods:

[0232] a) Evaporate in a vacuum using an HT source and at least one compound source of general formula (I).

[0233] b) Sequentially deposit HT and at least one compound of general formula (I), followed by inward diffusion of dopants through thermal treatment.

[0234] c) The HT layer is doped with a solution of at least one compound of general formula (I), followed by evaporation of the solvent by heat treatment.

[0235] d) Surface doping of the HT layer by applying a layer of at least one compound of general formula (I) to one or both surfaces of the HT layer.

[0236] e) Prepare a solution of a host and at least one compound of general formula (I), and form a film from the solution, for example by coating, casting or printing techniques or other film preparation techniques known to those skilled in the art.

[0237] Another object of the present invention is the use of the compound (I) or mixtures thereof as defined above, as follows:

[0238] -As an organic semiconductor

[0239] - As a redox dopant in organic semiconductor matrix materials, especially as a p-type dopant in hole transport layers.

[0240] -As an electron transport material

[0241] - As a charge injector in the charge injection layer

[0242] - As a cathode material in organic battery packs.

[0243] - As an electrochromic material.

[0244] Another object of the present invention is the use of Ce(III)-complex anions obtained by reducing the compound (I) as defined above or the charge-transfer complex of the compound (I) as defined above, together with an electron donor, as organic semiconductors or as electrochromic materials.

[0245] The following examples illustrate the invention but do not limit it in any way. Example

[0246] abbreviation:

[0247] TBME tert-butyl methyl ether

[0248] MTBE (methyl tert-butyl ether)

[0249] DCM dichloromethane

[0250] DME 1,2-dimethoxyethane

[0251] Spiro-TTB 2,2',7,7'-tetra-(N,N-diphenylamino)-9,9'-spirodifluorene

[0252] MeO-TPD N,N,N′,N′-Tetra(4-methoxy-phenyl)benzidine

[0253] Spiro-TAD 2,2′,7,7′-tetra(N,N-diphenylamino)-2,7-diamino-9,9-spirodifluorene

[0254] BPAPF N,N′-((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(N-([1,1′-biphenyl]-4-

[0255] )-[1,1′-biphenyl]-4-amine

[0256] Al (aluminum)

[0257] BPhen 4,7-diphenyl-1,10-phenanthroline

[0258] Cs

[0259] BAlq2 bis-(8-hydroxy-2-methylquinoline)-(4-phenylphenoxy)-aluminum

[0260] TPBI 2,2′,2″-(1,3,5-phenyltriyl)-tris(1-phenyl-1-H-benzimidazole)

[0261] PPy (Polypyrrole)

[0262] acac acetylacetone

[0263] TAPC 1,1-bis[(di-,4-tolylamino)phenyl]cyclohexane

[0264] ITO (Inert Tin Oxide)

[0265] EQE external quantum efficiency

[0266] PE power efficiency

[0267] nd Undefined / Unmeasured

[0268] Example 1:

[0269]

[0270] Ligands:

[0271] NaOMe (4 g, 73.1 mmol) was suspended in TBME (50 mL) containing ethyl heptafluorobutyrate (20 g, 82.6 mmol) and cooled to 0 °C. 1-(3,5-bis(trifluoromethyl)phenyl)ethyl-1-one (16.3 g, 63.6 mmol) was added dropwise to TBME (20 mL) over 30 minutes. The mixture was warmed to room temperature and stirred overnight. HCl (1 M, 80 mL) was added. The organic phase was separated and washed with saturated NaCl. The organic phase was dried over MgSO4, filtered, and volatiles were removed under vacuum. The crude diketone was distilled. The product was given as a pale yellow liquid (23 g, 80%).

[0272] Complexes:

[0273] NaOMe (762 mg, 73.1 mmol) was added to a solution of 1-(3,5-bis(trifluoromethyl)phenyl)-6,6,6,6,6,6,6-heptafluoro-1,3-dione (6.4 g, 14.1 mmol) in EtOH (50 mL). The solution was stirred for 5 minutes, and then a solution of cerium ammonium nitrate (1.93 g, 3.5 mmol) in EtOH (40 mL) was added. The deep red solution was stirred for 15 minutes, and then water (250 mL) and diethyl ether (250 mL) were added. The organic phase was separated, dried over MgSO4, and rotary evaporated under reduced pressure. The red oily material was prepared in hexane (50 mL), which crystallized as a deep red microcrystalline material (4.79 g, 70%). APCI-MS: 1945 [M+H]

[0274] Melting point: 140℃ (peak value) as determined by DSC at 10K / min.

[0275] Decomposition point: 261℃ (initial) as determined by DSC at 10K / min.

[0276] Cyclic voltammetry in acetonitrile yields the following potentials:

[0277] E 1 / 2 (vs.Fc / Fc+(MeCN): = +0.35V)

[0278] Compound 1 was co-evaporated with the hole transport material N,N′-((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(N-([1,1′-biphenyl]-4-yl)-[1,1′-biphenyl]-4-amine)(BPAPF).

[0279] Achieving 7.0·10 at a doping concentration of 5 mol% -5 Conductivity in S / cm.

[0280] Example 2:

[0281]

[0282] Ligands:

[0283] NaOMe (3.9 g, 72.8 mmol) was suspended in TBME (100 mL) and cooled to 0 °C. 2-chloro-2,2-difluoroethyl acetate (15 g, 94.6 mmol) and 1-(3,5-bis(trifluoromethyl)phenyl)ethyl-1-one (18.6 g, 72.8 mmol) were added dropwise to TBME (100 mL) over 30 minutes. After stirring at 0 °C for 15 minutes, HCl (1 M, 75 mL, 75 mmol) was added. The organic phase was separated and washed with saturated NaCl. The organic phase was dried (Na₂SO₄), filtered, and volatiles were removed under vacuum. The residue was distilled (108 °C, 8 mbar). The product was given as a colorless liquid (16.0 g, 43.4 mmol). APCI-MS: 369 [M+H].

[0284] Complexes:

[0285] 1-(3,5-bis(trifluoromethyl)phenyl)-4-chloro-4,4-difluorobut-1,3-dione (15.9 g, 43.1 mmol) was dissolved in TBME (100 mL) and cooled to 0 °C. NaH (0.93 g, 38.8 mmol) was added in small portions. A white precipitate formed and was filtered. 12.02 g of white solid was obtained. The white solid was dissolved in acetonitrile (50 mL) and cooled to 0 °C. Cerium ammonium nitrate (4.21 g, 7.68 mmol) was added and the suspension was stirred for 30 minutes. The suspension was filtered, washed with acetonitrile, and the filtrate was collected. Volatile substances were removed under vacuum, and the residue separated between n-octane and water. The suspension was filtered, and recrystallization from acetonitrile (-20 °C) yielded a red crystalline solid. mp 149 °C APCI-MS: 1610 [M+].

[0286] Melting point: 148℃ (peak value) as determined by DSC at 10K / min.

[0287] Decomposition point: 235℃ (initial) as determined by DSC at 10K / min.

[0288] Cyclic voltammetry in acetonitrile yields the following potentials:

[0289] E 1 / 2 (vs.Fc / Fc+(MeCN): = +0.39V)

[0290] Compound 2 was co-evaporated with the hole transport material N,N'-bis(9,9-dimethylfluorene-2-yl)-N,N'-diphenylbenzidine (BF-DPB).

[0291] At a doping concentration of 2.5 mol%, 2.1·10 has been achieved. -5 Conductivity in S / cm.

[0292] At a doping concentration of 5 mol%, 4.1·10 has been achieved. -5 Conductivity in S / cm.

[0293] Example 3:

[0294]

[0295] Ligands:

[0296] NaOMe (1.23 g, 22.8 mmol) was suspended in TBME (25 mL) containing ethyl heptafluorobutyrate (6.3 g, 26 mmol) and cooled to 0 °C. 1-(4-fluoro-3-(trifluoromethyl)phenyl)ethyl ketone (4.1 g, 20 mmol) was added dropwise to TBME (25 mL) over 30 minutes. The mixture was warmed to room temperature and stirred overnight. HCl (1 M, 25 mL) was added. The organic phase was separated and washed with saturated NaCl. The organic phase was dried over MgSO4, filtered, and volatiles were removed under vacuum. The crude diketone was distilled. The product was given as a colorless liquid (7.6 g, 95%).

[0297] Complexes:

[0298] 1-(4-fluoro-3-(trifluoromethyl)phenyl)-6,6,6,6,6,6,6-heptafluoro-1,3-dione (3.4 g, 8.6 mmol) was dissolved in EtOH (50 mL), and then EtONa (590 mg, 8.6 mmol) was added. The mixture was stirred for 5 minutes, and then cerium ammonium nitrate (1.19 g, 2.15 mmol) was added. The deep red solution was stirred for 15 minutes. The volatiles were then removed under vacuum, and the residue was redissolved in diethyl ether (100 mL) and washed with water (3 x 100 mL). The organic phase was then dried over MgSO4 and evaporated under reduced pressure. The crude complex (2 g, 53%) was recrystallized from hexane / chloroform (1:1).

[0299] Melting point: 132℃ (peak value) as determined by DSC at 10K / min.

[0300] Decomposition point: 267℃ (initial) as determined by DSC at 10K / min.

[0301] Cyclic voltammetry in acetonitrile yields the following potentials:

[0302] E 1 / 2 (vs.Fc / Fc+(MeCN): = +0.35V)

[0303] Compound 3 was co-evaporated with the hole transport material N,N'-bis(9,9-dimethylfluorene-2-yl)-N,N'-diphenylbenzidine (BF-DPB).

[0304] At a doping concentration of 2.1 mol%, 4.1·10 has been achieved. -5 Conductivity in S / cm.

[0305] At a doping concentration of 5.5 mol%, 7.0·10 has been achieved. -5 Conductivity in S / cm.

[0306] Example 4:

[0307]

[0308] Ligands:

[0309] Ethyl heptafluorobutyrate (8.5 g, 35.2 mmol) was dissolved in MTBE (30 mL) and cooled to 0 °C. After 30 minutes, 1-(4-chloro-3-(trifluoromethyl)phenyl)ethyl-1-one (6.02 g, 27.1 mmol) was added to MTBE (30 mL) and stirring continued for another 30 minutes. The reaction mixture was quenched with HCl (1 M, 40 mL, 40 mmol) and the organic phase was separated. The organic phase was washed with water and saturated NaCl and dried (MgSO4), filtered, and volatiles were removed under vacuum. The residue was distilled (120 °C, 18 mbar). A colorless liquid (8.4 g, 20.7 mmol) was obtained. APCI-MS: 419 [M+H].

[0310] Complexes:

[0311] 1-(4-chloro-3-(trifluoromethyl)phenyl)-heptafluoro-1,3-dione (4.00 g, 9.6 mmol) was dissolved in TBME (20 mL) and cooled to 0 °C. NaH (0.23 g, 9.6 mmol) was added aliquots, and volatiles were removed under vacuum. The residue was dissolved in acetonitrile (20 mL), cooled to 0 °C, and cerium ammonium nitrate (1.27 g, 2.33 mmol) was added. After 15 minutes, the suspension was filtered, and the filtrate was collected. Volatiles were removed, and the residue was dissolved in hexane / TBME (5:1), washed with water and saturated NaCl. The organic phase was dried (MgSO4), filtered, concentrated, and cooled to -20 °C. Red crystals were collected by filtration and recrystallized from hexane / toluene. Red powder, (1.8 g, 0.99 mmol) APCI-MS: 1814.

[0312] Melting point: 152℃ (peak value) as determined by DSC at 10K / min.

[0313] Decomposition point: 240℃ (initial) as determined by DSC at 10K / min.

[0314] Cyclic voltammetry in acetonitrile yields the following potentials:

[0315] E1 / 2(vs.Fc / Fc+(MeCN):=+0.32V

[0316] Compound 4 was co-evaporated with the hole transport material N4,N4,N4′,N4′-tetra(9,9-dimethyl-9H-fluorene-2-yl)-[1,1′-biphenyl]-4,4′-diamine (TDMFB).

[0317] At a doping concentration of 5.5 mol%, 8.2·10 has been achieved. -5 Conductivity in S / cm.

[0318] Example 5:

[0319]

[0320] Ligands:

[0321] 1,3-Dehydroadamantane (1.9 g, 14.7 mmol) was dissolved in diethyl ether (10 mL) and added to a solution of 4,4,5,5,5-pentafluoro-1-(4-(trifluoromethyl)phenyl)pentane-1,3-dione (4.92 g, 14.7 mmol) in diethyl ether (30 mL). The mixture was stirred overnight at room temperature. The solvent was then removed by rotation, and the resulting solid was prepared in hexane (10 mL) and then filtered. The microcrystalline material was dried under vacuum (3.78, 55%).

[0322] Complexes:

[0323] NaiH (120 mg, 5 mmol) was added to a solution of 2-((3r,5r,7r)-adamantane-1-yl)-4,4,5,5,5-pentafluoro-1-(4-(trifluoromethyl)phenyl)pentane-1,3-dione (2.34 g, 5 mmol) in TBME (15 mL). After 5 minutes, the solvent was removed by vortexing, and the oily residue was dissolved in MeCN (15 mL). Cerium ammonium nitrate (685 mg, 1.25 mmol) was added, and the mixture was stirred for 30 minutes. The red solution was then filtered, and the solvent was removed by vortexing. The oily red solid was prepared in hexane (10 mL), filtered, washed with hexane (5 mL), and dried under vacuum. The product was obtained as a red powder (937 mg, 37%).

[0324] Melting point: 162℃ (peak value) as determined by DSC at 10K / min.

[0325] Decomposition point: 180℃ (initial) as determined by DSC at 10K / min.

[0326] Cyclic voltammetry in acetonitrile yields the following potentials:

[0327] E1 / 2 (vs.Fc / Fc+(MeCN): = +0.30V)

[0328] Example 6:

[0329]

[0330] Ligands:

[0331] Ethyl 2-(3,5-bis(trifluoromethyl)phenyl)-2,2-difluoroacetate was synthesized according to Angew. Chem. Int. Ed. 2018, 57, 12819-12823.

[0332] Ethyl 2-(3,5-bis(trifluoromethyl)phenyl)-2,2-difluoroacetate (4.5 g, 13.4 mmol) was dissolved in TBME (25 mL) and the solution was cooled to 0 °C. NaOMe (0.72 g, 13.4 mmol) was added, and after 30 minutes, 1-(3,5-bis(trifluoromethyl)phenyl)ethyl-1-one (3.42 g, 13.4 mmol) dissolved in TBME (25 mL) was added to the suspension. The evaporator was evaporated under a stream of N2, and the residue was suspended in HCl (1 M, 200 mL, 200 mmol). The suspension was filtered, the white solid was washed with water, and dried under vacuum. A grayish-white solid, 6.42 g. APCI-MS: 546 [M+].

[0333] Complexes:

[0334] 1,4-bis(3,5-bis(trifluoromethyl)phenyl)-4,4-difluorobut-1,3-dione (3.00 g, 5.5 mmol) was dissolved in TBME (25 mL) and NaH (0.13 g, 5.5 mmol) was added. After gas escaping ceased, the volatiles were removed under vacuum, and the residue was dissolved in acetonitrile (25 mL). Cerium ammonium nitrate (0.76 g, 1.38 mmol) was added, and the suspension was stirred for 30 minutes. The suspension was filtered, and the filtrate was collected. The volatiles were removed under vacuum, and the residue was dissolved in hot petroleum ether and filtered. After cooling to -20 °C, the formed red crystals were collected. 1.89 g.

[0335] Melting point: 102℃ (peak value) as determined by DSC at 10K / min.

[0336] Decomposition point: 201℃ (initial) as determined by DSC at 10K / min.

[0337] Cyclic voltammetry in acetonitrile yields the following potentials:

[0338] E 1 / 2 (vs.Fc / Fc+(MeCN): = +0.40V)

[0339] Example 7:

[0340]

[0341] Ligands:

[0342] Trimethylacetyl acetonitrile (10 g, 80 mmol) in 20 mL of toluene was added dropwise to a suspension of NaH (3.9 g, 160 mmol) in 20 mL of toluene at 0 °C. After addition, the mixture was warmed to room temperature and stirred for 2 hours. 3′,5′-bis(trifluoromethyl)benzoyl chloride (22 g, 80 mmol) was added and the mixture was stirred overnight. HCl (1 M, 100 mL) was then added and the reaction mixture was extracted with 500 mL of EtOAc. The organic phase was washed with water and brine, dried over MgSO4, and evaporated under reduced pressure. The crude material was recrystallized from hot hexane (15.9 g, 42%). APCI-MS: 366 [M+H].

[0343] Complexes:

[0344] 2-(3,5-bis(trifluoromethyl)benzoyl)-4,4-dimethyl-3-oxopentanonitrile (3.00 g, 8.22 mmol) was dissolved in TBME (30 mL), and NaH (0.197 g, 8.22 mmol) was added aliquots at 0 °C. After stirring for 30 min, all volatiles were removed under vacuum. The oily residue was dissolved in acetonitrile (30 mL), and cerium ammonium nitrate (1.06 g, 1.93 mmol) was added at 0 °C. After 30 min, the red solution was filtered and the filtrate was collected. Volatiles were removed under vacuum, and the residue was prepared with hot heptane and filtered while hot. After cooling to -20 °C, deep red crystals formed, which were collected by filtration. 1.54 g, mp 204 °C APCI-MS: 1596 [M] + ].

[0345] Melting point: 204℃ (peak value) as determined by DSC at 10K / min.

[0346] Decomposition point: 229℃ (initial) as determined by DSC at 10K / min.

[0347] Cyclic voltammetry in acetonitrile yields the following potentials:

[0348] E 1 / 2 (vs.Fc / Fc+(MeCN): = +0.31V)

[0349] Example 8:

[0350]

[0351] Ligands:

[0352] NaOMe (3.5 g, 64.5 mmol) was suspended in TBME (50 mL) containing ethyl trifluoroacetate (10.3 g, 73 mmol) and cooled to 0 °C. 3′,4′,5′,6,-pentafluoroacetophenone (11.8 g, 56.1 mmol) was added dropwise to TBME (20 mL) over 30 minutes. The mixture was warmed to room temperature and stirred for 2 hours. HCl (1 M, 75 mL) was added. The organic phase was separated and washed with saturated NaCl. The organic phase was dried over MgSO4, filtered, and volatiles were removed under vacuum. The product was obtained as a pale yellow liquid (8.4 g, 49%).

[0353] Complexes:

[0354] NaH (390 mg, 16.3 mmol) was added to a solution of 4,4,4-trifluoro-1-(2,3,4,5,6-pentafluorophenyl)but-1,3-dione (5 g, 16.3 mmol) in 50 mL of TBME. The mixture was stirred for 10 min, and then the solvent was removed by rotary evaporation. The oily residue was redissolved in acetonitrile (40 mL), and then cerium ammonium nitrate (2.2 g, 4 mmol) was added. The mixture was stirred for 20 min, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude complex was extracted with hexane (20 mL) and then rotary evaporated. The product was obtained as a very viscous red liquid (4.8 g, 85%).

[0355] Cyclic voltammetry in acetonitrile yields the following potentials:

[0356] E 1 / 2 (vs.Fc / Fc+(MeCN): = +0.51V)

[0357] Example 9:

[0358]

[0359] Ligands:

[0360] 1-(bromomethyl)-3,5-bis(trifluoromethyl)benzene (20 g, 72.3 mmol), Pd(PPh3)2C12 (1.53 g, 2.18 mmol), and activated Zn (9.46 g, 144.6 mmol) were suspended in DME, and the suspension was cooled to 0 °C. After 30 minutes, 3,5-bis(trifluoromethyl)benzoyl chloride (22.2 g, 72.3 mmol) dissolved in 100 mL of DME was added, and the solution was allowed to reach room temperature. Stirring was continued for 12 hours, and saturated NH4Cl was added. The suspension was extracted with diethyl ether, and the phase was separated. The organic phase was washed with Na2CO3 (10% wt.), followed by two washes with water and saturated NaHCO3. The organic phase was dried (Na2SO4), filtered, and volatiles were removed under vacuum. The residue was recrystallized from heptane. 6.1 g of grayish-white crystals were obtained. APCI-MS: 469 [M+H].

[0361] Hexamethyldisilazane (2.1 g, 13.0 mmol) was dissolved in toluene (40 mL) and cooled to 0 °C. n-BuLi (1.6 M, 12.8 mmol, 8 mL) was added dropwise to hexane, and after complete addition, 1,2-bis(3,5-bis(trifluoromethyl)phenyl)ethyl-1-one (3 g, 4.3 mmol) was added. The solution was warmed to room temperature and stirred for 12 hours. Acetic acid (20 mL) was added, and the reaction mixture was diluted with water. The organic phase was separated and washed twice with water. The organic phase was dried (MgSO4), filtered, and volatiles were removed under vacuum. The residue was recrystallized from octane and then recrystallized a second time from EtOH:H2O6:1. 2.60 g, 3.7 mmol. APCI-MS: 708 [M+]. Complex:

[0362] 1,2,3-Tris(3,5-bis(trifluoromethyl)phenyl)prop-1,3-dione (2.43 g, 3.43 mmol) was dissolved in THF (25 mL), and then NaH (123 mg, 5.14 mmol) was added. The solid was filtered off and hexane was added to the filtrate. All volatiles were removed under vacuum. The residue was dissolved in a minimal amount of diethyl ether and diluted with hexane. After concentration, the resulting crystals (2.13 g) were collected by filtration. The white solid was dissolved in acetonitrile (20 mL) and cooled to 0 °C. Cerium ammonium nitrate (372 mg, 0.678 mmol) was added and the mixture was cooled to -20 °C. The suspension was filtered off and volatiles were removed under vacuum. 25 mg of red crystals were obtained by crystallization from toluene / hexane.

[0363] Melting point: 227℃ (peak value) as determined by DSC at 10K / min.

[0364] Decomposition point: 271℃ (initial) as determined by DSC at 10K / min.

[0365] Cyclic voltammetry in acetonitrile yields the following potentials:

[0366] E 1 / 2 (vs.Fc / Fc+(MeCN): = +0.38V)

[0367] Synthesis of 10:

[0368]

[0369] 4,4,4-trifluoro-1-(naphth-2-yl)but-1,3-dione is commercially available.

[0370] 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione (2.5 g, 9.4 mmol) was dissolved in EtOH (50 mL), and then NaOEt (640 mg, 9.4 mmol) was added. The mixture was stirred for 5 minutes, and then cerium ammonium nitrate (1.28 g, 2.3 mmol) was added. The deep red solution was stirred for 15 minutes and filtered. The volatiles were removed under vacuum, and the residue was redissolved in DCM (300 mL) and washed with water (100 mL). The organic phase was then dried over MgSO4 and evaporated under reduced pressure. The crude complex was recrystallized from hexane / chloroform (1:1) at -20 °C (1.27 g, 45%). APCI-MS: 1197 [M+H].

[0371] Melting point: 133℃ (peak value) as determined by DSC at 10K / min.

[0372] Decomposition point: 214℃ (initial) as determined by DSC at 10K / min.

[0373] Cyclic voltammetry in acetonitrile yields the following potentials:

[0374] E 1 / 2 (vs.Fc / Fc+(MeCN): = +0.24V)

[0375] Synthesis of 11:

[0376]

[0377] Ligands:

[0378] Tetrahydronaphthyl ketone (10 g, 68.4 mmol) was dissolved in TBME and added to a solution of ethyl pentafluoropropionate (17 g, 88.9 mmol) and NaOMe (3.7 g, 68.4 mmol) at 0 °C for 45 min. Stirring was continued for 30 min, followed by the addition of HCl (1 M, 70 mL, 70 mmol). The phase was separated, and the organic phase was washed with water and concentrated NaCl. The organic phase was dried (MgSO4), filtered, and volatiles were removed under vacuum. The oily residue was crystallized from petroleum ether (-20 °C). 8.5 g white solid. MPa 45 °C. APCI-MS: 293 [M+H].

[0379] Complexes:

[0380] 2-(pentafluoropropionyl)-3,4-dihydronaphthyl-1(2H)-one (3 g, 10.3 mmol) was dissolved in TBME (30 mL) and cooled to 0 °C. NaH (0.25 g, 10.3 mmol) was added in small portions, and volatiles were removed under vacuum. The residue was dissolved in acetonitrile (30 mL), cooled to 0 °C, and cerium ammonium nitrate (1.41 g, 2.58 mmol) was added. Stirring was continued for 1 hour, and the suspension was filtered. The filtrate was collected, and volatiles were removed under vacuum. The residue was crystallized from n-octane / toluene. 1.30 g APCI-MS: 1304 [M+].

[0381] Melting point: 142℃ (peak value) as determined by DSC at 10K / min.

[0382] Decomposition point: 220℃ (initial) as determined by DSC at 10K / min.

[0383] Cyclic voltammetry in acetonitrile yields the following potentials:

[0384] E 1 / 2 (vs.Fc / Fc+(MeCN): = +0.18V)

[0385] Example 12:

[0386]

[0387] Ligands:

[0388] The synthesis of 1-(4-(trifluoromethylsulfonyl)phenyl)ethyl-1-one was carried out according to Journal of Organic Chemistry, 2015, vol. 80, 15, 7658-7665.

[0389] Ethyl heptafluorobutyrate (3.18 g, 13.2 mmol) and NaOMe (0.52 g, 9.64 mmol) were dissolved in TBME (11 mL), and the reaction mixture was cooled to 0 °C. 1-(4-(trifluoromethylsulfonyl)phenyl)ethyl-1-one (2.21 g, 8.77 mmol) was dissolved in TBME (11 mL) and slowly added. After 15 minutes, the reaction mixture was diluted with 1 M HCl (10 mL), and then diluted with Et₂O and H₂O. The organic phase was separated and washed with H₂O and saturated NaCl. The organic phase was dried over MgSO₄, filtered, and volatiles were removed under vacuum. The residue was recrystallized from hexane to give the title product (3.00 g, 76%) as a yellow solid. APCI-MS 449 [M+H]⁺.

[0390] Complexes:

[0391] Heptafluoro-1-(4-((trifluoromethyl)sulfonyl)phenyl)-hex-4-yn-1,3-dione (3.00 g, 6.7 mmol) was dissolved in TBME (20 mL) and cooled to 0 °C. NaH (0.16 g, 6.7 mmol) was added. After gas evaporation ceased, the volatiles were removed under vacuum. The residue was dissolved in acetonitrile (20 mL) and cerium ammonium nitrate (0.91 g, 1.7 mmol) was added. After 30 min, the suspension was filtered, and the filtrate was dissolved in toluene / hexane (1:1). The organic phase was washed with water (2x) and saturated NaCl. The organic phase was dried over MgSO4, filtered, and the volatiles were removed under vacuum. The residue was recrystallized from DCM / petroleum ether to give the title product (1.29 g, 40%) as a red crystalline solid. APCI-MS: 1930 [M+].

[0392] Example 13:

[0393]

[0394] Ligand: 2-(4,4,4,4,4,4,4-heptafluoro-4λ) 8 (-But-2-ynyl)-2,3-dihydro-1H-indenolate

[0395] NaOMe (5.32 g, 98.5 mmol) was suspended in TBME (50 mL) containing ethyl heptafluorobutyrate (6.3 g, 26 mmol) and cooled to 0 °C. 1-Indanone (10 g, 75 mmol) was added dropwise to TBME (25 mL) over 30 minutes. The mixture was warmed to room temperature and stirred overnight. HCl (1 M, 100 mL) was added. The organic phase was separated and washed with saturated NaCl. The organic phase was dried over MgSO4, filtered, and volatiles were removed under vacuum. The crude diketone was distilled twice. The product was given as a colorless liquid (12.6 g, 51%).

[0396] Sodium diketone:

[0397] NaH (0.66 g, 0.66 mmol) was added to 2-(4,4,4,4,4,4,4-heptafluoro-4λ) at 0 °C. 8 (-But-2-acetylacetyl)-2,3-dihydro-1H-inden-1-one (7.5 g, 22.8 mmol) was in a solution of TBME (50 mL). After gas escaping ceased, the mixture was filtered. The filtrate was rotary evaporated under vacuum, and the oily residue was prepared in hexane. The product was obtained as a white solid (7.8 g, 98%).

[0398] Complexes:

[0399] 2-(4,4,4,4,4,4,4-heptafluoro-4λ) at 0℃ 8 Sodium 2,3-dihydro-1H-indanone (4 g, 11.4 mmol) was suspended in acetonitrile (50 mL). Cerium ammonium nitrate (1.56 g, 2.85 mmol) was added and the suspension was stirred for 30 minutes. The suspension was filtered and washed with water (50 mL) and hexane (50 mL). A deep purple crystalline solid was recrystallized from a hexane / diethyl ether mixture (1:1). (3.2 g, 77%)

[0400] Example 14:

[0401]

[0402] Ligands:

[0403] 1-(3-chloro-4-(trifluoromethyl)phenyl)-6,6,6,6,6,6,6-heptafluoro-6λ 8 -hex-4-ynyl-1,3-dione

[0404] NaOMe (1.68 g, 30.5 mmol) was suspended in 80 mL of TBME containing ethyl heptafluorobutyrate (7.4 g, 30.5 mmol) and cooled to 0 °C. 1-(3-chloro-4-(trifluoromethyl)phenyl)ethyl-1-one (5.22 g, 23.5 mmol) was added dropwise to 25 mL of TBME over 30 minutes. The mixture was warmed to room temperature and stirred for 2 hours. HCl (1 M, 30 mL) was added. The organic phase was separated and washed with saturated NaCl. The organic phase was dried over MgSO4, filtered, and volatiles were removed under vacuum. The crude diketone was distilled. The product was given as a colorless liquid (7.88 g, 80%).

[0405] Complexes:

[0406] At 0°C, 1-(3-chloro-4-(trifluoromethyl)phenyl)-6,6,6,6,6,6,6-heptafluoro-6λ 8 1,3-Hexyl-4-yne-1,3-dione (7.88 g, 18.85 mmol) was added to a cooled suspension of NaH (0.455 g, 18.9 mmol) in TBME (50 mL). After gas escaping ceased, the volatiles were removed under vacuum and the residue was dissolved in acetonitrile (20 mL). Cerium ammonium nitrate (2.58 g, 4.71 mmol) was added and the suspension was stirred for 30 min. The volatiles were removed and the residue was dissolved in diethyl ether (100 mL), washed with water and saturated NaCl. The organic phase was dried (MgSO4), filtered, and rotary evaporated. The red material was recrystallized from hexane (5.56 g, 65%).

[0407] Example 15:

[0408]

[0409] Ligands:

[0410] 1-(3-chloro-4-(trifluoromethyl)phenyl)-4,4,5,5,5-pentafluoropenta-1,3-dione

[0411] NaOMe (2.1 g, 38.2 mmol) was suspended in 50 mL of TBME containing ethyl pentafluoropropionate (7.33 g, 38.2 mmol) and cooled to 0 °C. 1-(3-chloro-4-(trifluoromethyl)phenyl)ethyl-1-one (6.54 g, 29.5 mmol) was added dropwise to 20 mL of TBME over 30 minutes. The mixture was warmed to room temperature and stirred for 1 hour. HCl (1 M, 40 mL) was added. The organic phase was separated and washed with saturated NaCl. The organic phase was dried over MgSO4, filtered, and volatiles were removed under vacuum. The crude diketone was distilled. The product was given as a colorless liquid (10.42 g, 96%).

[0412] Complexes:

[0413] A solution of 1-(3-chloro-4-(trifluoromethyl)phenyl)-4,4,5,5,5-pentafluoropenta-1,3-dione (8 g, 21.7 mmol) in TBME (20 mL) was added at 0 °C to a cooled suspension of NaH (0.52 g, 21.7 mmol) in TBME (20 mL). After gas escaping ceased, the volatiles were removed under vacuum and the residue was dissolved in acetonitrile (50 mL). Cerium ammonium nitrate (2.97 g, 5.4 mmol) was added and the suspension was stirred for 30 min. The volatiles were removed and the residue was dissolved in diethyl ether (100 mL), washed with water and saturated NaCl. The organic phase was dried (MgSO4), filtered, and rotary evaporated. The red oily material was sonicated in hexane. The resulting red solid recrystallized from hexane (3.4 g, 39%).

[0414] Example 16:

[0415]

[0416] Ligands:

[0417] 4,4,4-Trifluoro-1-(2,4,6-tris(trifluoromethyl)phenyl)but-1,3-dione

[0418] NaOMe (0.5 g, 9.4 mmol) was suspended in TBME (20 mL) containing ethyl trifluoroacetate (1.3 g, 9.4 mmol) and cooled to 0 °C. 1-(2,4,6-tris(trifluoromethyl)phenyl)ethyl-1-one (2.4 g, 7.4 mmol) was added dropwise to TBME (25 mL) over 30 minutes. The mixture was warmed to room temperature and stirred overnight. HCl (1 M, 15 mL) was added. The organic phase was separated and washed with saturated NaCl. The organic phase was dried over MgSO4, filtered, and volatiles were removed under vacuum. The crude diketone was distilled. The product was given as a colorless liquid (2.1 g, 67%).

[0419] Complexes:

[0420] 4,4,4-trifluoro-1-(2,4,6-tris(trifluoromethyl)phenyl)but-1,3-dione (2.1 g, 5 mmol) was added to a cooled suspension of NaH (0.12 g, 5 mmol) in TBME (20 mL) at 0 °C. After gas escaping ceased, the volatiles were removed under vacuum and the residue was dissolved in acetonitrile (25 mL). Cerium ammonium nitrate (0.68 g, 1.25 mmol) was added and the suspension was stirred for 30 min. The suspension was filtered and washed with water (50 mL). A red crystalline solid recrystallized from a mixture of hexane / dichloromethane (9:1) (0.6 g, 30%).

[0421] Melting point: 148℃ (peak value) as determined by DSC at 10K / min.

[0422] Decomposition point: 280℃ (initial) as determined by DSC at 10K / min.

[0423] Cyclic voltammetry in acetonitrile yields the following potentials:

[0424] E1 / 2(vs.Fc / Fc+(MeCN):=+0.6V

[0425] Example 17:

[0426]

[0427] Ligands:

[0428] 4,4,5,5,5-Pentafluoro-1-(4-fluoro-3-(trifluoromethyl)phenyl)pentapent-1,3-dione

[0429] NaOMe (1.4 g, 26 mmol) was suspended in TBME (50 mL) containing ethyl pentafluoropropionate (5 g, 26 mmol) and cooled to 0 °C. 1-(3-chloro-4-(trifluoromethyl)phenyl)ethyl-1-one (5.34 g, 26 mmol) was added dropwise to TBME (20 mL) over 30 minutes. The mixture was warmed to room temperature and stirred for 1 hour. HCl (1 M, 25 mL) was added. The organic phase was separated and washed with saturated NaCl. The organic phase was dried over MgSO4, filtered, and volatiles were removed under vacuum. The product was obtained as a pale yellow liquid (1.79 g, 20%).

[0430] Complexes:

[0431] 1.79 g (5.1 mmol) of 4,4,5,5,5-pentafluoro-1-(4-fluoro-3-(trifluoromethyl)phenyl)pentane-1,3-dione was dissolved in 50 mL of EtOH, followed by the addition of 1 M NaOH in 5.1 mL of EtOH. The mixture was stirred for 5 minutes, and then 0.69 g (1.27 mmol) of cerium ammonium nitrate was added. The deep red solution was stirred for 15 minutes. The volatiles were then removed under vacuum, and the residue was redissolved in diethyl ether (100 mL) and washed with water (3 x 100 mL). The organic phase was then dried over MgSO4 and evaporated under reduced pressure. The material was extracted in hexane, concentrated, and cooled to -20 °C. Red crystals were collected by filtration and dried under vacuum (0.8 g, 41%).

[0432] Sample preparation

[0433] Thin films and OLEDs were prepared by thermal evaporation at room temperature under ultra-high vacuum conditions (basal pressure <5×10-7 mbar) by controlling the evaporation rate using a quartz crystal microbalance (QCM).

[0434] Doped layers for conductivity measurement were prepared by co-deposition of the substrate and dopant, using two independent QCMs to control the evaporation rate. Films 30–50 nm thick with 10–20 wt% dopant were prepared on a glass substrate with a 50 nm thick gold electrode. The channel length was 100 μm. The samples were encapsulated with a glass cap and getter.

[0435] A bottom-emission OLED was fabricated by subsequently depositing an organic multilayer stack on a glass substrate with pre-patterned ITO electrodes (see page 5). A 100 nm layer of aluminum was deposited as the top electrode.

[0436] Measurement

[0437] Transverse conductivity was determined by current-voltage characteristics (-10V to 10V). The OLED was characterized in an integrating sphere using an SMU (Source Measure Unit) or current-driven and voltage measurements, along with photodiodes and a spectrometer, to investigate emission properties. Data are summarized in Table 1.

[0438] Table 1: Conductivity Measurement

[0439]

[0440] *Snaith, HJ (2021), Nature Materials 202120: 9, 20(9), 1248-1254.

[0441] OLED Measurement

[0442] The parameters and conditions are listed in Table 2.

[0443] Table 2:

[0444]

[0445] In the integrating sphere at 10mA / cm 2 The measurements were then taken. The results are listed in Table 3.

[0446] Table 3:

[0447]

Claims

1. Compounds of general formula (I) What 4+ (L1L2L3L4) 4- (I), in L1, L2, L3, and L4 are independently selected from bidentate ligands having the general formula (II). in Y represents CR 3 ; R 1 Represents CFR a R b C2F5, n-C3F7, phenyl, naphthyl, pyridyl, pyrimidinyl, triazine, among which The phenyl group is substituted by at least one group selected from F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2. The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from CN, NO2, F, Cl, Br, C1-C4-haloalkyl, OCF3, SCF3, SO2CF3, N=C(CF3)2, SF5, and N(SO2CF3)2. The pyridyl, pyrimidinyl, and triazine groups are substituted by at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2, and N(SO2CF3)2; or R 1 Together with the carbon atoms of the CO- groups to which they are bonded, Y forms a 5- to 7-membered ring, which may have a C=O or C(CH3)2 group as a ring member, and said 5- to 7-membered ring is fused with a phenyl group, wherein the fused phenyl group is unsubstituted or substituented by 1, 2, 3 or 4 R groups. 4 replace; R 2 Representing phenyl, naphthyl, pyridyl, pyrimidinyl, and triazine, among which The phenyl group is substituted by at least one group selected from F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2. The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from CN, NO2, F, Cl, Br, C1-C4-haloalkyl, OCF3, SCF3, SO2CF3, N=C(CF3)2, SF5, and N(SO2CF3)2. The pyridyl, pyrimidinyl, and triazine groups are substituted by at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2, and N(SO2CF3)2; or R 2 Together with the carbon atoms of the CO- groups to which they are bonded, Y forms a 5- to 7-membered ring, which may have a C=O or C(CH3)2 group as a ring member, and said 5- to 7-membered ring is fused with a phenyl group, wherein the fused phenyl group is unsubstituted or substituented by 1, 2, 3 or 4 R groups. 4 replace; R a and R b Each of these elements independently represents halogen, CF3, CN, and C6-C. 14 -aryl, which is unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4-haloalkyl, C1-C4-haloalkoxy, SCF3, SO2CF3, NO2, N=C(CF3)2, SF5, N(SO2CF3)2 and CN; R 3 Represents hydrogen, F, Cl, CN, CF3, OCF3, SCF3, methyl, ethyl, tert-butyl, adamantyl, phenyl, or a heteroaryl group having 4 to 5 carbon atoms, wherein the heteroaryl group has 1, 2, or 3 nitrogen atoms as ring members, and wherein the phenyl and heteroaryl groups are unsubstituted or surrounded by 1 or 2 identical or different groups R. 5 replace; R 4 Represents CN, NO2, SF5, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio, C1-C4-haloalkylsulfonyl, N=C(CF3)2 and N(SO2CF3)2; R 5 Representing CN, F, Cl, CF3, OCF3, SCF3, SO2CF3, NO2, N=C(CF3)2, SF5, and N(SO2CF3)2 The condition is that the compound does not include formula (Ia). Ce 4+ [(R 1 -C(-O)=C(R 3 )-C(=O)-R 2 )(R 1’ -C(-O)=C(R 3’ )-C(=O)-R 2’ )(R 1” -C(-O)=C(R 3” )-C(=O)-R 2” )(R 1’” -C(-O)=C(R 3”’ )-C(=O)-R 2”’ )] 4 -(I.a), wherein (R 1 R 2 R 3 ), (R 1’ R 2’ R 3’ ), (R 1” R 2” R 3” ) and (R 1”’ R 2”’ R 3”’ Each is selected from the definition given in one row of the table below:

2. The compound according to claim 1, wherein R 1 and R 2 Different meanings or If R 1 and R 2 Having the same meaning, R 1 and R 2 The group is selected from phenyl, wherein the phenyl group is substituted with at least one group selected from F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2, wherein R a It is F, and R b Selected from C6-C 14 -aryl, which is unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4-haloalkyl, C1-C4-haloalkoxy, SCF3, SO2CF3, NO2, N=C(CF3)2, SF5, N(SO2CF3)2 and CN.

3. The compound according to claim 1, wherein... R 1 Selected from CFR a R b C2F5 and n-C3F7 and R 2 Selected from phenyl, naphthyl, pyridyl, and pyrimidinyl, among which The phenyl group is substituted with at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2. The naphthyl group is either unsubstituted or substituted with 1 to 7 groups selected from CN, NO2, F, Cl, Br, C1-C4-haloalkyl, OCF3, SCF3, SO2CF3, N=C(CF3)2, SF5, and N(SO2CF3)2. The pyridyl and pyrimidinyl groups are substituted by at least one group selected from NO2, F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2. or R 2 Together with the carbon atoms of the CO- groups to which they are bonded, Y forms a 5- to 7-membered ring, which may have a C=O or C(CH3)2 group as a ring member, and said 5- to 7-membered ring is fused with a phenyl group, wherein the fused phenyl group is unsubstituted or substituented by 1, 2, 3 or 4 R groups. 4 replace; and R 1 Selected from CFR a R b C2F5 and n-C3F7 R a and R b Each of these elements independently represents halogen, CF3, CN, and C6-C. 14 -aryl, which is unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4-haloalkyl, C1-C4-haloalkoxy, SCF3, SO2CF3, NO2, N=C(CF3)2, SF5, N(SO2CF3)2 and CN; R 4 Represents CN, NO2, SF5, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, N=C(CF3)2 and N(SO2CF3)2.

4. The compound according to claim 1, wherein R 1 and R 2 Selected independently from CFR a R b And phenyl, wherein the phenyl group is substituted with at least one group selected from F, Cl, Br, CN, CF3, SF5, OCF3, SCF3, SO2CF3, N=C(CF3)2 and N(SO2CF3)2, wherein R 2 Not CFR a R b , R a and R b It has one of the meanings defined in claims 1 to 3.

5. The compound according to claim 1, wherein R a and R b Each of the following groups independently represents F, CF3, and A selected from A1 to A32. The ~ refers to the bonds that connect to the rest of the molecule.

6. The compound according to claim 1, wherein L1, L2, L3, and L4 have the same meaning and are selected from... Ad is adamantyl alkyl group. R 3 It contains CN, F, Cl, CF3, Ar, tert-butyl, and adamantyl. R 1 It is CFCl2, CF(CF3)2, n-C3F7, 2,2,3,3,4,4,5,5-octafluoro-1-(trifluoromethyl)cyclopentyl and 1,2,2,3,3,4,4,5,5,6,6-undecylfluorocyclohexyl. X is N(SO2CF3)2, SF5, OCF3, SCF3, CF(CF3)2, Z represents F, Cl, CF3, CN, Ar is selected from A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A1 7. A18, A19, A20, A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31 and A32 Ar1 is 7. An electronic component comprising a hole transport layer and / or a hole injection layer, said layer comprising at least one compound of general formula (I) as defined in any one of claims 1-6.

8. The electronic component according to claim 7, wherein it is in the form of an organic light-emitting diode, an organic solar cell, an organic photodetector, a photovoltaic cell, an organic diode or an organic transistor, or a perovskite solar cell.

9. The electronic component according to claim 8, wherein it is an organic transistor in the form of a thin-film transistor.

10. The electronic component according to any one of claims 7 to 9, having a layered structure comprising 2, 3, 4, 5, 6, 7 or more layers.

11. A doped semiconductor matrix material comprising at least one electron donor and at least one compound of formula (I) as defined in any one of claims 1 to 6.

12. The doped semiconductor matrix material according to claim 1, wherein the electron donor is selected from 4,4',4”-tris(N-(2-naphthyl)-N-phenyl-amino)triphenylamine (2-TNATA), 4,4',4”-tris(N-3-methylphenyl-N-phenyl-amino)triphenylamine (m-MTDATA), N,N,N',N'-tetra(4-methoxy-phenyl)benzidine (MeO-TPD), (2,2',7,7'-tetra-(N,N-diphenylamino)-9,9'-spirodifluorene (spiro-TTB), N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(naphthyl-1-yl)-N N'-bis(phenyl)-9,9-spirodifluorene, 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-spirodifluorene, 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, tris(triphenyl-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-fluorene-2-amine, N-(4-(6-(9,9′-spirobis[fluorene]-2-yl(9,9-dimethyl-9H-fluorene-2-yl)amino)-1,3,3-trimethyl-2,3-Dihydro-1H-indene-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluorene-2-yl)-9,9′-spirobis[fluorene]-2-amine, N-(4-(6-(dibenzo[b,d]furan-2-yl(9,9-dimethyl-9H-fluorene-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-indene-1 9-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-2-amine, 9-(4-(6-(9H-carbazol-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 N,4-Diphenylphenyl-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-inden-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-inden-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'-tetra(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′-spirobis[fluorene]-2-amine, (2,7-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobis[9H-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 A mixture of 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-yl)amine, N-([1,1′-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-fluoren-2-yl)amine, and mixtures thereof.

13. The doped semiconductor matrix material according to claim 12, wherein the molar ratio of matrix molecules to the compound of formula (I) is 10000:1 to 1:

1.

14. The following use of a compound of formula (I) as defined in any one of claims 1 to 6, or a mixture thereof: -As an organic semiconductor - As a redox dopant in organic semiconductor matrix materials - As a p-type dopant in the hole transport layer -As an electron transport material - As a charge injector in the charge injection layer - As a cathode material in organic battery packs. - As an electrochromic material.

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