Material for electronic device

Abstract

To provide a compound suitable for use in an electronic device.SOLUTION: A fluorenylamine compound of a specific formula, having different substituents at the 9 and 9' positions and represented by the following general formula (I), is provided.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present application relates to fluorenylamine compounds of certain formulas, each having different substitutions at the 9 and 9' positions. The compounds are suitable for use in electronic devices.

[0002] Electronic devices in the context of this application are understood to mean so-called organic electronic devices that contain organic semiconductor materials as functional materials. More specifically, they are understood to mean OLEDs (organic electroluminescent devices). The term OLED is understood to mean an electronic device that has one or more layers containing organic compounds and emits light when a voltage is applied. The general principles of the structure and function of OLEDs are known to those skilled in the art.

[0003] There is a strong interest in improving the performance data of electronic devices, especially OLEDs, and no completely satisfactory solutions have yet been found in these aspects.

[0004] The light-emitting layer and the layer with hole transport function have a great influence on the performance data of electronic devices.New compounds are required for these layers, especially hole transport compounds, and compounds that can function as hole transport matrix materials, especially for phosphorescent emitters, in light-emitting layers.For this purpose, compounds with high glass transition temperature, high stability, and high hole conductivity are especially sought.High stability of compounds is a prerequisite for achieving long life of electronic devices.

[0005] In the prior art, triarylamine compounds are particularly known as hole transport materials and hole transporting matrix materials for electronic devices. Known triarylamine compounds for use in electronic devices also include fluorenylamine compounds, i.e., triarylamine compounds in which at least one aryl group is a fluorenyl group.

[0006] However, there remains a need for alternative compounds suitable for use in electronic devices, particularly compounds that possess one or more of the above advantageous attributes. There remains a need for improvements in the performance data achieved when compounds are used in electronic devices, particularly with respect to device lifetime, operating voltage, and efficiency.

[0007] It has been found that certain fluorenylamine compounds have excellent suitability for use in electronic devices, especially for use in OLEDs, especially for use as hole transport materials and hole transport matrix materials for phosphorescent emitters in electronic devices.This compound leads to long device life, high efficiency and low operating voltage.More preferably, this compound has high glass transition temperature, high stability and high hole conductivity.

[0008] The discovered compounds are of formula (I)

[0009] [ka]

[0010] wherein the occurring variables are as follows: Z is -[Ar1] k When an -N(Ar2)(Ar3) group is attached to it, it is C, and Z is -[Ar1] k -N(Ar2)(Ar3) is in each case the same or different, CR1 or N, if no group is attached thereto; Ar1, in each occurrence, is the same or different and is an aromatic ring system having 6 to 40 aromatic ring atoms and substituted by an R3 radical, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted by an R3 radical; Ar2 is an aromatic ring system having 6 to 40 aromatic ring atoms and substituted by an R4 radical, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted by an R4 radical; Ar3 is an aromatic ring system having 6 to 40 aromatic ring atoms and substituted by an R4 radical, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted by an R4 radical; Ar4 is phenyl optionally substituted by an R2 radical or naphthyl optionally substituted by an R2 radical; R1 in each occurrence is the same or different and is selected from H, D, F, Cl, Br, I, C(=O)R5, CN, Si(R5)3, N(R5)2, P(=O)(R5)2, OR5, S(=O)R5, S(=O)2R5, a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; The above R1 radicals may be bonded to each other or may form a ring; the mentioned alkyl, alkoxy, alkenyl and alkynyl groups, as well as the mentioned aromatic and heteroaromatic ring systems, are each substituted by an R5 radical; one or more CH2 groups in the mentioned alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R5C=CR5-, -C≡C-, Si(R5)2, C=O, C=NR5, -C(=O)O-, -C(=O)NR5-, NR5, P(=O)(R5), -O-, -S-, SO or SO2; R2, in each occurrence, is the same or different and is selected from D, F, CN, Si(R5)3, N(R5)2, aromatic ring systems having 6 to 40 aromatic ring atoms and substituted by R5 radicals, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and substituted by R5 radicals; R3, in each occurrence, is the same or different and is selected from H, D, F, Cl, Br, I, C(=O)R5, CN, Si(R5)3, N(R5)2, P(=O)(R5)2, OR5, S(=O)R5, S(=O)2R5, a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; The above R3 radicals may be bonded to each other or may form a ring; the mentioned alkyl, alkoxy, alkenyl and alkynyl groups, as well as the mentioned aromatic and heteroaromatic ring systems, are each substituted by an R5 radical; one or more CH2 groups in the mentioned alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R5C=CR5-, -C≡C-, Si(R5)2, C=O, C=NR5, -C(=O)O-, -C(=O)NR5-, NR5, P(=O)(R5), -O-, -S-, SO or SO2; R4, in each occurrence, is the same or different and is selected from H, D, F, Cl, Br, I, C(=O)R5, CN, Si(R5)3, N(R5)2, P(=O)(R5)2, OR5, S(=O)R5, S(=O)2R5, a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; The above R4 radicals may be bonded to each other or may form a ring; the mentioned alkyl, alkoxy, alkenyl and alkynyl groups, as well as the mentioned aromatic and heteroaromatic ring systems, are each substituted by an R5 radical; one or more CH2 groups in the mentioned alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R5C=CR5-, -C≡C-, Si(R5)2, C=O, C=NR5, -C(=O)O-, -C(=O)NR5-, NR5, P(=O)(R5), -O-, -S-, SO or SO2; R5, in each occurrence, is the same or different and is selected from H, D, F, Cl, Br, I, C(=O)R6, CN, Si(R6)3, N(R6)2, P(=O)(R6)2, OR6, S(=O)R6, S(=O)2R6, a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; The above R5 radicals may be bonded to each other or may form a ring; the mentioned alkyl, alkoxy, alkenyl and alkynyl groups, as well as the mentioned aromatic and heteroaromatic ring systems, are each substituted by an R6 radical; one or more CH2 groups in the mentioned alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R6C=CR6-, -C≡C-, Si(R6)2, C=O, C=NR6, -C(=O)O-, -C(=O)NR6-, NR6, P(=O)(R6), -O-, -S-, SO or SO2; R6, in each occurrence, is the same or different and is selected from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by one or more radicals selected from F and CN; k is 0, 1, 2, 3 or 4, and when k=0, the Ar1 group is absent and the groups bonded to Ar1 in formula (I) are bonded directly to each other; i is 0, 1, 2, 3, 4 or 5; n is 0, 1, 2, 3 or 4; The two groups in formula (I)

[0011] [ka]

[0012] are not the same as the whole, including their respective substituents) matches.

[0013] When i=1, it means that the R2 group is attached to exactly one position on the benzene ring. When n=1, it means that the R2 group is attached to exactly one position on the benzene ring.

[0014] When i=2, 3, 4, or 5, it means that one R2 group is bonded to each of 2, 3, 4, or 5 different positions on the benzene ring. When n=2, 3, or 4, it means that one R2 group is bonded to each of 2, 3, or 4 different positions on the benzene ring.

[0015] When i=0 or n=0, this means that there is no R2 radical and only a hydrogen atom attached to the benzene ring.

[0016] The following definitions are applicable to chemical groups used in this application unless any further specific definition is given.

[0017] An aryl group in the context of the present invention is understood to mean either a single aromatic ring, i.e., benzene, or a fused aromatic polycycle, such as naphthalene, phenanthrene, or anthracene. A fused aromatic polycycle in the context of the present application consists of two or more single aromatic rings fused to one another. Fusion between rings is understood here to mean that the rings share at least one edge with one another. An aryl group in the context of the present invention contains 6 to 40 aromatic ring atoms, none of which are heteroatoms.

[0018] A heteroaryl group in the context of the present invention is understood to mean either a single heteroaromatic ring, such as pyridine, pyrimidine, or thiophene, or a fused heteroaromatic polycycle, such as quinoline or carbazole. A fused heteroaromatic polycycle in the context of the present application consists of two or more single aromatic or heteroaromatic rings fused together, at least one of the aromatic and heteroaromatic rings being a heteroaromatic ring. Fusion between rings is understood here to mean that the rings share at least one edge with each other. A heteroaryl group in the context of the present invention contains 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom in the heteroaryl group is preferably selected from N, O, and S.

[0019] The aryl or heteroaryl groups, each of which may be substituted by the above-mentioned radicals, are especially benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indophenyl, benzophenone, benzoisobenzothiophene, dibenzothiophene, pyrrole, indophenyl, benzophenone, benzoisobenzothiophene, dibenzothiophene, pyrrole, indophenyl, benzophenone, benzoisobenzothiophene, dibenzoisobenzothiophene, pyrrole, indophenyl, benzoisobenzothiophene, benzoisobenzothiophene, dibenzoisobenzothiophene, pyrrole, indophenyl, benzoisobenzothiophene, benzoisobenzothiophene, dibenzoisobenzothiophene, pyrrole, indophenyl, benzoisobenzothiophene, benzoisobenzothiophene, dibenzoisobenzothiophene, pyrrole, indophenyl, benzoisobenzothiophene, benzoisobenzofuran, dibenzoisobenzothiophene, pyrrole, indophenyl ...furan, pyrrole, indophenyl, benzoisobenzofuran, dibenzoiso benzoindole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, benzimidazolo[1,2-a]benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, oxazole, benzimidazole benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole is understood to mean groups derived from 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0020] An aromatic ring system in the context of this invention does not necessarily contain only aryl groups, but may also contain one or more additional non-aromatic rings fused to at least one aryl group. These non-aromatic rings contain only carbon atoms as ring atoms. Examples of groups encompassed by this definition are tetrahydronaphthalene, fluorene, and spirobifluorene. Additionally, the term "aromatic ring system" includes systems consisting of two or more aromatic ring systems bonded to each other via a single bond, such as biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quaterphenyl, and 3,5-diphenyl-1-phenyl. An aromatic ring system in the context of this invention contains 6 to 40 carbon atoms in the ring system but does not contain heteroatoms. The definition of "aromatic ring system" does not include heteroaryl groups.

[0021] A heteroaromatic ring system conforms to the definition of an aromatic ring system above, except that it must contain at least one heteroatom as a ring atom. As with aromatic ring systems, a heteroaromatic ring system need not contain only aryl and heteroaryl groups, but may also contain one or more additional non-aromatic rings fused to at least one aryl or heteroaryl group. A non-aromatic ring may contain only carbon atoms as ring atoms, or it may contain one or more additional heteroatoms, preferably selected from N, O, and S. An example of such a heteroaromatic ring system is benzopyranyl. Additionally, the term "heteroaromatic ring system" is understood to mean a system consisting of two or more aromatic or heteroaromatic ring systems bonded to each other via a single bond, such as 4,6-diphenyl-2-triazinyl. A heteroaromatic ring system in the context of the present invention contains 5 to 40 ring atoms selected from carbon and heteroatoms, with at least one of the ring atoms being a heteroatom. The heteroatoms in a heteroaromatic ring system are preferably selected from N, O, and S.

[0022] Thus, the terms "heteroaromatic ring system" and "aromatic ring system," as defined herein, differ from each other in that an aromatic ring system cannot have a heteroatom as a ring atom, while a heteroaromatic ring system must have at least one heteroatom as a ring atom, which may be present as a ring atom of either a non-aromatic or aromatic heterocyclic ring.

[0023] According to the above definitions, any aryl group is encompassed by the term "aromatic ring system" and any heteroaryl group is encompassed by the term "heteroaromatic ring system".

[0024] An aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms is understood to mean, in particular, a radical derived from the radicals mentioned above under the aryl radical and heteroaryl radical, and from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, indenocarbazole, or a combination of these radicals.

[0025] In the context of the present invention, linear alkyl groups having 1 to 20 carbon atoms and branched or cyclic alkyl groups having 3 to 20 carbon atoms and alkenyl or alkynyl groups having 2 to 40 carbon atoms are understood to mean groups in which the individual hydrogen atoms or CH groups may also be substituted by the groups mentioned above in the definition of the radicals, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, ... cyclohexyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl radical.

[0026] In the alkoxy or thioalkyl groups having 1 to 20 carbon atoms, individual hydrogen atoms or CH groups may also be replaced by the groups mentioned above in the definition of the radicals, preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i -butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0027] The expression that two or more radicals may join together to form a ring is to be understood in the context of this application to mean, inter alia, that the two radicals are bonded to one another by a chemical bond, but in addition, the expression should also be understood to mean that if one of the two radicals is hydrogen, the second radical is bonded to the position where the hydrogen atom was bonded, thereby forming a ring.

[0028] The compounds of formula (I) are preferably monoamines, which are understood to mean compounds containing a single triarylamino group and no further triarylamino groups, more preferably compounds containing a single amino group and no further amino groups.

[0029] Z is -[Ar1] k If no -N(Ar2)(Ar3) group is attached to it, it is preferably CR1.

[0030] Ar1 is preferably selected from aromatic ring systems having 6 to 20 aromatic ring atoms, optionally substituted with one or more R3 radicals, and heteroaromatic ring systems having 5 to 20 aromatic ring atoms, optionally substituted with one or more R3 radicals. Particularly preferred Ar1 groups are selected from divalent radicals derived from benzene, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which may be substituted with one or more R3 radicals. Most preferably, Ar1 is a divalent radical derived from benzene, optionally substituted in each case with one or more R3 radicals. The Ar1 groups may be selected identically or differently in each case.

[0031] Preferably, k is selected from 0 or 1; more preferably, k is 0.

[0032] Preferred when k=1 - (Ar1) k The - group has the formula:

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] wherein the dotted line represents the bond to the remainder of formula (I), and the groups at positions shown as unsubstituted are each substituted with an R radical, the R radical at these positions being preferably H. matches.

[0040] Preferably, the Ar2 and Ar3 groups are in each case the same or different and are selected from monovalent radicals derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, especially 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, 9-silafluorene, especially 9,9'-dimethyl-9-silafluorene and 9,9'-diphenyl-9-silafluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine, and triazine, each of which is substituted by one or more R4 radicals. Alternatively, the Ar2 and Ar3 groups may in each case be the same or different and are preferably selected from a combination of groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, especially 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, 9-silafluorene, especially 9,9'-dimethyl-9-silafluorene and 9,9'-diphenyl-9-silafluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, each of which is substituted by one or more R4 radicals.

[0041] Particularly preferred Ar2 and Ar3 groups, which are in each case the same or different, are selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, the groups mentioned being each substituted by one or more R4 radicals.

[0042] In a preferred embodiment, exactly one group selected from the Ar2 and Ar3 groups is phenyl substituted by an R4 radical, which is preferably selected from H, D, F, CN and an alkyl group having 1 to 10 carbon atoms, more preferably H. Such compounds have particularly good hole transporting properties.

[0043] Particularly preferred Ar2 and Ar3 groups are the same or different and have the formula:

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048]

change

[0049]

change

[0050]

change

[0051]

change

[0052]

change

[0053]

change

[0054]

change

[0055]

change

[0056]

change

[0057]

change

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] wherein the groups at positions shown as unsubstituted are substituted with R radicals, R at these positions is preferably H, and the dotted bond is the bond to the amine nitrogen atom. is selected from.

[0064] In a preferred embodiment, Ar2 and Ar3 in formula (I) are selected to be different.

[0065] Ar4 is preferably phenyl optionally substituted with an R2 radical or 1-naphthyl optionally substituted with an R2 radical, more preferably phenyl optionally substituted with an R2 radical, most preferably unsubstituted phenyl or 1-naphthyl, most preferably unsubstituted phenyl.

[0066] R1 is preferably the same or different in each case and is selected from H, D, F, CN, Si(R5)3, N(R5)2, linear alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; the alkyl and alkoxy groups mentioned, the aromatic ring systems mentioned, and the heteroaromatic ring systems mentioned are each substituted by an R5 radical; one or more CH2 groups in the alkyl or alkoxy groups mentioned may be replaced by -C≡C-, -R5C=CR5-, Si(R5)2, C=O, C=NR5, -NR5-, -O-, -S-, -C(=O)O- or -C(=O)NR5-. More preferably, R1 in each occurrence is the same or different and is selected from H, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, the aromatic ring system and the heteroaromatic ring system each being substituted by an R5 radical. Most preferably, R1 is H.

[0067] In a preferred embodiment, one or two, preferably one, R1 radical is selected from an aromatic ring system having 6 to 40 aromatic ring atoms and substituted by an R5 radical, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted by an R5 radical, and the other R1 radical is H. Particularly preferred embodiments of aromatic and heteroaromatic ring systems as R1 radicals in this case are phenyl, biphenyl, terphenyl, fluorenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl and N-phenylcarbazolyl, each substituted by an R5 radical, and these R5 radicals are preferably H. Preferably, the R1 radical selected from an aromatic or heteroaromatic ring system in formula (I) is attached to the fluorene at a position selected from the 5-8 positions in formula (I), more preferably at the 5-position.

[0068] Preferably, R1 is not N(R5)2. More preferably, the R1 radical containing the substituent does not contain an amino group.

[0069] R2 is preferably the same or different in each case and is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted by an R5 radical, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and substituted by an R5 radical. More preferably, R2 is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted by an R5 radical; most preferably, R2 is selected from phenyl, fluorenyl, especially 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, and naphthyl, the mentioned groups each being substituted by an R5 radical, in which case R5 is preferably H.

[0070] R3 is preferably the same or different in each case and is selected from H, D, F, CN, Si(R5)3, N(R5)2, linear alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; the alkyl and alkoxy groups mentioned, the aromatic ring systems mentioned, and the heteroaromatic ring systems mentioned are each substituted by an R5 radical; one or more CH2 groups in the alkyl or alkoxy groups mentioned may be replaced by -C≡C-, -R5C=CR5-, Si(R5)2, C=O, C=NR5, -NR5-, -O-, -S-, -C(=O)O- or -C(=O)NR5-. More preferably, R3, in each occurrence, is the same or different and is selected from H, N(R5)2, a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein the alkyl group, aromatic ring system, and heteroaromatic ring system are each substituted with an R5 radical. Most preferably, R3 is H.

[0071] R4 is preferably the same or different in each case and is selected from H, D, F, CN, Si(R5)3, N(R5)2, linear alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; the alkyl and alkoxy groups mentioned, the aromatic ring systems mentioned, and the heteroaromatic ring systems mentioned are each substituted by an R5 radical; one or more CH2 groups in the alkyl or alkoxy groups mentioned may be replaced by -C≡C-, -R5C=CR5-, Si(R5)2, C=O, C=NR5, -NR5-, -O-, -S-, -C(=O)O- or -C(=O)NR5-. More preferably, R4, in each occurrence, is the same or different and is selected from H, N(R5)2, a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein the alkyl group, aromatic ring system, and heteroaromatic ring system are each substituted with an R5 radical. Most preferably, R4 is H.

[0072] R5 is preferably the same or different in each case and is selected from H, D, F, CN, Si(R6)3, N(R6)2, linear alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; the alkyl and alkoxy groups mentioned, the aromatic ring systems mentioned, and the heteroaromatic ring systems mentioned are each substituted by an R6 radical; one or more CH2 groups in the alkyl or alkoxy groups mentioned may be replaced by -C≡C-, -R6C=CR6-, Si(R6)2, C=O, C=NR6, -NR6-, -O-, -S-, -C(=O)O- or -C(=O)NR6-. More preferably, R5, in each occurrence, is the same or different and is selected from H, a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein the alkyl group, aromatic ring system, and heteroaromatic ring system are each substituted with an R6 radical. Most preferably, R5 is H.

[0073] In a preferred embodiment, i = 0. In a preferred embodiment, n = 0. More preferably, i and n are each 0.

[0074] -[Ar1] k It is preferred that the -N(Ar2)(Ar3) group is attached to the fluorenyl group at position 1, 2 or 4 in formula (I), more preferably at position 2 or 4, and most preferably at position 4.

[0075] A preferred embodiment of formula (I) is the following formula:

[0076] [ka]

[0077] [ka]

[0078] (wherein the symbols and indices appearing are as defined above, and the R1 radical to which it is attached means that all positions on the benzene ring shown as unsubstituted are substituted with an R1 radical). Particularly preferably, in the above formula, i=0 and n=0. It is further preferred that R2 is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted with an R5 radical. Again, it is further preferred that R1 is H. Again, it is further preferred that Ar4 is phenyl or 1-naphthyl, preferably phenyl, each of which may be substituted, but preferably is unsubstituted, with an R2 radical.

[0079] Among the above formulas (IA) to (IH), formulas (IA) to (ID), (IG), and (IH) are preferred, and formulas (IC), (ID), (IG), and (IH) are even more preferred. Most preferred are formulas (IC) and (ID).

[0080] A preferred embodiment of formula (I) is the following formula:

[0081] [ka]

[0082] (wherein the symbols and indices appearing are as defined above, and the R1 radical to which it is attached means that all positions on the benzene ring shown as unsubstituted are substituted with an R1 radical). Particularly preferably, in the above formula, n=0. It is more preferred that R2 is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted with an R5 radical. It is more preferred that R1 is H. It is more preferred that Ar4 is phenyl or 1-naphthyl, preferably phenyl, each of which may be substituted, but is preferably unsubstituted, with an R2 radical.

[0083] Among the above formulae (I-1) to (I-3), formulae (I-1) and (I-2) are preferred.

[0084] A preferred embodiment of formula (I) is the following formula:

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] (wherein the symbols and indices appearing are as defined above, and the R radical to which it is attached means that all positions shown as unsubstituted on the benzene ring are substituted with an R radical). Preferably, R is H. It is particularly preferred that Ar is selected from divalent radicals derived from benzene, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which may be substituted with one or more R radicals. It is further preferred that Ar and Ar are in each case the same or different and are selected from groups of formulae (Ar-1) to (Ar-256) as defined above.

[0093] Of the above formulae, formulae (IA-1), (IA-2), (IB-1), (IB-2), (IC-1), (IC-2), (ID-1), (ID-2), (IE-1), (IE-2), (IF-1), (IF-2), (IG-1), (IG-2), (IH-1) and (IH-2) are particularly preferred.

[0094] Preferred embodiments of the compounds of formula (I) are shown below:

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098]

change

[0099]

change

[0100]

change

[0101]

change

[0102]

change

[0103]

change

[0104]

change

[0105]

change

[0106]

change

[0107]

change

[0108]

change

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] [ka]

[0117] [ka]

[0118] The compounds of formula (I) can be prepared by conventional synthetic methods in organic chemistry, such as the Buchwald coupling reaction and the Suzuki coupling reaction.

[0119] A preferred synthetic route for the compounds according to the present application is shown below: A person skilled in the art can modify this synthetic route within the scope of his or her general technical knowledge.

[0120] [ka]

[0121] In the first step, a metal organyl is added to a carbonyl derivative bearing a phenyl or naphthyl-substituted phenyl group and a phenyl group. This metal organyl is formed from a biphenyl substituted with two reactive groups, at least one of which is attached to the biphenyl at the ortho position. After the addition, cyclization is carried out under acidic conditions. This results in a fluorenyl derivative containing a phenyl group at the bridgehead carbon atom and a phenyl or naphthyl-substituted phenyl group, bearing a reactive group on one of its benzene rings. A diarylamino group can be introduced via this reactive group in a Buchwald reaction, or an aromatic or heteroaromatic ring system bearing a diarylamino group can be introduced in a two-step reaction. Two-step reactions include the Suzuki reaction, which introduces an aromatic or heteroaromatic ring system bearing a reactive group at the reactive group, and the Buchwald reaction, which introduces a diarylamino group at the reactive group on an aromatic or heteroaromatic ring system.

[0122] The reactive group is preferably selected from Cl, Br and I, more preferably Br.

[0123] The R groups are preferably the same or different in each occurrence and are selected from H, F, heteroaryl groups having 5 to 40 aromatic ring atoms, and aryl groups having 6 to 40 aromatic ring atoms. One or more R groups can be present on the benzene ring.

[0124] Preferably, the aryl group Ar4 in the scheme shown above is selected from phenyl, which is preferably unsubstituted.

[0125] Thus, the present application provides a method for preparing a compound of formula (I), characterized in that a biphenyl derivative having two reactive groups, at least one of which is in the ortho position, is metallated and then added to a carbonyl derivative containing a phenyl or naphthyl-substituted phenyl group and a phenyl group bonded to the carbonyl group. The method preferably is characterized in that subsequent cyclization is carried out under acidic conditions, thereby obtaining a fluorenyl derivative having a phenyl group on the bridgehead carbon atom and a phenyl or naphthyl-substituted phenyl group substituted with a reactive group. Preferably, this fluorenyl derivative is then reacted with a secondary amine having two substituents selected from aromatic and heteroaromatic ring systems in a Buchwald reaction to obtain a compound of formula (I). In an alternative, equally preferred embodiment, the fluorenyl derivative is reacted with an aromatic or heteroaromatic ring system having two reactive groups in a Suzuki reaction. In this embodiment, the fluorenyl derivative is then reacted in a Buchwald reaction with a secondary amine bearing two substituents selected from aromatic and heteroaromatic ring systems to give the compound of formula (I).

[0126] The above compounds of the present invention, especially those substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic esters, can find use as monomers for preparing corresponding oligomers, dendrimers or polymers. Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boronic acid, boronic esters, amines, alkenyl or alkynyl groups with terminal C-C double or C-C triple bonds, oxiranes, oxetanes, groups participating in cycloadditions, for example 1,3-dipolar cycloadditions, such as dienes or azides, carboxylic acid derivatives, alcohols and silanes.

[0127] Thus, the present invention further provides oligomers, polymers, or dendrimers containing one or more compounds of formula (I), wherein the attachment to the polymer, oligomer, or dendrimer may be located at any desired position substituted by R1, R2, R3, or R4 in formula (I). Depending on the attachment of the compound of formula (I), the compound becomes part of a side chain or part of the main chain of the oligomer or polymer. An oligomer in the context of the present invention is understood to mean a compound formed from at least three monomer units. A polymer in the context of the present invention is understood to mean a compound formed from at least 10 monomer units. The polymers, oligomers, or dendrimers of the present invention may be conjugated, partially conjugated, or non-conjugated. The oligomers or polymers of the present invention may be linear, branched, or dendritic. In structures having linear bonds, the units of formula (I) may be bonded to each other directly or through divalent groups, such as substituted or unsubstituted alkylene groups, heteroatoms, or divalent aromatic or heteroaromatic groups. In branched and dendritic structures, for example, three or more units of formula (I) can be bonded to each other through trivalent or higher valent groups, such as trivalent or higher valent aromatic or heteroaromatic groups, resulting in a branched or dendritic oligomer or polymer.

[0128] For repeat units of formula (I) in oligomers, dendrimers and polymers, the same preferences apply as described above for compounds of formula (I).

[0129] To prepare oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with other monomers.Suitable and preferred comonomers are selected from fluorene, spirobifluorene, paraphenylene, carbazole, thiophene, dihydrophenanthrene, cis- and trans-indenofluorene, ketone, phenanthrene, or two or more of these units.Polymers, oligomers and dendrimers typically contain further units, such as luminescent (fluorescent or phosphorescent) units, such as vinyltriarylamine or phosphorescent metal complexes, and / or charge transport units, especially those based on triarylamine.

[0130] The polymers, oligomers and dendrimers of the present invention have advantageous properties, among them long lifetime, high efficiency and good color coordinates.

[0131] The polymers and oligomers of the present invention are generally prepared by polymerization of one or more monomers, at least one of which provides the repeating units of formula (I) in the polymer. Suitable polymerization reactions are known to those skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions that result in CC and CN coupling are as follows: (A) Suzuki polymerization; (B) Yamamoto polymerization; (C) Stille polymerization; and (D) Hartwig-Buchwald polymerization.

[0132] How polymerization can be carried out by these methods and how the polymer can then be separated from the reaction medium and purified is known to those skilled in the art and is well described in the literature.

[0133] To process the compounds of the present invention from a liquid phase, for example by spin coating or printing, a formulation of the compounds of the present invention is required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanol. Sanon, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or a mixture of these solvents.

[0134] The present invention therefore further provides a formulation, in particular a solution, dispersion or emulsion, comprising at least one compound of formula (I) or at least one polymer, oligomer or dendrimer containing at least one unit of formula (I) and at least one solvent, preferably an organic solvent. The methods by which such solutions can be prepared are known to those skilled in the art.

[0135] The compound of formula (I) is suitable for use in electronic devices, especially organic electroluminescent devices (OLED).Depending on substitution, the compound of formula (I) can be used in various functions and layers.Preferably, it is used as hole transport material in hole transport layer and / or as matrix material in light-emitting layer, more preferably in combination with phosphorescent emitter.

[0136] Thus, the present invention further provides the use of a compound of formula (I) in an electronic device, preferably selected from the group consisting of organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic light emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field quenched devices (OFQDs), organic light emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), more preferably organic electroluminescent devices (OLEDs).

[0137] The present invention further provides an electronic device comprising at least one compound of formula (I), said electronic device preferably being selected from the devices described above.

[0138] Particularly preferred is an organic electroluminescent device comprising an anode, a cathode, and at least one light-emitting layer, characterized in that at least one organic layer is present in the device comprising at least one compound of formula (I). Preferred is an organic electroluminescent device comprising an anode, a cathode, and at least one light-emitting layer, characterized in that at least one organic layer in the device selected from a hole-transporting layer and a light-emitting layer comprises at least one compound of formula (I).

[0139] The hole-transporting layer is understood here to mean all layers disposed between the anode and the light-emitting layer, preferably the hole-injection layer, the hole-transport layer, and the electron-blocking layer. The hole-injection layer is understood here to mean the layer directly adjacent to the anode. The hole-transporting layer is understood here to mean the layer between the anode and the light-emitting layer, but not directly adjacent to the anode, and preferably not directly adjacent to the light-emitting layer. The electron-blocking layer is understood here to mean the layer between the anode and the light-emitting layer and directly adjacent to the light-emitting layer. The electron-blocking layer preferably has a high-energy LUMO and therefore prevents electrons from leaving the light-emitting layer.

[0140] In addition to the cathode, anode, and light-emitting layer, the electronic device may comprise further layers, such as, in each case, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, charge generation layers, and / or organic or inorganic p / n junctions. However, it should be noted that not all of these layers necessarily need to be present; the choice of layer always depends on the compounds used and, inter alia, on whether the device is a fluorescent or phosphorescent electroluminescent device.

[0141] The arrangement of layers in the electronic device is preferably as follows: -anode- -Hole injection layer- -Hole transport layer- -Optionally a further hole transport layer- -Emitting layer- -Optional hole blocking layer- -Electron transport layer- -Electron injection layer- -Cathode-.

[0142] At the same time, it should again be pointed out that not all of the layers mentioned need be present and / or further layers may additionally be present.

[0143] The organic electroluminescent device of the present invention may contain two or more emitting layers. More preferably, these emitting layers have several emission maxima between 380 nm and 750 nm, and produce white light as a whole; in other words, various emitting compounds capable of emitting fluorescence or phosphorescence and emitting blue, green, yellow, orange, or red light are used in the emitting layers. Particularly preferred is a three-layer system, i.e., a system having three emitting layers, one of which emits blue light in each case, one of which emits green light in each case, and one of which emits orange or red light in each case. The compound of the present invention is preferably present in the hole-transporting layer or the emitting layer. It should be noted that for the generation of white light, instead of multiple emitting compounds that emit colored light, individually used emitting compounds that emit over a wide wavelength range may also be suitable.

[0144] The compound of formula (I) is preferably used as a hole transport material. Here, the light-emitting layer may be a fluorescent light-emitting layer or a phosphorescent light-emitting layer. The light-emitting layer is preferably a blue fluorescent light-emitting layer or a green phosphorescent light-emitting layer.

[0145] When a device containing a compound of formula (I) contains a phosphorescent-emitting layer, it is preferred that this layer contains two or more, preferably exactly two, different matrix materials (mixed matrix system), preferred embodiments of which are described in more detail below.

[0146] When the compounds of formula (I) are used as hole transport materials in a hole transport layer, a hole injection layer or an electron blocking layer, the compounds can be used as pure materials, i.e., in a proportion of 100% in the hole transport layer, or in combination with one or more further compounds.

[0147] In a preferred embodiment, the hole transport layer comprising the compound of formula (I) additionally comprises one or more additional hole transport compounds. These additional hole transport compounds are preferably selected from triarylamine compounds, more preferably monotriarylamine compounds. Very particularly preferably, they are selected from the preferred embodiments of hole transport materials shown below. In the preferred embodiment described, the compound of formula (I) and the one or more additional hole transport compounds are preferably present in a proportion of at least 10% each, more preferably in a proportion of at least 20% each.

[0148] In a preferred embodiment, the hole-transporting layer comprising the compound of formula (I) additionally contains one or more p-dopants. The p-dopants used in accordance with the present invention are preferably organic electron acceptor compounds capable of oxidizing one or more other compounds in the mixture.

[0149] Particularly preferred p-dopants are quinodimethane compounds, azaindenofluorenediones, azaphenalenes, azatriphenylenes, I2, metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or metal from the third main group, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd, and Pt with ligands containing at least one oxygen atom as a binding site. Transition metal oxides are also preferred as dopants, preferably oxides of rhenium, molybdenum, and tungsten, more preferably Re2O7, MoO3, WO3, and ReO3. Even more preferred are complexes of bismuth in the (III) oxidation state, more particularly bismuth(III) complexes with electron-deficient ligands, more particularly carboxylate ligands.

[0150] The p-dopant is preferably substantially uniformly distributed in the p-doped layer. This can be achieved, for example, by co-evaporation of the p-dopant with the hole transport material matrix. The p-dopant is preferably present in the p-doped layer in a proportion of 1% to 10%.

[0151] Preferred p-dopants are especially the following compounds:

[0152] [ka]

[0153] In preferred embodiments, the device contains a hole injection layer that conforms to one of the following aspects: a) contains a triarylamine and a p-dopant; or b) contains a single electron-deficient material (electron acceptor). In a preferred embodiment of aspect a), the triarylamine is a monotriarylamine, especially one of the preferred triarylamine derivatives mentioned below. In a preferred embodiment of aspect b), the electron-deficient material is a hexaazatriphenylene derivative as described in US 2007 / 0092755.

[0154] The compounds of formula (I) may be present in the hole injection layer, hole transport layer and / or electron blocking layer of the device. When present in a hole injection layer or hole transport layer, the compounds are preferably p-doped, which means that they are in mixed form with a p-dopant in the layer, as described above.

[0155] More preferably, the compound of formula (I) is present in an electron blocking layer. In this case, the compound is preferably not p-doped. Even more preferably, in this case, the compound is preferably in the form of a single compound in the layer, preferably without the addition of further compounds.

[0156] In an alternative preferred embodiment, the compound of formula (I) is used as a matrix material in the light-emitting layer in combination with one or more light-emitting compounds, preferably phosphorescent compounds, which are preferably selected from red phosphorescent compounds and green phosphorescent compounds.

[0157] In this case, the ratio of the matrix material in the light-emitting layer is 50.0% to 99.9% by volume, preferably 80.0% to 99.5% by volume, and more preferably 85.0% to 97.0% by volume.

[0158] Correspondingly, the proportion of the luminescent compound is between 0.1% and 50.0% by volume, preferably between 0.5% and 20.0% by volume, and more preferably between 3.0% and 15.0% by volume.

[0159] The light-emitting layer of an organic electroluminescent device may also contain a system containing multiple matrix materials (mixed matrix system) and / or multiple light-emitting compounds. In this case, the light-emitting compound is generally the compound with a lower proportion in the system, and the matrix material is the compound with a higher proportion in the system. However, in individual cases, the proportion of a single matrix material in the system may be lower than the proportion of a single light-emitting compound.

[0160] The compound of formula (I) is preferably used as a component of a mixed matrix system for a phosphorescent emitter. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials has hole-transporting properties, and the other material has electron-transporting properties. It is further preferred that one of the materials is selected from compounds with a large energy difference between its HOMO and LUMO (wide bandgap material). The compound of formula (I) in the mixed matrix system is preferably a matrix material with hole-transporting properties. Correspondingly, when the compound of formula (I) is used as a matrix material for a phosphorescent emitter in the emissive layer of an OLED, a second matrix compound with electron-transporting properties is present in the emissive layer. The two different matrix materials may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, and most preferably 1:4 to 1:1.

[0161] However, the desired electron-transporting and hole-transporting properties of the mixed matrix component may also be primarily or entirely possessed by a single mixed matrix component, with additional mixed matrix components performing other functions.

[0162] The following classes of materials are preferably used for the above layers of the device: Phosphorescent emitters: The term "phosphorescent emitter" typically encompasses compounds in which light emission occurs via a spin-forbidden transition, such as a transition from an excited triplet state or a state with a higher spin quantum number, such as a quintet state.

[0163] Suitable phosphorescent emitters are especially compounds which, when appropriately excited, preferably emit light in the visible region and which also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. As phosphorescent emitters, it is preferred to use compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium, platinum or copper.

[0164] In the context of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent compounds.

[0165] Generally, all phosphorescent complexes that are used in phosphorescent OLEDs according to the prior art and that are known to those skilled in the art of organic electroluminescent devices are suitable for use in the devices of the present invention. Further examples of suitable phosphorescent emitters are shown in the table below:

[0166] [ka]

[0167] [ka]

[0168] [ka]

[0169] [ka]

[0170] [ka]

[0171] [ka]

[0172] [ka]

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] Fluorescent emitter: Preferred fluorescent compounds are selected from the arylamine class. In the context of the present invention, arylamine or aromatic amine is understood to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines, and aromatic chrysenediamines. Aromatic anthracenamines are understood to mean compounds in which a diarylamino group is directly bonded to an anthracene group, preferably at the 9-position. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are directly bonded to an anthracene group, preferably at the 9- and 10-positions. Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are similarly defined, with the diarylamino group being bonded to the pyrene, preferably at the 1- or 1- and 6-positions. Further preferred luminescent compounds are indenofluorene amines or diamines, benzoindenofluorene amines or diamines, and dibenzoindenofluorene amines or diamines, as well as indenofluorene derivatives with fused aryl groups.Also preferred are pyrene arylamines.Also preferred are benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives linked to furan or thiophene units.Examples of fluorescent emitters are illustrated in the following table:

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185] [ka]

[0186] Matrix materials for fluorescent emitters: Preferred matrix materials for fluorescent emitters are selected from the classes of oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene), especially oligoarylenes containing fused aromatic groups, oligoarylenevinylenes, polypodal metal complexes, hole-conducting compounds, electron-conducting compounds, especially ketones, phosphine oxides and sulfoxides; atropisomers, boronic acid derivatives, or benzanthracene. Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene, and / or pyrene, or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzophenanthrene, and / or pyrene, or atropisomers of these compounds. Oligoarylene in the context of the present invention is understood to mean a compound in which at least three aryl or arylene groups are linked together. Preferred matrix materials for fluorescent emitters are illustrated in the table below:

[0187] [ka]

[0188] [ka]

[0189] [ka]

[0190] [ka]

[0191] Matrix materials for phosphorescent emitters: Preferred matrix materials for phosphorescent emitters, in addition to the compounds of formula (I), are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives such as CBP (N,N-biscarbazolylbiphenyl), indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, dipolar matrix materials, silanes, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasiloles or tetraazasiloles, diazaphosphololes, bridged carbazole derivatives, triphenylene derivatives, or lactams.

[0192] Electron transport material: Suitable electron-transporting materials are for example the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials used in these layers according to the prior art.

[0193] The material used in the electron transport layer may be any material used as an electron transport material in the electron transport layer according to the prior art. Particularly preferred are aluminum complexes such as Alq3, zirconium complexes such as Zrq4, lithium complexes such as Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives. Preferred electron transport compounds are shown in the table below:

[0194] [ka]

[0195] [ka]

[0196] [ka]

[0197] Hole transporting materials: In addition to the compounds of formula (I), further compounds preferably used in the hole-transporting layer of the OLED of the present invention are indenofluoreneamine derivatives, amine derivatives, hexaazatriphenylene derivatives, amine derivatives with fused aromatic systems, monobenzoindenofluoreneamines, dibenzoindenofluoreneamines, spirobifluoreneamines, fluoreneamines, spirodibenzopyranamines, dihydroacridine derivatives, spirodibenzofurans and spirodibenzothiophenes, phenanthrediarylamines, spirotribenzotropolones, spirobifluorenes with metaphenyldiamine groups, spirobisacridines, xanthenediarylamines, and 9,10-dihydroanthracene pyro-compounds with diarylamino groups. Preferred hole-transporting compounds are shown in the table below:

[0198] [ka]

[0199] [ka]

[0200] [ka]

[0201] [ka]

[0202] [ka]

[0203] [ka]

[0204] Cathode: Preferred cathodes for electronic devices are metals, metal alloys, or multilayer structures composed of various metals with low work functions, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys composed of alkali metals or alkaline earth metals with silver, such as alloys composed of magnesium and silver. In multilayer structures, in addition to the metals mentioned, additional metals with relatively high work functions, such as Ag or Al, can also be used. In this case, metal combinations such as Ca / Ag, Mg / Ag, or Ba / Ag are commonly used. It may be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between the metallic cathode and the organic semiconductor. Examples of materials useful for this purpose include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Lithium quinolinate (LiQ) can also be used for this purpose. The thickness of this layer is preferably 0.5 to 5 nm.

[0205] anode: Preferred anodes are materials with a high work function. Preferably, the anode has a work function of more than 4.5 eV vs. vacuum. First, metals with high redox potentials are suitable for this purpose, such as Ag, Pt or Au. Second, metal / metal oxide electrodes (e.g., Al / Ni / NiO x , Al / PtO x) may be preferred. Depending on the application, at least one of the electrodes must be transparent or partially transparent to allow either irradiation of the organic material (organic solar cells) or light emission (OLEDs, O-lasers). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Furthermore, conductively doped organic materials, especially conductively doped polymers, are preferred. In addition, the anode may also consist of two or more layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0206] In a preferred embodiment, the electronic device is characterized in that one or more layers are coated by sublimation, in which case the material is deposited in a vacuum sublimation system at 10 -5 less than mbar, preferably 10 -6 It is applied by evaporation at an initial pressure of less than 10 mbar, but in this case the initial pressure can be lowered further, for example to 10 -7 It is also possible to have a pressure below mbar.

[0207] Likewise, electronic devices are preferred, characterized in that one or more layers are coated by the OVPD (organic vapor phase deposition) method or with the aid of carrier gas sublimation. In this case, the material is preferably 10 -5 It is applied at a pressure of between mbar and 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, in which the material is applied directly by a nozzle and is therefore structured (for example, MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0208] In addition, preferred is an electronic device characterized in that one or more layers are produced from a solution, for example, by spin coating, or by any printing method, such as screen printing, flexographic printing, nozzle printing or offset printing, but more preferably by LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, a soluble compound of formula (I) is required. High solubility can be achieved by suitable substitution of the compound.

[0209] More preferably, the electronic device of the present invention is fabricated by applying one or more layers from solution and applying one or more layers by sublimation.

[0210] After application of the layers, depending on the application, the device is structured, the contacts are connected and finally sealed to eliminate the damaging effects of water and air.

[0211] According to the present invention, electronic devices comprising one or more compounds of formula (I) can be used in displays, as light sources in lighting applications, and as light sources in medical and / or cosmetic applications.

[0212] [Example] A) Synthesis example Example 1-1: N,9-Bis({[1,1'-biphenyl]-4-yl})-N-(9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-fluoren-4-amine

[0213] [ka]

[0214] 9-{[1,1'-biphenyl]-4-yl}-4-bromo-9-phenylfluorene: 14.5 g (46.3 mmol) of 2,2'-dibromobiphenyl is dissolved in 150 ml of dry THF in a baking flask. The reaction mixture is cooled to -78 °C. At this temperature, 20.5 ml of a 2.3 M solution of n-BuLi in hexane (46.3 mmol) is slowly added dropwise. The mixture is stirred for another hour at -70 °C. Subsequently, 11.4 g of biphenyl-4-yl(phenyl)methanone (44.13 mmol) is dissolved in 80 ml of THF and added dropwise at -70 °C. After the addition is complete, the reaction mixture is allowed to warm gradually to room temperature, mixed with NH4Cl, and then concentrated on a rotary evaporator. 200 ml of acetic acid is carefully added to the concentrated solution, followed by 50 ml of fuming HCl. The mixture is heated to 75°C and maintained there for 6 hours. During this time, a white solid precipitates. The mixture is then allowed to cool to room temperature, and the precipitated solid is suction filtered and washed with methanol. The residue is dried under reduced pressure at 40°C. Yield: 19.5 g (41 mmol) (90% of theory).

[0215] The following compounds are prepared in a similar manner, with yields ranging from 40% to 90%:

[0216] [ka]

[0217] [ka]

[0218] [ka]

[0219] N,9-Bis({[1,1'-biphenyl]-4-yl})-N-(9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-fluoren-4-amine 10.0 g of N-{1,1'-biphenyl]-4-yl}-9,9-dimethylfluoren-2-amine (27.7 mmol) and 13.1 g of 9-{[1,1'-biphenyl]-4-yl}-4-bromo-9-phenylfluorene (27.7 mol) were dissolved in 300 ml of toluene. The solution was degassed and saturated with N2. 340 mg (0.83 mmol) of S-Phos and 250 mg (0.28 mmol) of Pd2(dba)3 were then added, followed by 4.6 g of sodium tert-butoxide (41.5 mmol). The reaction mixture was heated to boiling under a protective atmosphere for 3 hours. The mixture was then partitioned between toluene and water, and the organic phase was washed three times with water, dried over Na2SO4, and concentrated by rotary evaporation. The crude product is filtered through silica gel with toluene, and the remaining residue is recrystallized from heptane / toluene. The yield is 16.7 g (80% of theory). The material is finally sublimed under high vacuum; the purity is 99.9%.

[0220] The following compounds are prepared in a similar manner, with yields ranging from 65% to 90%:

[0221] [ka]

[0222] [ka]

[0223] [ka]

[0224] [ka]

[0225] Example 2-1: N-{[1,1'-biphenyl]-4-yl}-N-[4-(9-{[1,1'-biphenyl]-4-yl}-9-phenyl-9H-fluoren-4-yl)phenyl]-9,9-dimethyl-9H-fluoren-2-amine

[0226] [ka]

[0227] Intermediate III-1: 9-{[1,1'-biphenyl]-4-yl}-4-(4-chlorophenyl)-9-phenylfluorene 5.90 g (37.7 mmol) of 4-chlorophenylboronic acid and 15 g (37.7 mmol) of intermediate I-1 are suspended in 200 ml of THF and 38 ml of 2 M potassium carbonate solution (75.5 mmol). 0.87 g (0.76 mmol) of tetrakis(triphenylphosphine)palladium is added to this suspension, and the reaction mixture is heated under reflux for 12 hours. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 100 ml of water, and then concentrated to dryness. After filtering the crude product through silica gel with toluene, 15.46 g (95%) of intermediate III-1 are obtained.

[0228] The following compounds are prepared in a similar manner, with yields ranging from 40% to 90%:

[0229] [ka]

[0230] [ka]

[0231] [ka]

[0232] [ka]

[0233] N-{[1,1'-biphenyl]-4-yl}-N-[4-(9-{[1,1'-biphenyl]-4-yl}-9-phenyl-9H-fluoren-4-yl)phenyl]-9,9-dimethyl-9H-fluoren-2-amine Similar to Example 1-1, N-{[1,1'-biphenyl]-4-yl}-N-[4-(9-{[1,1'-biphenyl]-4-yl}-9-phenyl-9H-fluoren-4-yl)phenyl]-9,9-dimethyl-9H-fluoren-2-amine (Compound 2-1) and the following compounds are prepared in yields of 40% to 85%.

[0234] [ka]

[0235] [ka]

[0236] [ka]

[0237] B) Device example 1) General manufacturing method of OLED and evaluation of OLED characteristics A glass plaque coated with 50 nm thick structured ITO (indium tin oxide) is the substrate onto which the OLED is applied.

[0238] An OLED basically has the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emissive layer (EML) / electron transport layer (ETL) / electron injection layer (EIL), and finally a cathode. The cathode is formed by a 100 nm thick layer of aluminum. The exact structure of an OLED can be found in the table that follows. The materials needed to manufacture an OLED are listed in the table below.

[0239] All materials are applied by thermal evaporation in a vacuum chamber. In this case, the emissive layer consists of at least one matrix material (host material) and a luminescent dopant (emitter) that is added to the matrix material by co-evaporation in a specific volume fraction. A specification such as H:SEB(95%:5%) means that the material H is present in the layer in a volume fraction of 95% and SEB in a volume fraction of 5%.

[0240] Similarly, the electron transport layer and hole injection layer are also composed of a mixture of two materials. The structures of the materials used in the OLED are shown in Table 3.

[0241] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, the external quantum efficiency (EQE, measured in %) as a function of luminance calculated from the current-voltage-luminance characteristic assuming Lambertian emission characteristics, and the lifetime are determined. The parameter EQE @ 10 mA / cm 2 is 10mA / cm 2 The parameter U@10mA / cm refers to the external quantum efficiency achieved at 2 is 10mA / cm 2 The lifetime LT is defined as the time it takes for the luminance to drop to a specific percentage from the initial luminance during operation at a constant current density. The number LT80 here means that the recorded lifetime corresponds to the time it takes for the luminance to drop to 80% of its initial value. @60 or 40 mA / cm 2 The figures here indicate that the relevant lifetime is 60 or 40mA / cm 2 This means that the temperature is measured at

[0242] 2) Use of the compounds of the present invention in HIL / HTL and EBL of blue fluorescent and green phosphorescent devices An OLED having the following structure is fabricated:

[0243] [Table 1]

[0244] OLEDs I1 and I14 show the use of compounds HTM-4 and HTM-7 according to the present application in the HIL (p-doped) and HTL of a blue fluorescent OLED.

[0245] OLEDs I2 to I7 illustrate the use of compounds HTM-1 to HTM-6 according to the present application in the EBL of a blue fluorescent OLED.

[0246] OLEDs I8-I13 show the use of compounds HTM-1 to HTM-6 according to the present application in the EBL of a green phosphorescent OLED.

[0247] The OLED exhibits the following values ​​for operating voltage, EQE and lifetime:

[0248] [Table 2]

[0249] The OLEDs exhibit good lifetimes, high efficiencies and low operating voltages, and this result is obtained for all three OLED structures used and for all compounds according to the present application used above.

[0250] [Table 3-1]

[0251] [Table 3-2]

[0252] 3) Comparative experiment using compounds HTM-4 and Ref-1 The compound HTM-4 according to the present application is compared with the reference compound Ref-1. These compounds are identical except for the substitution at the bridgehead carbon of the fluorene: in the case of HTM-4, there is an asymmetric substitution with a phenyl group and a metabiphenyl group as substituents, whereas in Ref-1, there is a symmetric substitution with two phenyl groups at the mentioned positions.

[0253] As in item 2), an OLED stack is used, where the compound is present in the EBL in the stack that emits blue fluorescence. Here, Ref-1 is 10 mA / cm 2 at 3.7V, 10mA / cm 2 HTM-4 shows a better EQE of 8.9% at the same voltage (3.8V) in the equivalent configuration I5.

[0254] This demonstrates the advantages arising from the use of asymmetric substitution at the bridgehead carbon atom position, particularly the substitution at that atom by biphenyl and phenyl, compared to the symmetric substitution by two phenyl groups.

[0255] [Table 4]

[0256] 4) Comparative experiment using compounds HTM-7 and Ref-2 The compound HTM-7 according to the present application is compared with the reference compound Ref-2, which differs only in the substitution at the bridgehead carbon atom of the fluorene: Ref-2 has an alkyl substitution on the phenyl group at the bridgehead carbon atom mentioned, while HTM-7 has no alkyl substitution.

[0257] As used in section 2), an OLED structure is used in which compounds exist in the HIL and HTL in the blue fluorescent stack.

[0258] Here, the reference compound Ref-2 has a current of 10 mA / cm 2 The voltage is 4.2V.2 The LT80 measured at this voltage is 150 hours. In comparison, the HTM-7, in an equivalent configuration, shows a significantly better LT80 of 310 hours at the same voltage (4.3V).

[0259] This shows the improvement resulting from the loss of the alkyl group on the substituent at the bridgehead carbon atom. This improvement is not limited to the structure shown, but occurs generally.

[0260] [Table 5]

Claims

1. Formula (I) 【Chemistry 1】 wherein the variables occurring are as follows: Z is -[Ar1] ｋ When the -N(Ar2)(Ar3) group is attached thereto, it is C, and Z is -[Ar1] ｋ -N(Ar2)(Ar3) is in each case the same or different, CR1 or N, if the group is not attached thereto; Ar1, in each occurrence, is the same or different and is an aromatic ring system having 6 to 40 aromatic ring atoms and substituted by an R3 radical, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted by an R3 radical; Ar2 is an aromatic ring system having 6 to 40 aromatic ring atoms and substituted by an R4 radical, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted by an R4 radical; Ar3 is an aromatic ring system having 6 to 40 aromatic ring atoms and substituted by an R4 radical, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted by an R4 radical; Ar4 is phenyl optionally substituted by an R2 radical or naphthyl optionally substituted by an R2 radical; R1 is the same or different in each occurrence and is H, D, F, Cl, Br, I, C(=O)R5, CN, Si(R5) ３ , N(R5) ２ , P(=O)(R5) ２ ,OR5,S(=O)R5,S(=O) ２ R5 is selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; two or more R1 radicals may be bonded to each other or form a ring; the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups, and the aforementioned aromatic and heteroaromatic ring systems are each substituted by an R5 radical; one or more CH in the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups ２ The group is -RC=CR-, -C≡C-, Si(R) ２ , C=O, C=NR5, -C(=O)O-, -C(=O)NR5-, NR5, P(=O)(R5), -O-, -S-, SO or SO ２ may be replaced by; R2 is the same or different in each occurrence and is selected from the group consisting of D, F, CN, Si(R5) ３ , N(R5) ２ , an aromatic ring system having 6 to 40 aromatic ring atoms and substituted by an R5 radical, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted by an R5 radical; R3 is the same or different in each occurrence and is H, D, F, Cl, Br, I, C(=O)R5, CN, Si(R5) ３ , N(R5) ２ , P(=O)(R5) ２ ,OR5,S(=O)R5,S(=O) ２ R5 is selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; two or more R3 radicals may be bonded to each other or form a ring; the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups, and the aforementioned aromatic and heteroaromatic ring systems are each substituted by an R5 radical; one or more CH in the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups ２ The group is -RC=CR-, -C≡C-, Si(R) ２ , C=O, C=NR5, -C(=O)O-, -C(=O)NR5-, NR5, P(=O)(R5), -O-, -S-, SO or SO ２ may be replaced by; R4 is the same or different in each occurrence and is H, D, F, Cl, Br, I, C(=O)R5, CN, Si(R5) ３ , N(R5) ２ , P(=O)(R5) ２ ,OR5,S(=O)R5,S(=O) ２ R5 is selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; two or more R4 radicals may be bonded to each other or form a ring; the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups, and the aforementioned aromatic and heteroaromatic ring systems are each substituted by an R5 radical; one or more CH ２ The group is -RC=CR-, -C≡C-, Si(R) ２ , C=O, C=NR5, -C(=O)O-, -C(=O)NR5-, NR5, P(=O)(R5), -O-, -S-, SO or SO ２ may be replaced by; R5 is the same or different in each occurrence and is H, D, F, Cl, Br, I, C(=O)R6, CN, Si(R6) ３ , N(R6) ２ , P(=O)(R6) ２ ,OR6,S(=O)R6,S(=O) ２ R6 is selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; two or more R5 radicals may be bonded to each other or form a ring; the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups, and the aforementioned aromatic and heteroaromatic ring systems, are each substituted by an R6 radical; one or more CH in the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups ２ The group is -R6C=CR6-, -C≡C-, Si(R6) ２ , C=O, C=NR6, -C(=O)O-, -C(=O)NR6-, NR6, P(=O)(R6), -O-, -S-, SO or SO ２ may be replaced by; R6, in each occurrence, is the same or different and is selected from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; said alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by one or more radicals selected from F and CN; k is 0, 1, 2, 3 or 4, and when k=0, the Ar group is absent and the groups bonded to Ar in formula (I) are directly bonded to each other; i is 0, 1, 2, 3, 4 or 5; n is 0, 1, 2, 3 or 4; The two groups in formula (I) 【Chemistry 2】 are not the same as the whole, including their respective substituents) Compound.

2. 2. The compound according to claim 1, characterized in that it is a monoamine.

3. Z is the -[Ar1] ｋ 3. A compound according to claim 1 or 2, characterized in that the -N(Ar2)(Ar3) group is CR1 when not attached thereto.

4. 4. The compound according to claim 1, wherein k is 0.

5. When k=1, the -(Ar1) ｋ The - group is of the following formula: 【Chemistry 3-1】 【Chemistry 3-2】 【Chemistry 3-3】 [Chemistry 3-4] [Transformation 3-5] [Chemistry 3-6] wherein the dotted line represents the bond to the remainder of formula (I), and the groups at positions shown as unsubstituted are each substituted with an R radical, the R radical at these positions being preferably H.

4. The compound according to claim 1, wherein the compound corresponds to one of the following:

6. 6. Compounds according to any one of claims 1 to 5, characterized in that Ar2 and Ar3, in each case the same or different, are selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, in particular 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl and triazinyl-substituted phenyl, in which the mentioned groups are each substituted by one or more R4 radicals.

7. 7. A compound according to any one of claims 1 to 6, characterized in that exactly one group selected from the Ar2 and Ar3 groups is phenyl substituted by an R4 radical, preferably selected from H, D, F, CN and alkyl groups having 1 to 10 carbon atoms, more preferably H.

8. Ar2 and Ar3 are the same or different and have the following formula: 【Chemistry 4-1】 【Chemistry 4-2】 【Chemistry 4-3】 【Chemistry 4-4】 [Chemistry 4-5] [Chemistry 4-6] 【Chemistry 4-7】 【Chemistry 4-8】 【Chemistry 4-9】 【Chemistry 4-10】 【Chemistry 4-11】 【Chemistry 4-12】 【Chemistry 4-13】 【Chemistry 4-14】 【Chemistry 4-15】 【Chemistry 4-16】 【Chemistry 4-17】 【Chemistry 4-18】 【Chemistry 4-19】 wherein the groups at positions shown as unsubstituted are substituted with R radicals, R at these positions is preferably H, and the bonds shown with dotted lines are bonds to the amine nitrogen atoms. Compounds according to any one of claims 1 to 7, characterized in that they are selected from:

9. Compounds according to any one of claims 1 to 8, characterized in that Ar4 is phenyl optionally substituted by an R2 radical.

10. R1, in each occurrence, is the same or different and is selected from H, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein said aromatic ring system and said heteroaromatic ring system are each substituted by an R5 radical; and R2 is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted with an R5 radical; and R3 is the same or different in each occurrence and is H, N(R5) ２ , a straight chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein said alkyl group, said aromatic ring system, and said heteroaromatic ring system are each substituted with an R radical; and R4 is the same or different in each occurrence and is H, N(R5) ２ , a straight chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein said alkyl group, said aromatic ring system, and said heteroaromatic ring system are each substituted with an R radical; and 10. The compound according to claim 1, wherein R5, which is the same or different in each occurrence, is selected from H, a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, and wherein the alkyl group, the aromatic ring system, and the heteroaromatic ring system are each substituted by an R6 radical.

11. 11. Compounds according to any one of claims 1 to 10, characterized in that one or two R1 radicals are selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted by R5 radicals, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and substituted by R5 radicals, and the other R1 radical is H.

12. 12. The compound according to claim 1, wherein i and n are 0.

13. The -[Ar1] ｋ 13. A compound according to any one of claims 1 to 12, characterized in that the -N(Ar2)(Ar3) group is attached to the fluorenyl group in the 2- or 4-position in formula (I).

14. The following formula: 【Chemistry 5-1】 【Chemistry 5-2】 【Chemistry 5-3】 【Chemistry 5-4】 【Transformation 5-5】 [Chemistry 5-6] [Transformation 5-7] (wherein the symbols and subscripts appearing are as defined in any one of claims 1 to 13, and the R1 radical bonded thereto means that all positions shown as unsubstituted on the benzene ring are substituted with R1 radicals) 14. A compound according to any one of claims 1 to 13, characterized in that it corresponds to one of the following:

15. 15. A process for preparing a compound according to any one of claims 1 to 14, characterized in that a biphenyl derivative having two reactive groups, at least one of which is in the ortho position, is metallated and then added to a carbonyl derivative containing a phenyl group and a phenyl or naphthyl substituted phenyl group attached to the carbonyl group.

16. 15. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 14, wherein the bond to the polymer, oligomer or dendrimer may be located at any desired position substituted by R1, R2, R3 or R4 in formula (I).

17. A formulation comprising at least one compound according to any one of claims 1 to 14 or at least one polymer, oligomer or dendrimer according to claim 16 and at least one solvent.

18. An electronic device comprising at least one compound according to any one of claims 1 to 14 or at least one polymer, oligomer or dendrimer according to claim 16.

19. 20. The electronic device of claim 18, wherein the electronic device is an organic electroluminescent device comprising an anode, a cathode, and at least one light-emitting layer, and wherein the compound is present in a hole-transporting layer or a light-emitting layer of the device.

20. 20. The organic electroluminescent device of claim 19, wherein the compound is present in a hole-transporting layer which is a hole-transporting layer or an electron-blocking layer.

21. Use of a compound according to any one of claims 1 to 14 in an electronic device.

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