Cerium (iv) complexes and their use in organic electronic components

Abstract

The invention relates to an electronic component comprising a cerium IV complex; a doped semiconducting matrix material comprising a cerium IV complex and at least one electron donor; the use of a cerium IV complex, in particular as an organic semiconductor, as a dopant in an organic semiconducting matrix material, and as a charge injection agent in a charge injection layer; and new cerium IV complexes.

Description

[0001] The present invention relates to electronically doped semiconductor materials and electronic assemblies comprising cerium(IV) complexes. A further object of the present invention is the use of cerium(IV) complexes as electron acceptors, in particular as p-type dopants and electron transport materials in organic electronic assemblies. A further object of the present invention are novel cerium(IV) complexes. BACKGROUND

[0002] The field of organic electronics focuses on the development, characterization and application of new materials, both small molecules and polymers, which have certain desirable electronic properties for the fabrication of electronic assemblies. These electronic assemblies 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 excitonic solar cells, dye-sensitized solar cells (DSSCs) or perovskite solar cells; electrophotography, such as photoconductive materials in organic photoreceptors (OPCs); organic photodetectors; 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 influenced heavily by doping. Such organic semiconductor matrix materials can be formed from compounds with good electron donor properties (p-conductors) or from compounds with good electron acceptor properties (n-conductors). In contrast to inorganic semiconductors, organic semiconductors have a very low intrinsic charge carrier concentration. Therefore, organic semiconductor matrix materials are usually doped to achieve good semiconductor properties. For n-doping, strong electron donors (n-type dopants) are used, which transfer electrons to the LUMO of the semiconductor matrix (n-doping), thus creating free electrons (SOMO) on the matrix. For p-doping, strong electron acceptors (p-type dopants) are used, which remove electrons from the HOMO of the semiconductor matrix (p-doping), thus creating holes. In other words, for p-doping, the LUMO of the dopant must be lower than the HOMO energy of the matrix. The dopant acts as an acceptor, while leaving mobile holes (SOMO) in the matrix.

[0004] Known p-type dopants for electron donor materials are electron acceptors, such as tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone methylene (F4TCNQ), hexanitrile anthracene (HATNA); metal oxides, such as Mo03or W03; or axiallyene compounds, such as described in EP 2180029. The acceptor molecules create so-called holes in the semiconductor matrix material (hole transport material) by an electron transfer process, and the conductivity of the semiconductor matrix material (hole transport material) changes more or less depending on the number of holes and the mobility of the holes.

[0005] However, the previously described compounds or classes of compounds have disadvantages for technical use in the manufacture of doped semiconductors or in the manufacture of corresponding electronic components having such doped layers. The above-mentioned compounds or classes of compounds are, for example, too volatile, have too high an absorption coefficient, have an unstable evaporation rate and / or show low thermal stability. In addition, some of these compounds have a very high manufacturing cost.

[0006] Therefore, there is still a need for compounds which are easily accessible or manufacturable, suitable for doping of electron donor materials and do not have the above-mentioned disadvantages.

[0007] Only a few cerium(IV) complexes of diketonates are known. Some β-diketonate complexes of cerium(IV) are described in the literature. M. Ciampolini et al., J.C.S, Dalton, 1977, 1325; T.J. Pinnaviaia et al., Cornell University, Chemistry Dept., Ithaca, New York, 1965, 233; I. Baxter et al., J. Chem. Cryst. Vol. 28, No. 4, 1998, 267; N.A. Piro et al., Coord. Chem. Review, 260, 2014, 21; M. Delarosa et al., J. Coord. Chem., 55(7), 2002, 781; Jahr et al., Zeitschrift fur Chemie, Bd. 15, 1975, S 280-281; Snezhko et al., Material Science and Engineering, Vol. 18, 1993, S. 230-231; Brill et al., Liebigs Annalen der Chemie, 1979, S. 803-810 and WO 02 / 018394 describe the following cerium(IV) complexes:

[0008]

[0009] WO 02 / 018394 relates to precursor-derived reagent metal-organic compositions. The formation of cerium-doped (Ca, Sr)Ga2S2 films is described with a sulfur-containing solvent system and deposition in the presence of hydrogen sulfide gas.

[0010] Kunkely et al., Journal of Photochemistry and Photobiology A, Vol. 146, Issues 1-2, Pages 63-66, describe cerium(IV) 2,2,6,6-tetramethyl-3,5-heptane-dionate anions. It is further described that this complex has luminescent properties and is also photoactive. These properties are not related to p-dopants or redox-doping of transport layers.

[0011] US 2010 / 0038632 describes various complexes, including cerium(IV) complexes. In one aspect, no cerium(IV) complex according to the present application is explicitly mentioned. In another aspect, the large band gap of the cerium complexes mentioned in this document is not related to p-dopants.

[0012] So far, the use of cerium(IV) complexes in organic semiconducting materials is not known. In particular, the use of cerium(IV) complexes as p-dopants, as electron transport materials or as electron acceptors has not been described.

[0013] Surprisingly, it has now been found that cerium(IV) complexes can advantageously be used as p-dopants. Furthermore, it has been found that cerium(IV) complexes can be used as electron transport materials (ETM) in organic electronic components, such as organic light emitting diodes (OLEDs), photovoltaic cells, organic solar cells (OPV), organic diodes or organic transistors.

[0014] Furthermore, many diketonate cerium(IV) species can be well evaporated under vacuum, occasionally showing high thermal stability. Thus, they are basically suitable for both processing variants of organic electronic components, vacuum coating (vapor deposition) and solvent-based processing (solution processing). SUMMARY

[0015] A first object of the present application is an electronic component comprising a compound of the general formula (I.1)

[0016] Ce 4+ (L1L2L3L4) 4- (I.1)

[0017] or a mixture of at least two different compounds of the general formula (I.1), wherein L1, L2, L3and L4are independently of each other selected from bidentate ligands of the general formula (I.2),

[0018] wherein

[0019] X and W independently of one another denote O, S or NR 6 ;

[0020] Y denotes N or CR 3 ;

[0021] R 1 , R 2 independently of one another denote CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylmercapto, Ci-C6-haloalkylmercapto, NR 4a R 4b , C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, where the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, where aryl and heteroaryl are unsub stituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 8 ;

[0022] R 3 denotes hydrogen, CN, nitro, halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylmercapto, Ci-C6-haloalkylmercapto, NR 4a R 4b , C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, where the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, where aryl and heteroaryl are unsub stituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0023] R 4a R 4b independently of one another denote hydrogen, Ci-C6-alkyl or C6-C 14 -aryl, where aryl is unsub stituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0024] R 5 denotes CN, halogen, Ci-C4-alkyl or Ci-C4-haloalkyl;

[0025] R 6 denotes hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C6-C 14- aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, wherein aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0026] R 7 represents hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl or C6-C 14 - aryl, wherein aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0027] R 8 represents CN, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl or C6-C 14 - aryl, the C6-C 14 - aryl is unsubstituted or substituted by 1, 2 or 3 identical or different radicals selected from the group consisting of Ci-C4-alkyl and Ci-C4-haloalkyl.

[0028] It is a further object of the present application an electronic component comprising a compound of general formula (I)

[0029]

[0030] or mixtures thereof, wherein

[0031] X and W independently from each other represent O, S or NR 6 ;

[0032] Y represents N or CR 3 ;

[0033] R 1 , R 2 independently from each other represent CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylmercapto, Ci-C6-haloalkylmercapto, NR 4a R 4b , C6-C 14 - aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, wherein aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 8 ;

[0034] R3 This indicates hydrogen, CN, nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthiol, C1-C6-haloalkylthiol, and NR. 4a R 4b C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from N, NR 7 O, S, SO and SO2, wherein the aryl and heteroaryl groups are not substituted or are occupied by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0035] R 4a R 4b Each can be independently represented as hydrogen, C1-C6-alkyl, or C6-C 14 -aryl, wherein the aryl group is unsubstituted or surrounded by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0036] R 5 Indicates CN, halogen, C1-C4-alkyl, or C1-C4-haloalkyl;

[0037] R 6 Represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from N, NR 7 O, S, SO and SO2, wherein the aryl and heteroaryl groups are not substituted or are occupied by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0038] R 7 Indicates hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, or C6-C 14 -aryl, wherein the aryl group is unsubstituted or surrounded by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0039] R 8 Indicates CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C6-C 14 -Aryl, the C6-C 14 - The aryl group is either unsubstituted or substituted by one, two, or three identical or different groups selected from C1-C4-alkyl and C1-C4-haloalkyl groups.

[0040] It is a further object of the present application an electronic assembly comprising a compound of general formula (I)

[0041]

[0042] or mixtures thereof, wherein

[0043] X and W independently of each other represent O, S or NR 6 ;

[0044] Y represents N or CR 3 ;

[0045] R 1 , R 2 independently of each other represent CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, NR 4a R 4b , C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, wherein aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0046] R 3 represents hydrogen, CN, nitro, halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, NR 4a R 4b , C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, wherein aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0047] R 4a R 4b independently of each other represent hydrogen, Ci-C6-alkyl or C6-C 14 -aryl, wherein aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0048] R5 represents CN, halogen, Ci-C4-alkyl or Ci-C4-haloalkyl;

[0049] R 6 represents hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C6-Ci4-aryl or heteroaryl having 4 to 13 carbon atoms, wherein heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, which are selected from the group consisting of N, NR 14 , O, S, SO and SO2, wherein aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 7 ; 5

[0050] R 7 represents hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl or C6-Ci4-aryl, wherein aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 14 ; 5

[0051] A further object of the present application is a doped semiconductor matrix material comprising at least one electron donor and at least one compound of the formula (1.1) or (I), wherein the radicals X, W, Y, R 1 and R 2 have the meanings as given above and as defined below.

[0052] A further object of the present application is the use of the compound (1.1) or mixtures thereof or the compound (I) or mixtures thereof, wherein the radicals X, W, Y, R 1 and R 2 have the meanings as defined before and below,

[0053] - as organic semiconductor,

[0054] - as dopant in an organic semiconductor matrix material, in particular as p-type dopant in a hole transport layer,

[0055] - as charge injection agent in a charge injection layer,

[0056] - as positive electrode material for an organic battery,

[0057] - as electrochromic material.

[0058] A further object of the present application is the use of a Ce(III) complex anion obtained by reduction of the compound (1.1) or (I) as defined above and below or of a charge transfer complex of the compound (1.1) or (I) as defined above and below with an electron donor as an organic conductor, electrochromic material or ferrimagnet. ​​

[0059] A further object of the present application is a compound of general formula (I.1)

[0060] Ce 4+ (L1L2L3L4) 4- (I.1)

[0061] and mixtures thereof, wherein

[0062] L1, L2, L3and L4are independently of one another a bidentate ligand of general formula (I.2)

[0063] wherein

[0064] X and W independently of one another denote O, S or NR 6 ;

[0065] Y denotes N or CR 3 ;

[0066] R 1 , R 2 independently of one another denote 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 -aryl or heteroaryl having 4 to 13 carbon atoms, where the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, where aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 8 ;

[0067] R 3 denote 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 -aryl or heteroaryl having 4 to 13 carbon atoms, where the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, where aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0068] R 4a R4b independently of one another, hydrogen, C1-C6-alkyl or C6-C 14 - aryl, wherein the aryl group is unsubstituted or substituted by one, two, three, four or five identical or different radicals R 5 ;

[0069] R 5 represents CN, halogen, C1-C4-alkyl or C1-C4-haloalkyl;

[0070] R 6 represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C6-C 14 - aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has one, two or three identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, wherein the aryl and heteroaryl are unsubstituted or substituted by one, two, three, four or five identical or different radicals R 5 ;

[0071] R 7 represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C6-C 14 - aryl, wherein the aryl group is unsubstituted or substituted by one, two, three, four or five identical or different radicals R 5 ;

[0072] R 8 represents CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C6-C 14 - aryl, the C6-C 14 - aryl is unsubstituted or substituted by one, two or three identical or different radicals selected from the group consisting of C1-C4-alkyl and C1-C4-haloalkyl;

[0073] with the proviso that the following compounds are excluded:

[0074]

[0075] It is a further object of the present application compounds of general formula (I)

[0076]

[0077] and charge transfer complexes thereof, reduction products thereof and mixtures thereof, wherein

[0078] X and W independently of one another represent O, S or NR 6 ;

[0079] Y represents N or CR 3 ;

[0080] R 1 , R 2 independently of one another, 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 -aryl or heteroaryl having 4 to 13 carbon atoms, where the heteroaryl has 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, where aryl and heteroaryl are unsub stituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 8 ;

[0081] R 3 represents 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 -aryl or heteroaryl having 4 to 13 carbon atoms, where the heteroaryl has 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, where aryl and heteroaryl are unsub stituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0082] R 4a R 4b independently of one another, hydrogen, C1-C6-alkyl or C6-C 14 -aryl, where aryl is unsub stituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0083] R 5 represents CN, halogen, C1-C4-alkyl or C1-C4-haloalkyl;

[0084] R 6 represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, where the heteroaryl has 1, 2, or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7O, S, SO and SO2, where aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 substituted;

[0085] R 7 represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C6-C 14 - aryl, where aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 substituted;

[0086] R 8 represents CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C6-C 14 - aryl, the C6-C 14 - aryl is unsubstituted or substituted by 1, 2 or 3 identical or different radicals selected from C1-C4-alkyl and C1-C4-haloalkyl;

[0087] with the proviso that the following compounds are excluded:

[0088]

[0089] It is a further object of the present application compounds of general formula (I)

[0090]

[0091] and charge transfer complexes thereof, reduction products thereof and mixtures thereof, wherein

[0092] X and W independently of one another represent O, S or NR 6 ;

[0093] Y represents N or CR 3 ;

[0094] R 1 , R 2 independently of one another represent CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylmercapto, C1-C6-haloalkylmercapto, NR 4a R 4b , C6-C 14 - aryl or heteroaryl having 4 to 13 carbon atoms, where heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members selected from N, NR 7 O, S, SO and SO2, where aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 substituted;

[0095] R3 This indicates hydrogen, CN, nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthiol, C1-C6-haloalkylthiol, and NR. 4a R 4b C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from N, NR 7 O, S, SO and SO2, wherein the aryl and heteroaryl groups are not substituted or are occupied by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0096] R 4a R 4b Each can be independently represented as hydrogen, C1-C6-alkyl, or C6-C 14 -aryl, wherein the aryl group is unsubstituted or surrounded by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0097] R 5 Indicates CN, halogen, C1-C4-alkyl, or C1-C4-haloalkyl;

[0098] R 6 Represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from N, NR 7 O, S, SO and SO2, wherein the aryl and heteroaryl groups are not substituted or are occupied by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0099] R 7 Indicates hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, or C6-C 14 -aryl, wherein the aryl group is unsubstituted or surrounded by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0100] The condition is that the following compounds must be excluded:

[0101] Detailed Implementation

[0102] The present invention has the following advantages:

[0103] - The cerium-(IV) complexes according to the present application only have a low manufacturing cost.

[0104] - The cerium-(IV) complexes according to the present application are advantageously suitable as electron acceptors for use as p-type dopants and as electron transport materials in organic electronic components.

[0105] - The cerium-(IV) complexes according to the present application exhibit a better electrical conductivity compared to known electron acceptors.

[0106] - The cerium-(IV) complexes according to the present application show an improved thermal stability of their doped layers compared to the prior art.

[0107] - Furthermore, the cerium(IV) complexes according to the present application are characterized by a higher doping efficiency.

[0108] - The cerium-(IV)-complexes according to the present application only show a low absorption of the doped layer. Thus, parasitic absorption and emission can be reduced or even prevented.

[0109] - The cerium-(IV)-complexes according to the present application are suitable for the manufacture of organic and hybrid optoelectronic components both by solvent processing and vacuum reprocessing.

[0110] In the context of the present application, a bidentate (also called bidentate) ligand is a ligand which binds to a metal atom (cerium atom) with two atoms.

[0111] In the context of the present application, a homoleptic cerium(IV) compound is a complex in which all ligands are identical.

[0112] In the context of the present application, a heteroleptic cerium(IV) compound is a complex in which the meaning of at least one ligand is different from the remaining ligands.

[0113] In the context of the present application, the prefix C n -C m denotes the number of carbon atoms which the molecule or residue designated by it can comprise.

[0114] In the context of the present application, the term C1-C6-alkyl refers to unbranched or branched saturated hydrocarbon groups 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 1-ethyl-2-methylpropyl. C1-C4-alkyl refers for example to methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

[0115] In the context of the present application, the term C1-C6-alkoxy refers to unbranched or branched saturated C1-C6-alkyl bound via an oxygen atom as defined above. Preference is given to alkoxys having 1 to 4 carbon atoms, particularly preferably 1 or 2 carbon atoms. C1-C2-alkoxy is methoxy or ethoxy. 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 comprises the definitions given for C1-C4-alkoxy, furthermore for example 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.

[0116] In the context of the present application, the term C1-C6-alkylthio means a non-branched or branched saturated C1-C6-alkyl group as defined above bound via a sulfur atom. Preference is given to alkylthio groups having 1 to 4 carbon atoms, particularly preferably 1 or 2 carbon atoms. C1-C2-alkylthio is methylthio or ethylthio. C1-C4-alkylthio is, 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 comprises the definitions given for C1-C4-alkylthio and furthermore, for example, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or 1-ethyl-2-methylpropylthio.

[0117] In the context of the present application, the terms haloalkyl, haloalkoxy and haloalkylthio mean alkyl, alkoxy or alkylthio groups which are partially or completely halogenated. In other words, one or more hydrogen atoms bound to one or more carbon atoms of the alkyl, alkoxy or alkylthio group are replaced by halogen atoms, in particular fluorine or chlorine, for example 1, 2, 3, 4 or 5 hydrogen atoms.

[0118] The term "halogen" denotes fluorine, chlorine, bromine or iodine, respectively.

[0119] The term "CN" denotes a cyano group (-CºN).

[0120] In the context of the present application, the term "aryl" comprises mono- or polynuclear aromatic hydrocarbon radicals which usually have 6 to 14, particularly preferably 6 to 10 carbon atoms. Examples of aryl groups are, in particular, phenyl, naphthyl, indenyl, fluorenyl, anthryl, phenanthryl, naphthacenyl, pyrenyl, chrysenyl, triphenylenyl, tetracenyl, hexacenyl, picenyl, perylenyl, coronenyl, ovalenyl, etc., particularly preferably phenyl or naphthyl. In the context of the present application, the term "aryl" comprises mono- or polynuclear aromatic hydrocarbon radicals which usually have 6 to 14, particularly preferably 6 to 10 carbon atoms. Examples of aryl groups are, in particular, phenyl, naphthyl, indenyl, fluorenyl, anthryl, phenanthryl, naphthacenyl, pyrenyl, chrysenyl, triphenylenyl, tetracenyl, hexacenyl, picenyl, perylenyl, coronenyl, ovalenyl, etc., particularly preferably phenyl or naphthyl.

[0121] In the context of the present application, the term "heteroaryl" comprises a mono- or polynuclear aromatic hydrocarbon radical having 4 to 13 carbon atoms, wherein 1, 2 or 3 carbon atoms have been replaced by 1, 2 or 3 identical or different heteroatoms or heteroatom-containing radicals as ring members, the heteroatoms and heteroatom-containing radicals being selected from the group consisting of N, NR 7 , O, S, SO and SO2. The heteroaryl radical can be attached to the remainder of the molecule via a ring carbon or via a ring nitrogen. Examples of 5- or 6-membered aromatic heterocycles (also referred to as heteroaromatic rings or heteroaryl groups) are 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-triazol-2-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl. Examples of 8-, 9- or 10-membered aromatic heterobicycles are heteroaryl groups having one of the above-mentioned 5- or 6-membered heteroaromatic rings and another aromatic carbocyclic or 5- or 6-membered heterocyclic ring fused thereto, for example a fused benzene, thiophene, furan, pyrrole, pyrazole, imidazole, pyridine or pyrimidine ring. These bicyclic heteroarylenes include, for example, quinolinyl, isoquinolinyl, cinnolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuranyl (in particular 2-benzofuranyl), benzothienyl (in particular 2-benzothienyl), benzo[b]thiazolyl (in particular 2-benzo[b]thiazolyl), benzoxazolyl (in particular 2-benzoxazolyl), benzothiazolyl (in particular 2-benzothiazolyl), benzoimidazolyl (in particular 2-benzoimidazolyl), 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.

[0122] When # occurs in a preferred substructural formula representing a compound of the application, it denotes a bond to the remainder of the molecule.

[0123] Cerium compounds of the formula (I.1) and (I)

[0124] Compounds of the formula (I.1)

[0125] Ce 4+ (L1L2L3L4) 4- (I.1), wherein

[0126] L1, L2, L3 and L4 are as defined above and below, including compounds, wherein

[0127] - all four ligands L1, L2, L3and L4have the same meaning,

[0128] - three of the four ligands have the same meaning,

[0129] - two of the four ligands have the same meaning,

[0130] - all four ligands L1, L2, L3and L4have different meanings.

[0131] Preference is given to compounds of the formula (I.1), wherein L1, L2, L3and L4have the same meaning.

[0132] In the cerium compounds of the formula (I.1), L1, L2, L3and L4are independently of one another selected from bidentate ligands of the general formula (I.2). In the preferred embodiments of the compounds (I.1) described below, the definitions are directly derived from the preferred embodiments of the bidentate ligands (I.2) thereof.

[0133] Preference is given to compounds of the formula (I) and to ligands of the formula (I.2), wherein R 1 and R 2 are independently selected from the group consisting of CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylsulfanyl, C1-C6-haloalkylsulfanyl, NR 4a R 4b and from the group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18and A19:

[0134]

[0135] wherein # denotes the bond to the remainder of the ligand of the formula (I) and of the formula (I.2),

[0136] R A , R B , R C , R D and R E are independently selected from the group consisting of hydrogen, CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl and phenyl, which is unsubstituted or substituted by 1, 2 or 3 identical or different radicals selected from C1-C4-alkyl and C1-C4-haloalkyl;

[0137] R 4a , R 4b independently denote hydrogen, C1-C6-alkyl or C6-C 14 -aryl, wherein aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R5 substituted;

[0138] R 5 represents CN, halogen, C1-C4-alkyl or C1-C4-haloalkyl; and

[0139] R 7 represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C6-C 14 -aryl, wherein aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 substituted.

[0140] Another preferred embodiment are compounds of formula (I) and ligands of formula (I.2), wherein R 1 and R 2 are independently selected from the group consisting of CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylsulfanyl, C1-C6-haloalkylsulfanyl, NR 4a R 4b and the group A consisting of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14and A15, wherein

[0141] R A , R B , R C , R D and R E are independently selected from the group consisting of hydrogen, CN, halogen, C1-C4-alkyl and C1-C4-haloalkyl;

[0142] R 4a , R 4b are independently represent hydrogen, C1-C6-alkyl or C6-C 14 -aryl, wherein aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 substituted;

[0143] R 5 represents CN, halogen, C1-C4-alkyl or C1-C4-haloalkyl; and

[0144] R 7 represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C6-C 14 -aryl, wherein aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 substituted.

[0145] R A , R BR C R D R E are preferably selected from hydrogen, CN, fluorine, chlorine, Ci-C4-alkyl, Ci-C4-fluoroalkyl, Ci-C4-chloroalkyl and phenyl, which is unsubstituted or substituted by 1, 2 or 3 identical or different radicals selected from Ci-C4-haloalkyl.

[0146] Particularly preferably, the radicals R A R B R C R D R E are independently of one another selected from hydrogen, CN, fluorine and chlorine.

[0147] In another particular embodiment, the radicals R A R B R C R D R E are independently of one another selected from hydrogen, CN, fluorine, chlorine and phenyl which is substituted by 1 or 2 identical or different radicals selected from Ci-C2-haloalkyl.

[0148] Particularly preferably, the radicals R A R B R C R D R E all denote fluorine.

[0149] Also particularly preferably, the radicals R A R B R D R E are hydrogen and R C is 3,5-di(trifluoromethyl)phenyl.

[0150] Preferably, in the ligands of formula (I) and (I.2), R 1 R 2 are independently selected from Ci-C4-alkyl, Ci-C4-haloalkyl, A1and A5

[0151]

[0152] wherein # denotes the bond to the remainder of the ligand of formula (I) and (I.2), and wherein

[0153] R A R B R C R D R Eindependently selected from the group consisting of hydrogen, CN, fluorine, chlorine, C1-C4- alkyl, C1-C4-fluoroalkyl, C1-C4-chloroalkyl and phenyl, which is unsubstituted or substituted by one, two or three identical or different radicals selected from C1-C4-haloalkyl.

[0154] In another preferred embodiment of the ligand of formula (I) and (I.2), R 1 and R 2 are independently selected from the group consisting of A16and A17,

[0155]

[0156] wherein # denotes the bond to the remainder of the ligand of formula (I) and (I.2), and wherein

[0157] R A , R B and R C are independently selected from the group consisting of hydrogen, CN, fluorine, chlorine, C1-C4-alkyl, C1-C4-fluoroalkyl and C1-C4-chloroalkyl. Preferably, R A , R B and R C are hydrogen.

[0158] In a preferred embodiment, in the ligand of formula (I) and (I.2), R 1 and R 2 are independently selected from the group consisting of A1and A5

[0159]

[0160] wherein # denotes the bond to the remainder of the ligand of formula (I) and (I.2), and wherein

[0161] R A , R B , R C , R D and R E are independently selected from the group consisting of hydrogen, CN, fluorine, chlorine, C1-C4-alkyl, C1-C4-fluoroalkyl, C1-C4-chloroalkyl and phenyl, which is unsubstituted or substituted by one, two or three identical or different radicals selected from C1-C4-haloalkyl.

[0162] In a particularly preferred embodiment of the ligand of formula (I) and (I.2), R 1 and R 2 are independently selected from the group consisting of A1and A5, wherein R A , R B , R C , R D and R Eindependently selected from CN, fluorine and chlorine.

[0163] In another particularly preferred embodiment of formula (I), R 1 and R 2 are independently selected from A1and A5, wherein R A , R B , R C , R D and R E are independently selected from CN, fluorine and chlorine.

[0164] In another preferred embodiment of the ligand of formula (I) and formula (I.2), R 1 and R 2 are independently selected from C1-C4-alkyl, C1-C4-fluoroalkyl, C1-C4-chloroalkyl and A1, wherein R A , R B , R C , R D and R E are independently selected from CN, fluorine and chlorine.

[0165] In another preferred embodiment, in formula (I), R 1 and R 2 are independently selected from C1-C4-alkyl, C1-C4-fluoroalkyl, C1-C4-chloroalkyl and A1, wherein R A , R B , R C , R D and R E are independently selected from CN, fluorine and chlorine.

[0166] In a particular embodiment, in the ligand of formula (I) and formula (I.2), R 1 and R 2 are independently selected from A1and A5, wherein R A , R B , R C , R D and R E are fluorine.

[0167] In a particular embodiment, in formula (I), R 1 and R 2 are independently selected from A1and A5, wherein R A , R B , R C , R D and R E are fluorine.

[0168] In another preferred embodiment, in formula (I) and in the ligand of formula (I.2), R 1and R 2 is A1, wherein R A , R B , R D and R E are hydrogen, and R C is 3,5-di(trifluoromethyl)phenyl.

[0169] In another preferred embodiment, in formula (I) R 1 and R 2 are A1, wherein R A , R B , R D and R E are hydrogen, and R C is 3,5-di(trifluoromethyl)phenyl.

[0170] Preferred are compounds of formula (I) and ligands of formula (I.2), wherein Y denotes a group CR 3 , and R 3 is selected from the group B consisting of B1, B2, B3, B4, B5, B6, B7, B8, B9, B10, B11, B12, B13, B14 and B15

[0171]

[0172] wherein # denotes the bond to the remainder of the molecule of formula (I) and formula (I.2);

[0173] R F , R G , R H , R I and R J are independently selected from the group consisting of hydrogen, CN, halogen, Ci-C4-alkyl and Ci-C4-haloalkyl; and

[0174] R 7 denotes hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl or Ci-C 14 -aryl, wherein aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 .

[0175] The radicals R F , R G , R H , R I and R J are, independently of one another, preferably selected from the group consisting of hydrogen, CN, fluorine, chlorine, Ci-C4-alkyl, Ci-C4-fluoroalkyl and Ci-C4chloroalkyl.

[0176] In a preferred embodiment, the radicals RA , R B , R C , R D and R E independently represent CN, fluorine or chlorine.

[0177] In the ligands of formula (I) and (I.2), Y preferably represents a group CR 3 wherein R 3 is selected from hydrogen, CN, nitro, halogen, CF3and B1

[0178]

[0179] wherein # represents the bond to the remainder of the ligand of formula (I) and (I.2), and wherein

[0180] R F , R G , R H , R I and R J are independently selected from hydrogen, CN, fluorine and chlorine.

[0181] In the ligands of formula (I) and (I.2), Y preferably represents a group CR 3 wherein R 3 represents B1

[0182]

[0183] wherein # represents the bond to the remainder of the ligand of formula (I) and (I.2), and wherein

[0184] R F , R G , R H , R I and R J are independently selected from CN, fluorine and chlorine.

[0185] In another preferred embodiment, Y represents a group CR 3 wherein R 3 is selected from hydrogen, CN, nitro, fluorine, chlorine and CF3.

[0186] The groups R 4a and R 4b are, if present, preferably selected from hydrogen and Ci-C4-alkyl.

[0187] The group R 5 is, if present, preferably selected from CN, fluorine, chlorine, Ci-C4-alkyl and Ci-C4-haloalkyl.

[0188] The group R 6preferably selected from hydrogen and C1-C4-alkyl.

[0189] the radical R 7 preferably selected from hydrogen and C1-C4-alkyl and C1-C4-haloalkyl.

[0190] In a preferred first embodiment A, preferably compounds of formula (I) and ligands of formula (I.2) are preferred, wherein

[0191] X and W represent S or O, in particular O;

[0192] Y represents CR 3 , wherein R 3 is selected from the group consisting of hydrogen, CN, nitro and halogen, in particular fluorine, CN and nitro;

[0193] R 1 and R 2 independently of one another represent CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylsulfanyl, C1-C6-haloalkylsulfanyl, NR 4a R 4b , in particular C1-C4-alkyl or C1-C4-haloalkyl.

[0194] In a preferred second embodiment B, preferably compounds of formula (I) and ligands of formula (I.2) are preferred, wherein

[0195] X and W represent S or O, in particular O;

[0196] Y represents CR 3 , wherein R 3 is selected from the group consisting of hydrogen, CN, nitro and halogen, in particular fluorine, CN and nitro;

[0197] R 1 and R 2 independently of one another represent CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylsulfanyl, C1-C6-haloalkylsulfanyl, NR 4a R 4b , in particular C1-C4-alkyl or C1-C4-haloalkyl.

[0198] In a preferred second embodiment B, preferably compounds of formula (I) and ligands of formula (I.2) are preferred, wherein

[0199] X and W represent S or O, in particular O;

[0200] Y represents CR 3 , wherein R 3represents B1, B2, B3, B4, B5, B6, B7, B8, B9, B10, B11, B12, B13, B14 or B15, in particular B1 ;

[0201] R 1 and R 2 independently of one another represent CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, NR 4a R 4b in particular represent Ci-C4-alkyl or Ci-C4-haloalkyl.

[0202] Particularly preferred are compounds of formula (I) wherein

[0203] X and W represent S or O, in particular O;

[0204] Y represents CR 3 wherein R 3 represents B1, B2, B3, B4, B5, B6, B7, B8, B9, B10, B11, B12, B13, B14 or B15, in particular B1 ;

[0205] R 1 and R 2 independently of one another represent CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, NR 4a R 4b in particular represent Ci-C4-alkyl or Ci-C4-haloalkyl.

[0206] In a preferred third embodiment C, preferred are compounds of formula (I) and ligands of formula (I.2) wherein

[0207] X and W represent S or O, in particular O;

[0208] Y represents CR 3 wherein R 3 represents B1, B2, B3, B4, B5, B6, B7, B8, B9, B10, B11, B12, B13, B14 or B15, in particular B1 ;

[0209] R 1 and R 2 independently of one another represent A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14 or A15, in particular A1 or A5.

[0210] Particularly preferred are compounds of formula (I), wherein

[0211] X and W represent S or O, in particular O;

[0212] Y represents CR 3 , in particular B1 ; 3 , in particular B1 ;

[0213] R 1 and R 2 independently of one another represent A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14 or A15, in particular A1 or A5.

[0214] In a preferred fourth embodiment D, preferred are compounds of formula (I) and ligands of formula (I.2), wherein

[0215] X and W represent S or O, in particular O;

[0216] Y represents CR 3 , in particular B1 ; 3 selected from the group consisting of hydrogen, CN, nitro and halogen, in particular fluorine, CN and nitro;

[0217] R 1 and R 2 independently of one another represent A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14 or A15, in particular A1 or A5.

[0218] Particularly preferred are compounds of formula (I), wherein

[0219] X and W represent S or O, in particular O;

[0220] Y represents CR 3 , in particular B1 ; 3 selected from the group consisting of hydrogen, CN, nitro and halogen, in particular fluorine, CN and nitro;

[0221] R 1 and R 2 independently of one another represent A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14 or A15, in particular A1 or A5.

[0222] In a preferred fifth embodiment E, preferred are compounds of formula (I) and ligands of formula (I.2), wherein

[0223] X and W represent S or O, in particular O;

[0224] Y represents CR 3 wherein R 3 is selected from the group consisting of hydrogen, CN, nitro and halogen, in particular fluorine, CN and nitro;

[0225] R 1 represents A1;

[0226] R 2 represents CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylmercapto, Ci-C6-haloalkylmercapto, NR 4a R 4b , in particular Ci-C4-alkyl or Ci-C4-haloalkyl.

[0227] Particularly preferred are compounds of the formula (I), in which

[0228] X and W represent S or O, in particular O;

[0229] Y represents CR 3 wherein R 3 is selected from the group consisting of hydrogen, CN, nitro and halogen, in particular fluorine, CN and nitro;

[0230] R 1 represents A1;

[0231] R 2 represents CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylmercapto, Ci-C6-haloalkylmercapto, NR 4a R 4b , in particular Ci-C4-alkyl or Ci-C4-haloalkyl.

[0232] In a preferred sixth embodiment F, preference is given to compounds of the formula (I) and ligands of the formula (I.2), in which

[0233] X and W represent S or O, in particular O;

[0234] Y represents CR 3 wherein R 3 is selected from the group consisting of hydrogen, CN, nitro and halogen, in particular hydrogen;

[0235] R 1 and R 2 independently of one another represent A16or A17.

[0236] Particularly preferred are compounds of the formula (I), in which

[0237] X and W represent S or O, in particular O;

[0238] Y represents CR 3 wherein R 3 is selected from the group consisting of hydrogen, CN, nitro and halogen, in particular hydrogen;

[0239] R 1 and R 2 independently of one another represent A16or A17.

[0240] In a preferred seventh embodiment G, preference is given to compounds of the formula (I) and ligands of the formula (I.2), wherein

[0241] X and W represent S or O, in particular O;

[0242] Y represents CR 3 wherein R 3 is selected from the group consisting of hydrogen, CN, nitro and halogen, in particular hydrogen;

[0243] R 1 represents A16or A17;

[0244] R 2 represents CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylmercapto, Ci-C6-haloalkylmercapto, NR 4a R 4b , in particular Ci-C4-alkyl or Ci-C4-haloalkyl.

[0245] Particular preference is given to compounds of the formula (I), wherein

[0246] X and W represent S or O, in particular O;

[0247] Y represents CR 3 wherein R 3 is selected from the group consisting of hydrogen, CN, nitro and halogen, in particular hydrogen;

[0248] R 1 represents A16or A17;

[0249] R 2 represents CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylmercapto, Ci-C6-haloalkylmercapto, NR 4a R 4b , in particular Ci-C4-alkyl or Ci-C4-haloalkyl.

[0250] Particular preference is given to compounds of the formula (I.a'):

[0251] 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'), where

[0252] (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.

[0253] Table 1:

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262] Compounds of formula (Ia) are particularly preferred.

[0263]

[0264] Where R 1R 2 R 3 as defined in table 2:

[0265] table 2:

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274] Particularly preferred are compounds of formula (I. a) wherein R 1 R 2 R 3 as defined in table 3:

[0275] table 3:

[0276]

[0277]

[0278] In formula (I. a) the four ligands L1, L2, L3and L4bound to the cerium atom have the same meaning.

[0279] The homoleptic compounds of formula (I. 1) and (I) are prepared by reacting a beta-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. The beta-diketone ligand is commercially available or it can be prepared by synthesis known to the skilled person.

[0280] The heteroleptic compounds of formula (I. 1) are made from:

[0281] - mixing two different homoleptic cerium compounds in a suitable solvent,

[0282] - mixing a homoleptic cerium compound with a ligand different from the ligand of said compound or an alkali / alkaline earth metal salt thereof,

[0283] - vapor deposition of two different homoleptic cerium compounds,

[0284] - Vapor deposition of homoleptic cerium compounds with ligands different from the ligands of the compounds (vapor co-condensation).

[0285] Components

[0286] In the context of the present application, electronic components are understood to be discrete or integrated electronic components which exploit the properties of the compounds of the general formula (1.1) or (I) or of a semiconductor matrix material containing the compounds of the general formula (1.1) or (I). In a particular embodiment, the electronic components have a layered structure which particularly comprises 2, 3, 4, 5, 6, 7 or more layers, wherein at least one layer contains at least one compound of the general formula (1.1) or (I). In particular, the electronic components have a layered structure which particularly comprises 2, 3, 4, 5, 6, 7 or more layers, wherein at least one layer contains at least one compound of the general formula (I). Each layer can also contain inorganic materials, or the components can also comprise layers which consist entirely of inorganic materials.

[0287] Preferably, the electronic components are selected from the group consisting of organic field effect transistors (OFETs), organic electroluminescent devices, organic solar cells (OSCs), devices for electrophotography, organic photodetectors, organic photoconductors, light-emitting electrochemical cells (LECs) and organic laser diodes. The organic field effect transistors (OFETs) are preferably organic thin film transistors (OTFTs). The organic electroluminescent devices are preferably organic light emitting diodes (OLEDs). The organic solar cells are preferably exciton solar cells, dye-sensitised solar cells (DSSCs) or perovskite solar cells. The devices for electrophotography are preferably photoconductive materials in organic photoconductors (OPCs).

[0288] Preferably, the electronic components according to the application are in the form of organic light emitting diodes, organic solar cells, photovoltaic cells, organic diodes or organic transistors, preferably in the form of field effect transistors or thin film transistors or perovskite solar cells.

[0289] The electronic components can preferably be in the form of organic electroluminescent devices, in particular organic light emitting diodes (OLEDs). Organic electroluminescent devices comprise an anode, a cathode and at least one emission layer. In addition to these layers, it can also comprise further 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. Interlayers, for example with exciton blocking function, can also be inserted between two emission layers. Not all of these layers must be present.

[0290] A preferred embodiment is an electronic component, in particular in the form of an OLED, wherein the layer comprising the compound of formula (I.1) or (I) is a hole transport layer or a hole injection layer. In particular, the electronic component, in particular in the form of an OLED, wherein the layer comprising the compound of formula (I) is a hole transport layer, a hole injection layer or an electron blocking layer. Generally, a hole injection layer is a layer that facilitates the injection of electrons from the cathode into the organic semiconducting matrix material. The hole injection layer can be placed directly adjacent to the cathode. A hole transport layer transports holes from the cathode to the emission layer and is located between the hole injection layer and the emission layer.

[0291] A preferred embodiment is an electronic component, in particular in the form of an OLED, wherein the layer comprising the compound of formula (I.1) or (I) is a hole transport layer or a hole injection layer. In particular, the electronic component, in particular in the form of an OLED, wherein the layer comprising the compound of formula (I) is a hole transport layer, a hole injection layer or an electron blocking layer. Generally, a hole injection layer is a layer that facilitates the injection of electrons from the cathode into the organic semiconducting matrix material. The hole injection layer can be placed directly adjacent to the cathode. A hole transport layer transports holes from the cathode to the emission layer and is located between the hole injection layer and the emission layer.

[0292] - a layer having electron transport layer properties (electron transport layer, ETL),

[0293] - a layer comprising a hole conducting material (hole transport layer, HTL), which layers do not necessarily have to absorb radiation,

[0294] - exciton and hole blocking layers (e.g. EBL), which layers must not absorb, and

[0295] - a multiplier layer.

[0296] A preferred embodiment is an electronic component, in particular in the form of an OLED, wherein the layer comprising the compound of formula (I.1) or (I) is a hole transport layer or a hole injection layer. In particular, the electronic component, in particular in the form of an OLED, wherein the layer comprising the compound of formula (I) is a hole transport layer, a hole injection layer or an electron blocking layer. Generally, a hole injection layer is a layer that facilitates the injection of electrons from the cathode into the organic semiconducting matrix material. The hole injection layer can be placed directly adjacent to the cathode. A hole transport layer transports holes from the cathode to the emission layer and is located between the hole injection layer and the emission layer.

[0297] A particular embodiment is an electronic component, in particular in the form of an organic solar cell, wherein the layer comprising at least one compound of formula (I.1 ) or (I) is part of a PN junction connecting a light absorbing unit to a further light absorbing unit in a tandem device or a multiple stack device, and / or connecting a positive or negative electrode to a light absorbing unit's PN junction. In particular, the electronic component is in the form of an organic solar cell, wherein the layer comprising at least one compound of formula (I) is part of a PN junction connecting a light absorbing unit to a further light absorbing unit in a tandem device or a multiple stack device, and / or connecting a positive or negative electrode to a light absorbing unit's PN junction.

[0298] Semiconductor host material

[0299] The compounds of formula (I.1 ) or (I), and charge transfer complexes, reduction products thereof, according to the present application and used according to the present application can be used as dopants in organic semiconductor matrix materials, in particular as p-type dopants in hole transporting layers. The doped semiconductor matrix material preferably comprises at least one electron donor and at least one compound of formula (I.1 ) or (I) as defined above. The electron donor is preferably selected from the group consisting of:

[0300] 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(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(naphthalen-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-spirobifluorene, 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(phenanthren-9-yl)-N,N'-bis(phenyl)-benzidine, 1,3,5-tris{4-[bis(9,9-dimethyl-fluoren-2-yl)amino]phenyl}benzene, tris(bisbiphenyl-4-yl)amine, diaminoterphenylene, diaminotrimethylphenylindanes, N,N'-bis(9,9-dimethylfluoren-2-yl)-N,N'-diphenylbenzidine (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'-spirobis[fluoren]-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-carbazol-3-yl)phenyl)-9H-fluoren-2-amine, and mixtures thereof.

[0301] Suitable diaminoterphenylenes are described in DE 102 012 007 795. Diaminotrimethylphenylindanes are described in WO 2018 / 206769.

[0302] In particular, the electron donor is selected from 4,4',4"-tris(N-(2-naphthyl)-N- phenylamino)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'-Tetra-(N,N-diphenylamino)-9,9'- spirobifluorene (spiro-TTB), N,N'-Bis(naphthalen-1-yl)-N,N'-bis(phenyl)- benzidine, N,N'-Bis(naphthalen-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(phenanthren-9-yl)-N,N'-bis(phenyl)-benzidine, 1,3,5-Tris{4-[bis(9,9-dimethyl- fluorene-2-yl)amino]phenyl}benzene, Tris(bisbiphenyl-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-inden-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-inden-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- inden-5-amine, N-(4-(6-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3- trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)- 9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9'-spirobis[fluoren]-2-yl(9,9-dimethyl-9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1 H-inden-1 -yl)phenyl)-N-(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-1 H-inden-1 -yl)phenyl)-9H-carbazole, N-([1,1 '-biphenyl]-4-yl)-3-(4-([1,1 '-biphenyl]-4-yl(4-methoxyphenyl)amino)phenyl)-N-(4-methoxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1 H-inden-5-amine, 3-(4-(bis(6-methoxy-[1,1 '-biphenyl]-3-yl)amino)phenyl)-N,N-bis(6-methoxy-[1,1 '-biphenyl]-3-yl)-1,1,3-trimethyl-2,3-dihydro-1 H-inden-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-1 H-inden-1 -yl)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, N,N-di([1,1 '-biphenyl]-4-yl)-4'-(6-(4-(di([1,1 '-biphenyl]-4-yl)amino)phenyl]-1,3,3-trimethyl-2,3-dihydro-1 H-inden-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-1 H-inden-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-1 H-inden-1 -yl)phenyl)-N-(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'-diphenylbenzidine (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-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-spirodi[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-9H-fluorene-2-amine and N-(4-(6-(bis(9,9-dimethyl-9H-fluorene)...) A mixture of N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-1H-indene-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluorene-2-yl)-9,9-dimethyl-9H-fluorene-2-amine and mixtures thereof.

[0303] Of course, other suitable organic semiconductor matrix materials can also be used, especially hole-conducting materials with semiconductor properties.

[0304] Doping

[0305] Doping can be carried out in a manner that makes the molar ratio of the matrix molecules to the compound of formula (I.1) or (I) 10000:1 to 1:1, preferably 1000:1 to 2:1, and particularly 5:1 to 100:1. Specifically, doping can be carried out in a manner that makes the molar ratio of the matrix molecules to the compound of formula (I) 10000:1 to 1:1, preferably 1000:1 to 2:1, and particularly 5:1 to 100:1.

[0306] Preparation of doped semiconductor host materials

[0307] The doping of a specific matrix material (hereinafter also referred to as the hole-conducting matrix HT) with a compound of general formula (I.1) or (I) used according to the present invention can be prepared by one or a combination of the following methods:

[0308] a) Evaporation in a vacuum of a mixture of HT source and at least one compound of general formula (I.1) and (I) source (especially at least one compound of general formula (I)).

[0309] b) Sequentially deposit HT and at least one compound of general formula (I.1) or (I) (especially at least one compound of general formula (I)), followed by thermal treatment to allow the dopant to diffuse inward.

[0310] c) The HT layer is doped with a solution of at least one compound of general formula (I.1) or (I) (especially at least one compound of general formula (I)), and then the solvent is evaporated by heat treatment.

[0311] d) applying a layer of at least one compound of the general formula (I.1 ) or (I), in particular of at least one compound of the general formula (I), on one or both surfaces of the HT layer to surface-dope the HT layer.

[0312] e) preparing a solution of the host and at least one compound of the general formula (I.1 ) or (I), in particular of at least one compound of the general formula (I), and forming a film from the solution, for example by means of coating, casting or printing techniques or other film preparation techniques known to the person skilled in the art.

[0313] A further object of the present application is the use of the compound (I.1 ) or mixtures thereof, or the use of the compound (I) or mixtures thereof, in particular of the compound (I) or mixtures thereof as defined above:

[0314] - as organic semiconductors,

[0315] - as dopants in organic semiconducting matrix materials, in particular as p-type dopants in hole transporting layers,

[0316] - as electron transporting materials,

[0317] - as charge injection agents in charge injection layers,

[0318] - as positive electrode materials in organic batteries,

[0319] - as electrochromic materials.

[0320] A further object of the present application is the use of Ce(III) complex anions obtained by reduction of the compound (I.1 ) or (I) as defined above or of charge transfer complexes of the compound (I.1 ) or (I) as defined above with electron donors as organic conductors or electrochromic materials.

[0321] A further object of the present application is the compound of the general formula (I.1 )

[0322] Ce 4+ (L1L2L3L4) 4- (I.1)

[0323] and mixtures thereof, wherein

[0324] L1, L2, L3and L4are independently of each other bidentate ligands of the general formula (I.2)

[0325] wherein

[0326] X and W independently of each other denote O, S or NR 6 ;

[0327] Y denotes N or CR 3 ;

[0328] R 1 , R 2 independently of one another, denote CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, NR 4a R 4b , C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, wherein aryl and heteroaryl are unsub stituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 8 ;

[0329] R 3 denotes hydrogen, CN, nitro, halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylsulfanyl, Ci-C6-haloalkylsulfanyl, NR 4a R 4b , C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7 , O, S, SO and SO2, wherein aryl and heteroaryl are unsub stituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0330] R 4a R 4b independently of one another, denote hydrogen, Ci-C6-alkyl or C6-C 14 -aryl, wherein aryl is unsub stituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 ;

[0331] R 5 denotes CN, halogen, Ci-C4-alkyl or Ci-C4-haloalkyl;

[0332] R 6 denotes hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from the group consisting of N, NR 7O, S, SO and SO2, where aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 substituted;

[0333] R 7 represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C6-C 14 - aryl, where aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 substituted;

[0334] R 8 represents CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C6-C 14 - aryl, the C6-C 14 - aryl is unsubstituted or substituted by 1, 2 or 3 identical or different radicals selected from C1-C4-alkyl and C1-C4-haloalkyl;

[0335] with the proviso that the following compounds are excluded:

[0336]

[0337] It is a further object of the present application compounds of general formula (I)

[0338]

[0339] and charge transfer complexes thereof, reduction products thereof and mixtures thereof, wherein

[0340] X and W independently of one another represent O, S or NR 6 ;

[0341] Y represents N or CR 3 ;

[0342] R 1 , R 2 independently of one another represent 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 - aryl or heteroaryl having 4 to 13 carbon atoms, where heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from N, NR 7 , O, S, SO and SO2, where aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 8 substituted;

[0343] R3 This indicates hydrogen, CN, nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthiol, C1-C6-haloalkylthiol, and NR. 4a R 4b C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from N, NR 7 O, S, SO and SO2, wherein the aryl and heteroaryl groups are not substituted or are occupied by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0344] R 4a R 4b Each can be independently represented as hydrogen, C1-C6-alkyl, or C6-C 14 -aryl, wherein the aryl group is unsubstituted or surrounded by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0345] R 5 Indicates CN, halogen, C1-C4-alkyl, or C1-C4-halogenated alkyl;

[0346] R 6 Represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from N, NR 7 O, S, SO and SO2, wherein the aryl and heteroaryl groups are not substituted or are occupied by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0347] R 7 Indicates hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, or C6-C 14 -aryl, wherein the aryl group is unsubstituted or surrounded by 1, 2, 3, 4 or 5 identical or different groups R. 5 replace;

[0348] R 8 Indicates CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C6-C 14 -Aryl, the C6-C 14 - The aryl group is either unsubstituted or substituted by one, two, or three identical or different groups selected from C1-C4-alkyl and C1-C4-haloalkyl groups;

[0349] with the proviso that the following compounds are excluded:

[0350]

[0351] The following examples serve to illustrate the present application and are in no way intended to limit the same.

[0352] Example

[0353] Synthesis of 1 :

[0354]

[0355] 1,3-Bis(perfluorophenyl)propane-1,3-dione was prepared according to the literature (R. Filler et al., J. Org. Chem. 35(4), 1970, 930).

[0356] 1,3-Bis(perfluorophenyl)propane-1,3-dione (1.61 g, 4.00 mmol) was dissolved in ethanol (50 ml) and 1 M NaOH in ethanol (4 ml, 4 mmol) was added. The solution was stirred for 5 minutes and then cerium(IV) ammonium nitrate (0.55 g, 1 mmol) was added. The dark red solution was stirred for 2 hours. The volatiles were removed under vacuum and the residue was suspended in hexane (40 ml). After 10 minutes of reflux, the suspension was filtered hot and the filtrate was allowed to cool to room temperature. The dark red crystals were isolated by vacuum filtration and dried under vacuum. The solid was recrystallized from hexane, filtered and dried (0.77 g, 0.43 mmol, 44% yield).

[0357] 1 H NMR (300 MHz, CDCI3) δ 6.09.

[0358] 19 F NMR (282 MHz, CDCI3) δ -139.25, -139.31, -149.63, -149.70, -149.78, -160.69, -160.70, -160.73, -160.78, -160.80, -160.85, -160.88, -160.89.

[0359] Melting point: 183 °C

[0360] Cyclovoltametry in dichloromethane shows the following:

[0361] E 1 / 2 (vs Fc / Fc + ) = +0.13 V

[0362] Cyclovoltametry in acetonitrile shows the following:

[0363] E 1 / 2 (versus Fc / Fc + ) = +0.1 V

[0364] Sample preparation:

[0365] The substrates (lxl cm lab glass) were cleaned in an ultrasonic bath with acetone, ethanol and isopropanol.

[0366] The following solutions / concentrations were used for the solvent treatment:

[0367] 1. Spiro-MeO-TAD (N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4-methoxyphenyl)-9,9'- spirobi[9H-fluorene]-2,2',7,7'-tetramine) in chlorobenzene: 30 mg / ml

[0368] 2. Doping agent 1 and Spiro-MeO-TAD and in chlorobenzene: 3 mg / ml (doping agent 1) and 30 mg / ml Spiro-MeO-TAD

[0369] A spin coater from Swiss Sawatec AG was used to coat the layers. For this purpose, the substrate surface was wetted with the solution (one drop was placed in the middle of the substrate). The spin coating was performed at 1000 rpm for 60 seconds under a closed lid and an open ventilation slot. Subsequently, gold metal contacts were deposited by evaporation in vacuum (10 -7 millibar) (30 nm, ).

[0370] Conductivity of Spiro-MeO-TAD without doping agent: < 1 · 10 -9 S / cm

[0371] Conductivity of Spiro-MeO-TAD with 10 wt% of 1 as doping agent: 8.4 · 10 -5 S / cm

[0372] The compound has been solution processed together with the hole transport material CAS [1364603-07-5]. At a doping concentration of 4 mol%, a conductivity of 2.6 · 10 -6 S / cm has been achieved.

[0373] Synthesis of 2:

[0374]

[0375] The compound 2 is commercially available and sublimates without decomposition. The sublimation temperature T subl is 130 to 140 °C (pressure: 2 · 10 -6 millibar).

[0376] 3 was synthesized according to the literature (Lava R. Kadel, John R. Kromer, Curtis E. Moore, David M. Eichhorn Polyhedron 125, 2017, 206-218).

[0377]

[0378] 2-benzoyl-3-oxo-3-phenylpropionitrile was prepared according to the literature (Lava R. Kadel, John R. Kromer, Curtis E. Moore, David M. Eichhorn Polyhedron 125, 2017, 206-218).

[0379] 2-benzoyl-3-oxo-3-phenylpropionitrile (0.50 g, 2 mmol) was dissolved in ethanol (15 ml) and 1 M NaOH in ethanol (2 ml, 2 mmol) was added. The solution was stirred for 5 minutes and then cerium(IV) ammonium nitrate (0.27 g, 0.5 mmol) dissolved in ethanol (5 ml) was added. The dark red solution was stirred for 15 minutes and then filtered. The dark solid was washed with water (100 ml) and ethanol (10 ml) and dried. 460 mg of a dark red solid was obtained.

[0380] Cyclic voltammetry in dichloromethane showed the following potentials:

[0381] E 1 / 2 (vs. Fc / Fc + ) = +0.03 V

[0382] 4 was synthesized according to the literature (C. M. Silvernail et al. Polyhedron 20, 2001, 3113).

[0383]

[0384] 4,4-dimethyl-3-oxo-2-trimethylacetyl pentanenitrile was prepared according to the literature (C. M. Silvernail et al. Polyhedron 20, 2001, 3113).

[0385] 4,4-dimethyl-3-oxo-2-trimethylacetyl pentanenitrile (0.84 g, 4 mmol) was dissolved in ethanol (30 ml) and 1 M NaOH in ethanol (4 ml, 4 mmol) was added. The solution was stirred for 5 minutes and then cerium(IV) ammonium nitrate (0.55 g, 1 mmol) dissolved in ethanol (10 ml) was added. The dark red solution was stirred for 15 minutes. The solvent was removed under vacuum. The residue was extracted with diethyl ether (50 ml) and filtered. The solvent of the filtrate was removed under vacuum. Dark red solid, 500 mg, 51% yield.

[0386] Compound 4 was sublimed. A dark red solid was obtained. The sublimation temperature T subl was 160 °C (pressure: 2-10-6 millibar).

[0387] Cyclic voltammetry in dichloromethane showed the following potentials:

[0388] E 1 / 2 (vs. Fc / Fc + ) = -0.08 V

[0389] Synthesis of 5:

[0390]

[0391] Diisopropylamine (3 g, 30 mmol) was dissolved in 25 mL of dry toluene. The solution was cooled to 0°C and n-BuLi (n-butyllithium, 1.6 M in hexane, 19 mL, 30 mmol) was added. After 10 minutes, 3',5'-bis(trifluoromethyl)acetophenone (7.68 g, 30 mmol) was added. After 1 minute, 3',5'-bis(trifluoromethyl)benzoyl chloride (5.5 g, 20 mmol) was added and the cooling bath was removed. After 2 minutes, concentrated acetic acid (10 mL) was added, followed by 20 mL of water and 10 mL of toluene. The two phases were separated and the organic phase was dried over MgS04and spun down under reduced pressure. The crude diketone was recrystallized from hexane (yield of 1,3-bis(3,5-bis(trifluoromethyl)phenyl)propane-1,3-dione was 3.2 g, 6.45 mmol, 33%).

[0392] 1,3-Bis(3,5-bis(trifluoromethyl)phenyl)propane-1,3-dione (2.57 g, 5.18 mmol) was dissolved in ethanol (100 ml) and 1 M NaOH in ethanol (5.2 ml, 5.2 mmol) was added. The solution was stirred for 5 minutes, then a solution of cerium ammonium nitrate (0.71 g, 1.3 mmol) in ethanol (40 ml) 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 dichloromethane (DCM, 300 ml) and washed with water (100 ml). The organic phase was then dried over MgS04and concentrated under reduced pressure. Hexane (400 mL) was added to produce purple crystals which were filtered and dried under vacuum (2.5 g, 1.17 mmol, 90% yield).

[0393] Melting point: 237 °C (onset), determined by DSC at 10 K / min.

[0394] Cyclic voltammetry in acetonitrile showed the following potentials:

[0395] E 1 / 2 (vs. Fc / Fc + (MeCN): = -0.04 V

[0396] Compound 5 was co-evaporated with the hole transporting material Spiro-MeO-TPD (2,7-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobi[9H-fluorene]). At a doping concentration of 3 mol% the conductivity has reached 8.2 · 10 -5 S / cm.

[0397] The compound was co-evaporated with the hole transporting material MeO-TPD (N,N,N',N'-Tetrakis(4-methoxy-phenyl)benzidine). At a doping concentration of 3 mol% the conductivity has reached 5.2 · 10 -5 S / cm.

[0398] Synthesis of 6

[0399]

[0400] 1-(3,5-bis(trifluoromethyl)phenyl)-4,4,4-trifluorobutane-1,3-dione was prepared according to the literature (Liu et al., Molecules 2016, 21, 828).

[0401] 1-(3,5-bis(trifluoromethyl)phenyl)-4,4,4-trifluorobutane-1,3-dione (2 g, 5.68 mmol) was dissolved in ethanol (50 ml) and 1 M NaOH in ethanol (5.6 ml, 5.6 mmol) was added. The solution was stirred for 5 minutes and then a solution of cerium(IV) ammonium nitrate (0.78 g, 1.42 mmol) in ethanol (20 ml) was added. The dark red solution was stirred for 15 minutes and filtered. The volatiles were removed under vacuum and the residue was re-dissolved in dichloromethane (300 ml) and washed with water (100 ml). The organic phase was then dried over MgS04and concentrated under reduced pressure. Hexane (50 mL) was added to the mixture and the mixture was stored at -20 °C overnight. The isolated solid was then re-crystallized from hot hexane (1 g, 0.64 mmol, 45%).

[0402] Melting point: 155 °C, determined with DSC at 10 K / min (peak).

[0403] Cyclic voltammetry in acetonitrile shows the following potentials:

[0404] E 1 / 2 (vs. Fc / Fc+ (MeCN): = +0.35 V

[0405] Compound 6 was co-evaporated with the hole transporting material BF-DPB (N,N'-bis(9,9-dimethyl-fluoren-2-yl)-N,N'-diphenyl-benzidine). At a doping concentration of 6 mol% the conductivity has reached 7.2 · 10 -6S / cm.

[0406] The compound was co-evaporated with the hole transporting material MeO-TPD. At a doping concentration of 9 mol%, the conductivity has reached 1.6-10 -4 S / cm.

[0407] The compound was co-evaporated with the hole transporting material BPAPF. At a doping concentration of 13 mol%, the conductivity has reached 3-10 -5 S / cm.

[0408] Synthesis of 7

[0409]

[0410] 4,4,4-Trifluoro-1-(thiophen-2-yl)butane-1,3-dione is commercially available.

[0411] 4,4,4-Trifluoro-1-(thiophen-2-yl)butane-1,3-dione (1.8 g, 8.1 mmol) was dissolved in ethanol (40 ml) and 1M NaOH in ethanol (8.1 ml, 8.1 mmol) was added. The solution was stirred for 5 minutes, then a solution of cerium(IV) ammonium nitrate (1.11 g, 2 mmol) in ethanol (20 ml) was added. The dark red precipitate was stirred for 15 minutes and filtered. The solid was rinsed with water (100 ml). The latter was re-dissolved in dichloromethane (400 ml) and washed with water (2 x 200 ml). The organic phase was then dried over MgS04and concentrated under reduced pressure. Hexane (300 mL) was added to yield purple crystals which were filtered, rinsed with hexane (50 ml), pentane (50 ml) and dried under vacuum (1.5 g, 1.46 mmol, 73% yield).

[0412] Melting point: 209 °C (peak) at 10 K / min with DSC.

[0413] Cyclic voltammetry in acetonitrile shows the following potentials:

[0414] E 1 / 2 (vs. Fc / Fc + (MeCN): = +0.20 V

[0415] Synthesis of 8

[0416]

[0417] 4,4,4-Trifluoro-1-(furan-2-yl)butane-1,3-dione is commercially available.

[0418] A solution of 4,4,4-trifluoro-1-(furan-2-yl)butane-1,3-dione (1.57 g, 7.6 mmol) was dissolved in ethanol (40 ml) and 1 M NaOH in ethanol (7.6 ml, 7.6 mmol) was added. The solution was stirred for 5 minutes, then a solution of cerium(IV) ammonium nitrate (1.04 g, 1.9 mmol) in ethanol (20 ml) was added. The dark red precipitate was stirred for 15 minutes and filtered. The solid was rinsed with water (100 ml). The latter was re-dissolved in dichloromethane (300 ml) and washed with water (100 ml). The organic phase was then dried over MgS04and concentrated under reduced pressure. Hexane (200 mL) was added to yield purple crystals which were filtered, rinsed with pentane (100 mL) and dried under vacuum (yield: 1.2 g, 1.32 mmol, 66%).

[0419] Melting point: 166 °C (peak) at 10 K / min with DSC.

[0420] Cyclic voltammetry in acetonitrile shows the following potentials:

[0421] E 1 / 2 (vs. Fc / Fc + (MeCN): = +0.24 V

[0422] Synthesis of 9

[0423]

[0424] A solution of 4,4,4-trifluoro-1-(furan-2-yl)butane-1,3-dione (1.57 g, 7.6 mmol) was dissolved in ethanol (40 ml) and 1 M NaOH in ethanol (7.6 ml, 7.6 mmol) was added. The solution was stirred for 5 minutes, then a solution of cerium(IV) ammonium nitrate (1.04 g, 1.9 mmol) in ethanol (20 ml) was added. The dark red precipitate was stirred for 15 minutes and filtered. The solid was rinsed with water (100 ml). The latter was re-dissolved in dichloromethane (300 ml) and washed with water (100 ml). The organic phase was then dried over MgS04and concentrated under reduced pressure. Hexane (200 mL) was added to yield purple crystals which were filtered, rinsed with pentane (100 mL) and dried under vacuum (yield: 1.2 g, 1.32 mmol, 66%).

[0425] Dissolve 1-(3,5-bis(trifluoromethyl)phenyl)-4,4,5,5,5-pentafluoropentane-1,3-dione (2.22 g, 5.52 mmol) in ethanol (50 ml) and add 1 M NaOH in ethanol (5.5 ml, 5.5 mmol). Stir the solution for 5 minutes then add a solution of cerium ammonium nitrate (0.76 g, 1.38 mmol) in ethanol (15 ml). Stir the deep red solution for 15 minutes and filter. Evaporate the solution under reduced pressure. Extract the red oil with hexane (10 ml) and allow to crystallise overnight at room temperature. Recrystallise the isolated solid from hot hexane and store at -20 °C (yield 2.02 g, 1.16 mmol, 84%).

[0426] Melting point: 129 °C (peak) at 10 K / min by DSC.

[0427] Cyclic voltammetry in acetonitrile shows the following potentials:

[0428] E 1 / 2 (vs Fc / Fc + (MeCN): = +0.46 V

[0429] Synthesis of 10

[0430]

[0431] Dissolve 1-(3',5'-bis(trifluoromethyl)-[1,1 '-biphenyl]-4-yl)ethan-1 -one (4 g, 12 mmol) in THF (50 mL). Cool the mixture to 0 °C and add NaH (1.44 g, 60 mmol). Stir the reaction mixture for 20 minutes then add ethyl 2,2,3,3,3-pentafluoropropionate (6.9 g, 36 mmol). Remove the cold bath and stir the mixture overnight. Concentrate the solution under reduced pressure, add water (20 mL) then add HCI (6 M, 15 mL). Extract the mixture with ethyl acetate (300 mL). Dry the organic phase over MgS04and spin. Purify the crude material by filtration over silica (DCM as eluent) to give 1-(3',5'-bis(trifluoromethyl)-[1,1 '-biphenyl]-4-yl)-4,4,4-trifluorobutane-1,3-dione as a pale red solid (yield: 3.2 g, 62%).

[0432] Dissolve 1-(3',5'-bis(trifluoromethyl)-[1,1 '-biphenyl]-4-yl)-4,4,5,5,5- pentafluoropentane-1,3-dione (1.52 g, 3.17 mmol) in ethanol (50 ml) and add 1 M NaOH in ethanol (3.2 ml, 3.2 mmol). Stir the solution for 5 minutes then add a solution of cerium(IV) ammonium nitrate (0.43 g, 0.79 mmol) in ethanol (20 ml). Stir the deep red solution for 15 minutes and filter. Remove the volatiles under vacuum and redissolve the residue in DCM (250 ml) and wash with water (100 ml). Dry the organic phase over MgS04and spin under reduced pressure. Redissolve the mixture in DCM (50 mL) and add hexane (200 mL). Concentrate the solution under reduced pressure and store at -20 °C to give dark red crystals which are filtered and dried under vacuum (yield 0.6 g, 0.3 mmol, 37%).

[0433] Melting point: 214 °C (peak) measured with DSC at 10 K / min.

[0434] Cyclic voltammetry in acetonitrile shows the following potentials:

[0435] E 1 / 2 (vs. Fc / Fc + : = +0.43 V

[0436] Synthesis of 11

[0437]

[0438] Dissolve methyl 4-cyano-3-(trifluoromethyl)benzoate (2.09 g, 9.12 mmol) in THF (50 mL). Cool the mixture to 0 °C and add NaH (706 mg, 29.4 mmol). Stir the reaction mixture for 20 minutes then add 1-(3,5-bis(trifluoromethyl)phenyl)ethan-1-one (1.95 g, 7.6 mmol). Remove the cold bath and stir the mixture overnight. Concentrate the solution under reduced pressure, add water (10 mL) then HCl (6 M, 10 mL). Extract the mixture with ethyl acetate (40 mL). Dry the organic phase over MgS04and spin. Purify the crude material by recrystallisation from hot EtOH to give a colourless microcrystalline solid (1.32 g, 39%).

[0439] Complex:

[0440] Dissolve 4-(3-(3,5-bis(trifluoromethyl)phenyl)-3-oxopropionyl)-2- (trifluoromethyl)benzonitrile (1.32 g, 2.91 mmol) in EtOH (50 ml) and add 1 M NaOH in EtOH (2.9 ml, 2.9 mmol). Stir the solution for 5 minutes then add a solution of cerium ammonium nitrate (0.4 g, 0.73 mmol) in EtOH (20 ml). Stir the deep red solution for 15 minutes and concentrate under reduced pressure. Filter the deep red precipitate and rinse with water (50 mL), EtOH (5 mL) and hexane (15 mL). Dry the isolated solid under vacuum (1.06 g, 1.16 mmol, 75%).

[0441] Fc / Fc + The potential was measured in acetonitrile at +0.10 V.

[0442] Synthesis of 12 (mixture of homoleptic and heteroleptic cerium complexes)

[0443]

[0444] Dissolve a 1 : 1 mixture of ligand L 1 (1.00 g) and L 2 (1.02 g) in 10 ml of EtOH. Add 9.2 ml of 1 M NaOH solution in EtOH in one portion under stirring. Add 1.26 g of cerium ammonium nitrate (CAN) dissolved in 10 ml of EtOH dropwise. Filter off the red precipitate and wash twice with water. After drying, analyze the red powder by mass spectrometry (atmospheric pressure chemical ionization APCI-, Advion ASAP mass spectrometer). The mass spectrum indicates that two homoleptic complexes Ce(L 1 )4and Ce(L 2 )4as well as all possible heteroleptic complexes as described above are formed.

[0445] Synthesis of 13: (heteroleptic cerium complex)

[0446]

[0447] Dissolve 52 mg of ligand salt NaL 3 in 10 ml of EtOH and add 216 mg of complex Ce(L 2 )4. To the resulting suspension add 5 ml of THF and a homogenous red solution is formed. Mass spectrometric analysis (atmospheric pressure chemical ionization APCI-, Advion ASAP mass spectrometer) of the solution shows that the new complex Ce(L 2 )3L 3 is formed in part.

Claims

1. An electronic component comprising a hole transport layer and / or a hole injection layer, said hole transport layer and hole injection layer comprising at least one compound of said general formula (I), or a mixture thereof, wherein X and W represent O; Y represents CR 3 ; R 1 R 2 Each can be independently represented as CN, C1-C6-alkyl, C1-C6-haloalkyl, C6-C 14 -aryl or heteroaryl having 4 to 13 carbon atoms, wherein the heteroaryl has 1, 2 or 3 identical or different heteroatoms or heteroatom-containing groups as ring members, selected from N, NR 7 O and S, wherein the aryl and heteroaryl groups are not substituted or are occupied by 1, 2, 3, 4 or 5 identical or different groups R. 8 replace; R 3 represents hydrogen, CN, halogen, Ci-C6-alkyl or Ci-C6-haloalkyl; R 5 represents CN, halogen, C1-C4-alkyl or C1-C4-haloalkyl; R 7 represents hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl or C6-Ci0-aryl; or 14 - aryl, wherein aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 substituents; R 8 represents CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C6-C 14 - aryl, said C6-C 14 - aryl is unsubstituted or substituted by 1, 2 or 3 identical or different radicals selected from the group consisting of C1-C4-alkyl and C1-C4-haloalkyl.

2. The electronic assembly according to claim 1, wherein R 1 and R 2 are independently selected from the group A consisting of CN, Ci-C6-alkyl, Ci-C6-haloalkyl and A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18 and A19. Where # represents the bond with the remaining molecules in formula (I); R A , R B , R C , R D and R E are independently selected from hydrogen, CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl and phenyl, which is unsub- stituted or substituted by one, two or three identical or different radicals selected from C1-C4-alkyl and C1-C4-haloalkyl; R 5 represents CN, halogen, Ci-C4-alkyl or Ci-C4-haloalkyl; and R 7 represents hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl or C6-Ci0-aryl. 14 - aryl, wherein aryl is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different radicals R 5 substituents.

3. Electronic component according to claim 2, wherein in A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14 and A15 the radicals R A , R B , R C , R D and R E are independently of each other selected from hydrogen, CN, fluorine, chlorine, Ci-C4-alkyl, Ci-C4-fluoroalkyl, Ci-C4-chloroalkyl and phenyl, which is unsubstituted or substituted by 1, 2 or 3 identical or different radicals selected from Ci-C4-haloalkyl.

4. Electronic assembly according to any of the preceding claims 1 to 3, wherein in the ligand of formula (I) Y represents a group CR 3 wherein R 3 is selected from hydrogen, CN, halogen and CF3.

5. The electronic assembly according to any one of the preceding claims 1 to 3, wherein in the ligand of formula (I), R 1 and R 2 are independently selected from the group consisting of Ci-C4-alkyl, Ci-C4-haloalkyl, A1, A5, A16, and A17, wherein # denotes the bond to the remainder of the molecule of formula (I), and wherein R A , R B , R C , R D and R E are independently selected from hydrogen, CN, fluorine, chlorine, Ci-C4-alkyl, Ci-C4-fluoroalkyl, Ci-C4-chloroalkyl and phenyl, which phenyl is unsubstituted or substituted by 1, 2 or 3 identical or different radicals selected from Ci-C4-haloalkyl.

6. Electronic assembly according to the preceding claim 5, wherein in the ligand of formula (I) Y represents a group CR 3 , and wherein R 3 is selected from hydrogen, CN, halogen and CF3.

7. The electronic component according to claim 1, wherein the compound of formula (I) is selected from the compounds of formula (Ia). wherein R 1 , R 2 and R 3 are each selected from the definitions given in one row of the following table:

8. The electronic component according to any one of claims 1-3, 6 and 7, wherein it is in the form of an organic light-emitting diode, an organic solar cell, a photovoltaic cell, an organic diode or an organic transistor.

9. The electronic component according to claim 4 is in the form of an organic light-emitting diode, an organic solar cell, a photovoltaic cell, an organic diode, or an organic transistor.

10. The electronic component according to claim 5 is in the form of an organic light-emitting diode, an organic solar cell, a photovoltaic cell, an organic diode, or an organic transistor.

11. The electronic component according to claim 8 is in the form of a thin-film transistor or a perovskite solar cell.

12. The electronic component according to claim 9 is in the form of a thin-film transistor or a perovskite solar cell.

13. The electronic component according to claim 10 is in the form of a thin-film transistor or a perovskite solar cell.

14. The electronic component according to any one of claims 1-3, 6, 7 and 9-13, having a layered structure comprising 2, 3, 4, 5, 6, 7 or more layers.

15. A doped semiconductor matrix material comprising at least one electron donor and at least one compound of formula (I) according to any one of claims 1-7.

16. The doped semiconductor matrix material of claim 15, 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'-Tetrakis(4-methoxy-phenyl)benzidine (MeO-TPD), (2,2',7,7'-Tetra-(N,N-diphenylamino)-9,9'-spirobifluorene (spiro-TTB), N,N'-Bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine, N,N'-Bis(naphthalen-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-spirobifluorene, 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(phenanthren-9-yl)-N,N'-bis(phenyl)-benzidine, 1,3,5-Tris{4-[bis(9,9-dimethyl-fluoren-2-yl)amino]phenyl}benzene, Tris(bisbiphenyl-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-inden-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-inden-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-inden-5-amine, N-(4-(6-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H- inden-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-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-inden-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluoren-2- amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)- 9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3- dihydro-1H-inden-1-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2- yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)- 9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3- dihydro-1H-inden-1-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2- yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)- 9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3- dihydro-1H-inden-1-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2- yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)- 9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3- dihydro-1H-inden-1-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2- yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)- 9,9-dimethyl-9H-fluoren-2-amine, N-(4-(6-(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1 H-inden-1 -yl)phenyl)-N-(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-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-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-spirobis[9H-fluorene] (spiro-MeO-TPD), a mixture of N-(4-(5-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluoren-2-amine and N-(4-(6-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)-1,3,3-trimethyl-2,3-dihydro-1H-inden-1-yl)phenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluoren-2-amine, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine and mixtures thereof.

17. Use of a compound (I) or a mixture thereof according to any one of claims 1-7, for use as a dopant in an organic semiconductor matrix material.

18. The use according to claim 17, wherein the compound (I) or a mixture thereof is a p-type dopant in a hole transport layer.

19. A compound of general formula (I): in X and W represent O; Y represents CR 3 ; R 1 represents A1 wherein # indicates the bond with the remaining molecules in equation (I). R A , R B , R C , R D and R E are independently of each other selected from hydrogen, CN, fluorine, chlorine, Ci-C4-fluoroalkyl, Ci-C4-chloroalkyl; R 2 represents Ci-C6-haloalkyl; R 3 represents hydrogen and CN; The condition is that the following compounds must be excluded:

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