Substituted aromatic amines for use in organic electroluminescent devices

Abstract

To provide a specific fluorene derivative, its use in an electronic device, and an electronic device comprising the fluorene derivative.SOLUTION: Provided is a compound of formula (I-E-1). Further provided are a method for producing the compound of formula (I-E-1), and oligomers, polymers, or dendrimers and formulations or compositions comprising one or more of the compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present application relates to fluorene compounds of formula (I) as defined below, their use in electronic devices, particularly organic electroluminescent devices, such as organic light-emitting devices (OLEDs), and electronic devices comprising compounds of formula (I). Furthermore, the present application relates to methods for producing said compounds, as well as oligomers, polymers or dendrimers and formulations or compositions comprising one or more of said compounds.

[0002] Electronic devices in the context of the present application are understood to mean what are called "organic electronic devices", which contain organic semiconductor materials as functional materials. More particularly, these devices are understood to mean organic electroluminescent (EL) devices, especially organic light-emitting diodes (OLEDs).

[0003] The general structure and mode of operation of organic electroluminescent devices are known to those skilled in the art and are described, for example, in US 4,539,507, US 5,151,629, EP 0,676,461 and WO 98 / 27136. Generally, organic electroluminescent devices contain spaced apart electrodes separated by one or more layers comprising organic compounds, thereby forming a so-called organic light-emitting structure, which emits electromagnetic radiation, typically light, in response to the application of a potential difference between the electrodes.

[0004] There is a strong interest in improving the performance data, especially lifetime, efficiency and operating voltage, of electronic devices, especially EL devices, such as OLEDs, and it has not yet been possible to find any completely satisfactory solutions in these aspects.

[0005] Layers with hole transport functionality, such as hole injection layers, hole transport layers, electron blocking layers, and even light-emitting layers, have a significant impact on the performance of electronic devices. New materials with hole transport properties are continually being explored for use in these layers.

[0006] In the course of the present invention, it has been found that fluorene compounds or derivatives having an amine or bridging amine group at the 2-position of the fluorene basic structure and further substituents selected from specific chemical groups at one or more of the 5-, 6-, and 8-positions, preferably at the 5-position, are highly suitable for use as materials with hole transport function, in particular for use as materials for hole transport layers, electron blocking layers, and light-emitting layers, especially for use in electron blocking layers. In this context, an electron blocking layer is understood to be a layer that is directly adjacent to the light-emitting layer on the anode side and functions to block electrons present in the light-emitting layer from entering the hole transport layer of an EL device.

[0007] When used in electronic devices, particularly EL devices such as OLEDs, they provide excellent results in terms of device lifetime, operating voltage, and quantum efficiency. These compounds also feature very good hole conduction properties, very good electron blocking properties, high glass transition temperatures, high oxidative stability, good solubility, high thermal stability, and low sublimation temperatures.

[0008] Therefore, the present application provides a compound of formula (I)

[0009] [ka]

[0010] wherein the variables are defined as follows: Z 1 may be the same or different in each occurrence, and CR 1 , C.R. 2 and N; Z 2 may be the same or different in each occurrence, and CR 2 and N; Ar L are aromatic ring systems with 6 to 40 aromatic ring atoms (these are substituted with one or more radicals R 4and heteroaromatic ring systems having 5 to 40 aromatic ring atoms (which may be substituted by one or more radicals R 4 and optionally substituted by Ar 1 , Ar 2 are identical or different aromatic ring systems having 6 to 40 aromatic ring atoms (which are substituted with one or more radicals R 4 and heteroaromatic ring systems having 5 to 40 aromatic ring atoms (which may be substituted by one or more radicals R 4 and optionally substituted by E is a single bond or -C(R 4 )2-, -N(R 4 )-, -O-, and -S-; R 1 may be the same or different in each occurrence, and Si(R 5 )3, selected from linear alkyl, alkoxy or thioalkyl groups having 1 to 20 C atoms, branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, wherein the alkyl, alkoxy and thioalkyl groups, and the aromatic and heteroaromatic ring systems, are in each case selected from one or more radicals R 5 may be substituted by; R 2 are the same or different at each occurrence and are H, D, F, Cl, Br, I, C(=O)R 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5, SCN, SF5, linear alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 2 may be linked to each other to form a ring; said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems may in each case be linked to one or more radicals R 5 and one or more CH groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be substituted in each case by -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=S, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), -O-, -S-, SO or SO2; R 3 are the same or different at each occurrence and are H, D, F, Cl, Br, I, C(=O)R 4 , CN, Si(R 4 )3, NO2, P(=O)(R 4 )2, S(=O)R 4 , S(=O)2R 4 , a linear alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl and alkynyl groups are in each case independently one or more radicals R 5 and one or more CH groups in said alkyl, alkoxy, thioalkyl, alkenyl and alkynyl groups may be substituted in each case by -R 5 C=CR 5 -, -C≡C-, Si(R 5)2, C=O, C=S, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), -O-, -S-, SO or SO2, in which in said alkyl, alkoxy, thioalkyl, alkenyl and alkynyl groups one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2), or aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, in which said aromatic and heteroaromatic ring systems are in each case composed of one or more radicals R 5 or an aryloxy group having 5 to 60 aromatic ring atoms or an arylalkyl group having 5 to 60 aromatic ring atoms, wherein the aryloxy and arylalkyl groups are in each case substituted by one or more radicals R 5 and wherein the two radicals R 3 may be linked together to form a ring, thereby constructing a spiro compound at the 9-position of the fluorene group, in which case spirobifluorene is excluded; R 4 are the same or different in each occurrence, H, D, F, C(=O)R 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 , a linear alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C 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 two or more radicals R 4may be linked to each other to form a ring; said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems may in each case be linked to one or more radicals R 5 and one or more CH groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be substituted in each case by -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=S, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), -O-, -S-, SO or SO2; R 5 are the same or different in each occurrence, H, D, F, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , a linear alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C 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 two or more radicals R 5 may be linked to each other to form a ring; said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems may in each case be linked to one or more radicals R 6 and one or more CH groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be substituted in each case by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=S, C=NR 6 , -C(=O)O-, -C(=O)NR 6-, NR 6 , P(=O)(R 6 ), -O-, -S-, SO or SO2; R 6 are identical or different in each occurrence and are selected from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 C atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 6 may be linked together to form a ring; said alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted with F and CN; m is 0 or 1, where when m=0, the group E is absent and the group Ar 1 and Ar 2 are not connected; n is 0 or 1; where, when n=0, the group Ar L does not exist, and the nitrogen atom is directly linked to the fluorene group) and wherein the group Z 1 At least one of the 1 The present invention relates to a compound characterized in that:

[0011] Although only one resonance form of the fluorene base structure is shown in formula (I), it will be apparent to those skilled in the art that other resonance structures exist in which there are alternating single and double bonds between the atoms forming the aromatic ring to account for the delocalization of electrons within the fluorene base structure, and all such resonance structures are equivalent and therefore within the scope of the present invention.

[0012] The following definitions apply generally to the chemical groups used. They only apply unless a more specific definition is given.

[0013] An aryl group in the sense of the present invention contains 6 to 40 aromatic ring atoms, none of which are heteroatoms. An aryl group here is understood to mean either a simple aromatic ring, such as benzene, or a fused aromatic polycycle, such as naphthalene, phenanthrene, or anthracene. A fused aromatic polycycle in the sense of the present application consists of two or more simple aromatic rings fused together.

[0014] A heteroaryl group in the sense of the present invention contains 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O and S. A heteroaryl group here is understood to mean either a simple heteroaromatic ring, such as pyridine, pyrimidine or thiophene, or a fused heteroaromatic polycycle, such as quinoline or carbazole. A fused heteroaromatic polycycle in the sense of the present application consists of two or more simple heteroaromatic rings fused together.

[0015] The aryl or heteroaryl radicals may in each case be substituted by the above-mentioned radicals and may be linked to an aromatic or heteroaromatic ring system via any desired position, in particular benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene , isobenzothiophene, dibenzothiophene, pyrrole, indole, 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, naphthimidazole, phenanthrimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, oxazo 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 This is understood to mean groups derived from diazole, 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.

[0016] An aryloxy group in the sense of the present invention is understood to mean an aryl group, as defined above, which is bonded via an oxygen atom.

[0017] An arylalkyl group in the sense of the present invention is understood to mean an aryl group, as defined above, to which is attached an alkyl group, as defined below.

[0018] An aromatic ring system within the meaning of the present invention contains 6 to 40 carbon atoms in the ring system and does not contain any heteroatoms as aromatic ring atoms. Therefore, an aromatic ring system within the meaning of the present application does not include any heteroaryl groups. An aromatic ring system within the meaning of the present invention does not necessarily contain only aryl groups, and is intended to be understood to mean a system in which multiple aryl groups may be connected by non-aromatic units, such as one or more optionally substituted C, Si, N, O, or S atoms. In such cases, the non-aromatic units preferably account for less than 10% of the non-H atoms relative to the total number of non-H atoms in the entire aromatic ring system. Thus, for example, some systems, such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether, and stilbene, are also intended to be considered aromatic ring systems within the meaning of the present invention, as are systems in which two or more aryl groups are connected by, for example, linear or cyclic alkyl, alkenyl, or alkynyl groups, or by silyl groups. Furthermore, systems in which two or more aryl groups are linked to one another via a single bond are also considered to be aromatic ring systems within the meaning of the present invention, such as some systems, such as biphenyl and terphenyl.

[0019] Preferably, the aromatic ring system is understood to be a chemical group, and the aryl groups that make up the chemical group are conjugated to each other. This means that the aryl groups are connected to each other via a single bond or via a linking unit that has a free pi-electron pair that can participate in conjugation. The linking unit is preferably selected from a nitrogen atom, a single C=C unit, a single C≡C unit, multiple C=C units and / or C≡C units that are conjugated to each other, -O-, and -S-.

[0020] A heteroaromatic ring system in the sense of the present invention contains 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O, or S. A heteroaromatic ring system is defined in the same way as the aromatic ring system described above, except that at least one heteroatom must be present as one of the aromatic ring atoms. This distinguishes it from aromatic ring systems defined herein, which cannot contain any heteroatoms as aromatic ring atoms.

[0021] Aromatic ring systems having 6 to 40 aromatic ring atoms or heteroaromatic ring systems having 5 to 40 aromatic ring atoms are in particular radicals derived from the aryl or heteroaryl groups mentioned above or from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene and indenocarbazole.

[0022] For the purposes of the present invention, linear alkyl groups having 1 to 20 C atoms or branched or cyclic alkyl groups having 3 to 20 C atoms or alkenyl or alkynyl groups having 2 to 20 C atoms are, in addition, optionally substituted at the individual H atoms or CH groups by the groups mentioned above under the definition of the radical, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, butyl, 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 radicals.

[0023] Alkoxy or thioalkyl groups having 1 to 20 carbon atoms are 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, sec-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.

[0024] Preferably, in the compound of formula (I), Z 1 is CR 1 and CR 2 is selected from.

[0025] Furthermore, preferably, Z 2 is CR 2 is.

[0026] Furthermore, there may be up to two groups Z per aromatic ring of the compound of formula (I). 1 and up to three groups Z 2 and are preferably N. More preferably, in compounds of formula (I), there are a maximum of two groups Z 1 and up to three groups Z 2 and is N.

[0027] In a preferred embodiment of the present invention, the group Ar L is selected from aromatic ring systems having 6 to 30 aromatic ring atoms, which are substituted with one or more radicals R 4 More preferably, Ar L is selected from divalent radicals derived from benzene, biphenyl, terphenyl, naphthyl, fluorenyl, indenofluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl, each of which is bound to one or more radicals R 4 Most preferably, Ar L is a divalent radical derived from benzene, which is formed by one or more radicals R 4 may be substituted by:

[0028] Preferred groups Ar L is expressed by the following formula Ar L -1~Ar L -82

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] wherein the dotted line represents the attachment of the divalent group to the remainder of formula (I). matches.

[0036] Of the above groups, particularly preferred are those of formula Ar L -1, Ar L -2, Ar L -3, Ar L -4, Ar L -15, Ar L -20, Ar L -25, and Ar L -36 is a group of one of

[0037] Of the above groups, particularly preferred are those of formula Ar L -76, Ar L -77, Ar L -78, Ar L -79, Ar L -80, Ar L -81 and Ar L -82 is a group of one of

[0038] The index n is preferably 0, which is the value of the group Ar L is absent, so that the fluorene and amine nitrogen atoms are directly linked to each other.

[0039] Preferably, the group Ar 1 and Ar 2 at least one of which is selected from radicals containing at least two rings selected from aromatic and heteroaromatic rings, which radicals are selected from one or more radicals R 4 That is, the group Ar 1 and Ar 2At least one of the groups Ar is an aromatic ring system containing two or more simple aromatic rings as an aryl group, or a heteroaromatic ring system containing two or more simple aromatic rings, at least one of which contains a heteroatom as one of the aromatic ring atoms to form a simple heteroaromatic ring as a heteroaryl group. 1 or Ar 2 In the at least one radical of the formula (I), the two aromatic or heteroaromatic rings may be fused together, and -C(R 4 )2-, -N(R 4 They may be linked to each other via a divalent group selected from ———, —O—, and —S—.

[0040] More preferably, the group Ar 1 or Ar 2 The at least one radical of the group Ar 1 and Ar 2 At least one of the aryl groups is an aromatic ring system containing two or more simple aromatic rings, which may be fused together, and -C(R 4 )2-, -N(R 4 They may be linked to each other via a divalent group selected from ———, —O—, and —S—.

[0041] Even more preferably, the group Ar 1 and Ar 2 are selected from radicals containing at least two rings, which may be identical or different, selected from aromatic and heteroaromatic rings, each of which is substituted with one or more radicals R 4 That is, the group Ar 1 and Ar 2 are either aromatic ring systems containing two or more simple aromatic rings as aryl groups, or heteroaromatic ring systems containing two or more simple aromatic rings, at least one of which contains a heteroatom as one of the aromatic ring atoms to form a simple heteroaromatic ring as heteroaryl groups.1 and Ar 2 In both of the above radicals, the two aromatic or heteroaromatic rings may be fused together, and -C(R 4 )2-, -N(R 4 They may be linked to each other via a divalent group selected from ———, —O—, and —S—.

[0042] Ar group 1 and Ar 2 It is particularly preferred that the radicals of each group contain at least two aromatic rings, i.e. the group Ar 1 and Ar 2 are the same or different and are selected from aromatic ring systems containing two or more simple aromatic rings as aryl groups, wherein the group Ar 1 and Ar 2 In one or both of the aromatic rings, the aromatic ring may be fused, and -C(R 4 )2-, -N(R 4 They may be linked to each other via a divalent group selected from ———, —O—, and —S—.

[0043] According to another aspect, said aromatic or heteroaromatic rings are preferably not fused or linked.

[0044] Preferably, the group Ar 1 and Ar 2 are identical or different and are radicals derived from the following groups (each of which may contain one or more radicals R 4 or two or three radicals derived from the groups below (each of which may be optionally substituted by one or more radicals R 4and optionally substituted by: phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, and triazinyl.

[0045] Particularly preferred groups Ar 1 and Ar 2 are the same or different and are selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, 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, each of which may be selected from one or more radicals R 4 It may be optionally substituted by:

[0046] Preferred groups Ar 1 and Ar 2 are the same or different and are represented by the following formula:

[0047] [ka]

[0048] [ka]

[0049]

change

[0050]

change

[0051]

change

[0052]

change

[0053]

change

[0054]

change

[0055]

change

[0056]

change

[0057]

change

[0058]

change

[0059]

change

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] (wherein the group is a group R 4 may be substituted with, but is preferably unsubstituted at these positions, the dotted line symbolizing the point of attachment to the nitrogen atom) is selected from the group

[0066] Particularly preferred groups Ar 1 and Ar 2 is a group conforming to one of the above formulae Ar-1, Ar-2, Ar-4, Ar-5, Ar-74, Ar-78, Ar-82, Ar-117, Ar-134, Ar-139, Ar-150, Ar-172 and Ar-207, with the proviso that Ar 1 and Ar 2 is not identical to Ar-1.

[0067] Further particularly preferred groups Ar 1 and Ar 2is a group conforming to one of the above formulae Ar-253, Ar-254, Ar-255, Ar-256, Ar-257, Ar-258, Ar-259, Ar-260, Ar-261, Ar-261, Ar-262, Ar-263, Ar-264, Ar-265, Ar-266 and Ar-267.

[0068] According to a preferred embodiment, the index m is 0, which means that the group Ar 1 and Ar 2 is not linked by the group E.

[0069] According to an alternative embodiment, which may be preferred under certain conditions, the index m is 1, which corresponds to the group Ar 1 and Ar 2 is linked by the group E.

[0070] Ar group 1 and Ar 2 is linked by group E, then group Ar 1 and Ar 2 are preferably the same or different and selected from phenyl and fluorenyl, each of which may be selected from one or more groups R 4 Furthermore, in such cases, the group Ar 1 and Ar 2 The group E connecting each group Ar 1 and Ar 2 Above, each group Ar is preferably phenyl or fluorenyl. 1 and Ar 2 Above, the group Ar 1 and Ar 2 Preferably, E is located at the ortho position relative to the bond to the amine nitrogen atom of R. Furthermore, preferably, in such a case, E is located at the ortho position relative to the bond to the amine nitrogen atom of R. 4 )2, NR 4 , O and S, the hexacyclic ring bearing the amine nitrogen atom is a group Ar 1 and Ar 2 and E; if E is a single bond, a pentacyclic ring is formed.

[0071] Ar group 1 and Ar 2 is linked by a group E, the moiety

[0072] [ka]

[0073] A particularly preferred embodiment of the formula

[0074] [ka]

[0075] [ka]

[0076] (wherein the group is a group R 4 may be substituted with, but is preferably unsubstituted at these positions, the dotted line symbolizing the point of attachment to the nitrogen atom) is selected from.

[0077] When m=0, particularly preferred moieties in formula (I) are

[0078] [ka]

[0079] is expressed by the following formula:

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] (wherein the group is a group R 4 Although it may be substituted with , it is preferably unsubstituted at these positions, and the dotted line symbolizes the point of attachment to the fluorene moiety of formula (I). matches.

[0087] Formula (I) is preferably represented by formulas (IA) to (IG)

[0088] [ka]

[0089] wherein the occurring variables are as defined above. matches one of the following:

[0090] Among the formulae (IA) to (IG), the formulae (IA) and (IE) are preferred, and the formula (IA) is particularly preferred.

[0091] More preferably, formula (I) is represented by formulas (IA-1) to (IG-1):

[0092] [ka]

[0093] wherein the occurring variables are as defined above. matches one of the following:

[0094] Among the formulae (IA-1) to (IG-1), the formulae (IA-1) and (IE-1) are preferred, with the formula (IA-1) being particularly preferred.

[0095] base R 2 are preferably identical or different and selected from H, F, linear alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 30 aromatic ring atoms and heteroaromatic ring systems having 5 to 30 aromatic ring atoms, wherein said alkyl groups, aromatic ring systems and heteroaromatic ring systems are in each case bound to one or more radicals R 5 More preferably, the group R 2 are the same or different and are selected from H, F, methyl, tert-butyl, and phenyl, biphenyl, dibenzofuran, dibenzothiophene, terphenyl. Most preferably, the group R 2 is H and phenyl.

[0096] Even more preferably, formula (I) is represented by the formulae (IA-2) to (IK-2):

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] wherein the occurring variables are as defined above. matches one of the following:

[0101] Among the formulae (IA-2) to (IK-2), the formulae (IA-2) and (IE-2) are preferred, with the formula (IA-2) being particularly preferred.

[0102] Particularly preferred embodiments of formula (I) are those of formulae (IA-2-1), (IA-2-2), (IE-2-1), (IE-2-2), (ID-2-1), (ID-2-2), (II-2-1), (II-2-2), (IH-2-1) and (IH-2-2)

[0103] [ka]

[0104] [ka]

[0105] wherein the occurring variables are as defined above. matches one of the following:

[0106] Formulae (IA-2-1) and (IA-2-2) are particularly preferred.

[0107] Preferably, in formulae (IA-2-1) and (IE-2-1), Ar L is selected from divalent radicals derived from benzene, biphenyl, terphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, each of which is substituted with one or more radicals R 4 may be substituted by:

[0108] R 4 are preferably the same or different and are selected from H, F, CN, Si(R 5)3, selected from linear alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 4 may be linked to each other to form a ring; said alkyl groups and said aromatic and heteroaromatic ring systems may in each case be linked to one or more radicals R 5 may be substituted by:

[0109] Preferably, R 1 are the same or different at each occurrence,

[0110] [ka]

[0111] wherein m is 1 and E is a single bond, an aromatic ring system having 6 to 30 aromatic ring atoms, and a heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein the aromatic and heteroaromatic ring systems are in each case bound to one or more radicals R 5 (which may be substituted by is selected from.

[0112] More preferably, R 1 are the same or different at each occurrence,

[0113] [ka]

[0114] wherein m is 1, E is a single bond, phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, 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, each of which may be selected from the group consisting of one or more radicals R 5 (which may be optionally substituted by is selected from.

[0115] base R 1 As an aspect

[0116] [ka]

[0117] For the group of formula (I), the subscript m is 1 and E is a single bond.

[0118] [ka]

[0119] The same group Ar as mentioned above in the context of L , Ar 1 , Ar 2 and the preferred embodiments for the index n apply.

[0120] Thus, the 5-ring containing the amine nitrogen atom is bonded to the group Ar 1 , Ar 2 and E, a single bond.

[0121] Preferred specific groups R 1 are the following groups R-1 to R-187

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] [ka]

[0133] [ka]

[0134] (wherein the group is a group R 5 Although it may be substituted with , it is preferably unsubstituted at these positions, and the dotted line symbolizes the point of attachment to the fluorene moiety of formula (I). is a group that conforms to

[0135] According to the present invention, the group R 1 is particularly preferably the same at each occurrence.

[0136] In a more preferred embodiment, R 1 is selected from aromatic ring systems having 6 to 24 aromatic ring atoms, which in each case are joined by one or more radicals R 5 may be substituted by:

[0137] Even more preferably, R 1 is selected from phenyl, biphenyl, terphenyl and quaterphenyl, each of which is selected from one or more radicals R 5 It may be optionally substituted by:

[0138] Particularly preferably, R 1 is selected from phenyl, biphenyl and terphenyl, each of which is selected from one or more radicals R 5 It may be optionally substituted by:

[0139] Very particularly preferably, R 1 is selected from biphenyl and terphenyl, each of which is substituted with one or more radicals R 5 It may be optionally substituted by:

[0140] Even more preferably, R 1 is selected from terphenyl, which is selected from one or more radicals R 5 It may be optionally substituted by:

[0141] a group R according to one of the formulas R-2 to R-2b 1 and a group R conforming to one of the formulas R-3 to R-8a 1 are especially preferred biphenyl and terphenyl groups, respectively.

[0142] In a further preferred embodiment, R 1 is selected from aromatic groups having two or more aromatic rings, which in each case are joined by one or more radicals R 5 may be substituted by:

[0143] In a particularly preferred embodiment of the invention, in the compounds of formula (I), the group R 1 is the group R 1 a part as defined above with respect to

[0144] [ka]

[0145] (The subscript m is 1 and E is a single bond.) Not selected from.

[0146] Furthermore, in a particularly preferred embodiment of the present invention, the compound of formula (I) is characterized as being a monoamine compound.

[0147] Preferably, R 3 are identical or different in each occurrence and are a linear alkyl group having 1 to 20 C atoms or a cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl group or the cyclic alkyl group is selected from the group consisting of one or more radicals R 5or aromatic or heteroaromatic ring systems having 6 to 30 aromatic ring atoms, wherein the aromatic and heteroaromatic ring systems are in each case substituted by one or more radicals R 5 and wherein the two radicals R 3 may be linked together to form a ring, thereby constructing a spiro compound at the 9-position of the fluorene group, excluding spirobifluorenes.

[0148] More preferably, R 3 are identical or different in each occurrence and are linear alkyl groups having 1 to 10 C atoms, wherein the alkyl group is a group selected from the group consisting of one or more radicals R 5 or an aromatic ring system having 6 to 24 aromatic ring atoms, which in each case is substituted by one or more radicals R 5 and wherein the two radicals R 3 may be linked together to form a ring, thereby constructing a spiro compound at the 9-position of the fluorene group, excluding spirobifluorenes.

[0149] According to a particularly preferred embodiment of the present invention, two groups R 3 are not linked to each other to form a ring.

[0150] Furthermore, according to a particularly preferred embodiment of the present invention, the group R 3 is the same for each occurrence.

[0151] According to the invention, particular preference is given to groups R selected from linear alkyl groups having 1 to 10 C atoms. 3 and even more preferably, the alkyl chain is substituted with one or more deuterium atoms, and most preferably, any of the hydrogen atoms of the alkyl group is replaced with a deuterium. 3 The most preferred alkyl group containing deuterium as a group is -CD3.

[0152] In another preferred embodiment of the present invention, R 3 is a deuterated phenyl group (-C6D5).

[0153] The compounds according to the invention exhibiting deuterium substitutions show improved performance data when used in electronic devices, such as OLEDs, in particular the voltage, efficiency, as well as the device lifetime, and also the shelf life and stability of the compounds can be improved.

[0154] Thus, the subject of the present invention is a compound of formula (I) comprising at least one deuterated group. Preferably, the compound of formula (I) comprises at least one deuterated group which is a deuterated methyl group (-CD3), where the deuterated methyl group is most preferably attached to the 9-position carbon atom of the fluorene.

[0155] Particularly preferred groups R 3 The following groups R-188 to R-202

[0156] [ka]

[0157] wherein the group is a radical R 5 Although it may be substituted with , it is preferably unsubstituted at these positions, and the dotted line symbolizes the point of attachment to the fluorene moiety of formula (I). is a group that conforms to

[0158] The particularly preferred groups R shown above 3 Among these, the groups conforming to the formula R-188 (methyl) and R-193 (phenyl) are the most preferred groups R 3 is.

[0159] R 5 are preferably the same or different and are selected from H, F, CN, Si(R 6)3, selected from linear alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 5 may be linked to each other to form a ring; said alkyl groups and said aromatic and heteroaromatic ring systems may in each case be linked to one or more radicals R 6 may be substituted by:

[0160] Particularly preferred specific compounds are the following compounds, which conform to the above formula (IA-2-2), where R 3 , R 1 , Ar 1 and Ar 2 are defined as shown in the following list (wherein formulae Ar-1 to Ar-207 and R-1 to R-66 are as defined above):

[0161] [ka]

[0162] [ka]

[0163] [ka]

[0164] [ka]

[0165] [ka]

[0166] [ka]

[0167] [ka]

[0168] [ka]

[0169] [ka]

[0170] [ka]

[0171] [ka]

[0172] [ka]

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] (*The biphenyl group conforms to one of the formulae R2, R2a and R2b as defined above; **The terphenyl group conforms to one of the formulas R-3 to R-8a as defined above. More preferred specific compounds are 3 The compounds C-1 to C-1260 in the above table are compounds in which is -CD3. The technical effects observable in the case of such compounds have been described above.

[0177] More preferred are compounds corresponding to the compounds C-1 to C-1260 listed above, except that they are derived from the formula (IA-2-1) shown above, wherein Ar L is phenylene, preferably 1,4-phenylene, and R 3 , R 1 , Ar 1 and Ar 2 are defined as shown for the corresponding compounds C-1 to C-1260.

[0178] More preferred are compounds corresponding to the compounds C-1 to C-1260 listed above, except that they are derived from the formula (IE-2-2) shown above, wherein R 3 , R 1 , Ar 1 and Ar 2 are defined as shown for the corresponding compounds C-1 to C-1260, and both groups R 1 are identical.

[0179] In a further preferred embodiment of the present invention, the compound of formula (I) comprises two fluorene groups. Even more preferred are compounds of formula (I) that contain exactly two fluorene groups, i.e., the compound does not contain any further fluorene groups. Z 1 and Z 2 But, CR 2 Preferred are compounds of formula (I) defined as (forming the first fluorene group), wherein m=0 and Ar 1 or Ar 2 Only one of the groups contains or is a fluorene group (second fluorene group), and very preferably, 1 or Ar 2and only one of the groups Ar-139 to Ar-200, Ar-202, Ar-203, Ar-226, Ar-227, Ar-250 to Ar-252 and Ar-264 to Ar-266 is selected from the group Ar-139 to Ar-200, Ar-202, Ar-203, Ar-226, Ar-227, Ar-250 to Ar-252 and Ar-264 to Ar-266, which are not substituted by a group R 4 may be substituted with.

[0180] It is further preferred if the compound of formula (I) comprising two fluorene groups exhibits identical substitutions at the 9-position of the two fluorene groups. Particularly preferred substituents for all four groups at the 9-position of the two fluorene groups are selected from -CH, -CD, phenyl (-CH) and -CD.

[0181] In a further preferred embodiment of the present invention, the compound of formula (I) comprises two fluorene groups and one dibenzofuran group. Even more preferred are compounds of formula (I) that contain exactly two fluorene groups and one dibenzofuran group, i.e., the compound does not contain any further fluorene or dibenzofuran groups. Z 1 and Z 2 But, CR 2 Preferred are compounds of formula (I) defined as (forming the first fluorene group), wherein m=0 and Ar 1 contains or is a fluorene group (second fluorene group), and Ar 2 comprises or is a fluorene group, and very preferably Ar 1 is selected from the groups Ar-139 to Ar-200, Ar-202, Ar-203, Ar-226, Ar-227, Ar-250 to Ar-252 and Ar-264 to Ar-266, and Ar 2 is selected from Ar-63 to Ar-66, Ar-71 to Ar-85, Ar-99, Ar-100, Ar-102, Ar-103, Ar-204, Ar-205, Ar-206, and very preferably Ar 2 is selected from Ar-63 to Ar-66, Ar-71 to Ar-85, Ar-99, Ar-100, Ar-102, and Ar-103, and particularly preferably, Ar 2is selected from Ar-71 to Ar-83 and Ar-85, very particularly preferably Ar 2 is Ar-78, and Ar 1 and Ar 2 both of which have a group R 4 may be substituted with.

[0182] It is further preferred if the compound of formula (I) comprising two fluorene groups and one dibenzofuran group exhibits identical substitutions at the 9-position of the two fluorene groups. Particularly preferred substituents for all four groups at the 9-position of the two fluorene groups are selected from -CH, -CD, phenyl (-CH) and -CD.

[0183] In yet another preferred embodiment of the present invention, the compound of formula (I) contains one fluorene group and two dibenzofuran groups. Even more preferred are compounds of formula (I) that contain only one fluorene group and two dibenzofuran groups, i.e., the compound does not contain any further fluorene or dibenzofuran groups. Z 1 and Z 2 But, CR 2 Preferred are compounds of formula (I) defined as (forming the first fluorene group), wherein m=0 and Ar 1 contains or is a dibenzofuran group (first dibenzofuran group), and Ar 2 contains or is a dibenzofuran group (second dibenzofuran group), and very preferably, Ar 1 and Ar 2 are identical or different and are selected from the groups Ar-63 to Ar-66, Ar-71 to Ar-85, Ar-99, Ar-100, Ar-102, Ar-103, Ar-204, Ar-205, Ar-206, very preferably from Ar-63 to Ar-66, Ar-71 to Ar-85, Ar-99, Ar-100, Ar-102, Ar-103, particularly preferably from Ar-71 to Ar-83 and Ar-85, and very particularly preferably from Ar 1 and Ar 2are both Ar-78 and Ar 1 and Ar 2 both of which have a group R 4 may be substituted with.

[0184] It is further preferred if the compound of formula (I) comprises one fluorene group and two dibenzofuran groups, wherein particularly preferred substituents for the two groups at the 9-position of the fluorene group are selected from -CH3, -CD3, phenyl (-C6H5) and -C6D5.

[0185] In yet another preferred embodiment of the present invention, the compound of formula (I) comprises one fluorene group and one dibenzofuran group. Even more preferred are compounds of formula (I) containing only one fluorene group and one dibenzofuran group, i.e., the compound does not contain any further fluorene or dibenzofuran groups. Z 1 and Z 2 But, CR 2 Preferred are compounds of formula (I) defined as (forming the first fluorene group), wherein m=0 and Ar 1 or Ar 2 and only one of them contains or is a dibenzofuran group, and very preferably Ar 1 or Ar 2 are selected from the groups Ar-63 to Ar-66, Ar-71 to Ar-85, Ar-99, Ar-100, Ar-102, Ar-103, Ar-204, Ar-205, Ar-206, very preferably from Ar-63 to Ar-66, Ar-71 to Ar-85, Ar-99, Ar-100, Ar-102, Ar-103, particularly preferably from Ar-71 to Ar-83 and Ar-85, and very particularly preferably from Ar 1 or Ar 2 Only one of them is Ar-78, and Ar 1 and Ar 2 both of which have a group R 4 may be substituted with.

[0186] It is further preferred if the compound of formula (I) comprises one fluorene group and one dibenzofuran group, wherein particularly preferred substituents for the two groups at the 9-position of the fluorene group are selected from -CH3, -CD3, phenyl (-C6H5) and -C6D5.

[0187] Preferred compounds according to formula (I) are shown in the table below:

[0188] [ka]

[0189] [ka]

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193] [ka]

[0194] [ka]

[0195] [ka]

[0196] [ka]

[0197] [ka]

[0198] [ka]

[0199] [ka]

[0200] [ka]

[0201] [ka]

[0202] The compounds of the present application are prepared by using standard methods known in the art of organic synthesis, such as halogenation and metal-catalyzed coupling reactions, particularly the Suzuki and Buchwald reactions.

[0203] The following scheme illustrates a preferred synthetic method for the synthesis of compounds according to formula (I) of the present application. According to this synthetic method, a fluorene derivative A, preferably having a leaving group at the 2-position, is converted to a compound of formula Ar by a C-N coupling reaction, preferably a Buchwald coupling reaction. 2 -NH-Ar 1 with a diarylamino derivative B of:

[0204] [ka]

[0205] The following scheme illustrates another preferred synthetic method for synthesizing compounds of formula (I) according to the present application, wherein a fluorene derivative C, preferably having leaving groups at the 5- and 2-positions, is converted to a compound of formula R by Suzuki coupling reaction. 1 -B(OH)2 with a boronic acid D. Thereafter, a boronic acid of formula Ar is reacted with a boronic acid of formula Ar at the 2-position of the resulting intermediate E. 2 -NH-Ar 1 Buchwald coupling reaction with a diarylamino derivative of the formula (I) of the present application gives the corresponding compound:

[0206] [ka]

[0207] The variables appearing in these schemes are as defined above.

[0208] The above reaction results in a compound according to formula (I) of the present application.

[0209] Therefore, a further aspect of the present invention is a process for preparing a compound according to formula (I), comprising introducing a diarylamino group by C-N coupling reaction of a fluorene derivative halogenated at the 2-position with a diarylamine derivative.

[0210] The synthetic methods for obtaining the fluorine derivatives A and C, and the diarylamine derivative C, used in the synthesis of the compounds according to the invention are known to those skilled in the art.

[0211] In particular, the compounds according to formula (I) of the present invention can be prepared by reacting alkyl 5-halo-2-iodobenzoates as starting compounds with arylboronic acids via Suzuki coupling reaction.

[0212] Particularly preferably, the process for preparing the compounds according to formula (I) of the present invention comprises: a) General formula (II)

[0213] [ka]

[0214] (wherein X=Cl or Br) and a methyl 5-halo-2-iodobenzoate represented by the formulas (III-1) to (III-5):

[0215] [ka]

[0216] (In the formula, R 1 are identical or different on each occurrence and are as defined above, but are preferably selected from phenyl, biphenyl, terphenyl or quaterphenyl, each of which may be selected from one or more radicals R as defined above. 5 may be optionally substituted by; X is Cl or Br to obtain a 5-halobenzoate methyl ester derivative, and then c) a reaction step of converting the ester derivative into a tertiary alcohol by using an alkyl or aryl magnesium halide, and then d) carrying out an acid-catalyzed cyclization to obtain a fluorene derivative halogenated at the 2-position, and then e) A reaction step of reacting a fluorene derivative with a diarylamine derivative to obtain a compound of formula (I). Includes:

[0217] The alkyl or aryl magnesium halide in step b) is preferably, but not limited to, methyl or phenyl magnesium chloride, as commonly used in Grignard reactions. The acid for catalyzing the cyclization in step c) can be, for example, BF3·Et2O. The catalyst for the Suzuki coupling reaction in step a) can be, but is not limited to, Pd(P(Ph3))4. The reaction conditions for carrying out the Suzuki coupling reaction, Grignard reaction, and cyclization are known to those skilled in the art.

[0218] Illustrative examples of arylboronic acids that may be used are the following compounds:

[0219] [ka]

[0220] In an alternative preferred method, the compound according to formula (I) of the present invention is a-1) a reaction step of reacting a biphenyl halogenated at least at the 2- and 4-positions with a diaryl, dialkyl or arylalkyl ketone derivative, such as a benzophenone derivative, using an organometallic compound, and then b-1) a reaction step of carrying out an acid-catalyzed cyclization to obtain a fluorene derivative halogenated at the 2-position, and then c-1) A reaction step of reacting a fluorene derivative with a diarylamine derivative to obtain a compound of formula (I) It can be prepared by

[0221] The fluorene derivative halogenated at the 2-position can be prepared according to the above reaction steps a) to c) or steps a-1) to b-1), or can be obtained, obtained or isolated from the above reaction step c) or b-1).

[0222] Therefore, the present invention provides compounds of formula (IV-A) to (IV-L)

[0223] [ka]

[0224] [ka]

[0225] (In the formula, R 1 are the same or different at each occurrence and are selected from phenyl, biphenyl, terphenyl or quaterphenyl, each of which is selected from one or more radicals R as defined above. 5 may be optionally substituted by; R 3 are the same or different at each occurrence and are selected from methyl-CD3, and phenyl or deuterated phenyl (CD6), each of which is selected from one or more radicals R as defined above. 5 may be optionally substituted by; X is Cl or Br Further provided is a fluorene derivative that meets one of the following formulas:

[0226] Particularly preferred fluorene derivatives of the present invention conform to one of the following formulae:

[0227] [ka]

[0228] [ka]

[0229] The compounds of formula (I) above, especially those substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic esters, can find use as monomers for the production of 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 involved in cycloadditions, for example 1,3-dipolar cycloadditions, such as dienes or azides, carboxylic acid derivatives, alcohols and silanes.

[0230] Thus, the present invention further provides an oligomer, polymer or dendrimer containing one or more compounds of formula (I), wherein the bond to the polymer, oligomer or dendrimer is R 1 , R 2 , R 3 , R 4 , R 5 or R 6The units of formula (I) may be located at any desired position, substituted by. Depending on the linkage of the compounds of formula (I), the compounds may be part of a side chain or part of the main chain of an 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 with linear linkages, the units of formula (I) may be directly linked to each other or may be linked to each other via a divalent group, for example via a substituted or unsubstituted alkylene group, via a heteroatom, or via a divalent aromatic or heteroaromatic group. In branched and dendritic structures, for example, three or more units of formula (I) can be linked via trivalent or higher valent groups, for example via trivalent or higher valent aromatic or heteroaromatic groups, to give branched or dendritic oligomers or polymers.

[0231] For repeat units of formula (I) in oligomers, dendrimers and polymers, the same preferences apply as those set out above for compounds of formula (I).

[0232] To prepare oligomers or polymers, the monomers of the invention are homopolymerized or copolymerized with further monomers. Suitable and preferred comonomers are fluorene (for example according to EP 842208 or WO 2000 / 22026), spirobifluorene (for example according to EP 707020, EP 894107 or WO 2006 / 061181), paraphenylene (for example according to WO 1992 / 18552), carbazole (for example according to WO 2004 / 070772 or WO 2004 / 113468), thiophene (for example according to EP 1028136), dihydrogen fluorene (for example according to WO 2004 / 070772 or WO 2004 / 113468 ...), dihydrogen fluorene (for example according to WO 2004 / 070772), dihydrogen fluorene (for example according to WO 2004 / 0 The polymers, oligomers and dendrimers are typically selected from among phenanthrenes (e.g., according to WO 2005 / 014689 or WO 2007 / 006383), cis- and trans-indenofluorenes (e.g., according to WO 2004 / 041901 or WO 2004 / 113412), ketones (e.g., according to WO 2005 / 040302), phenanthrenes (e.g., according to WO 2005 / 104264 or WO 2007 / 017066), or from a plurality of these units. The polymers, oligomers and dendrimers typically contain further units, such as luminescent (fluorescent or phosphorescent) units, such as vinyltriarylamines (e.g., according to WO 2007 / 068325) or phosphorescent metal complexes (e.g., according to WO 2006 / 003000), and / or charge transport units, especially those based on triarylamines.

[0233] The polymers and oligomers of the present invention are generally prepared by polymerization of one or more monomers, at least one of which provides a repeating unit 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 the formation of C-C or C-N bonds are Suzuki polymerization, Yamamoto polymerization, Stille polymerization, and Hartwig-Buchwald polymerization.

[0234] The compound according to the present invention can be used or applied with other organic functional materials, which are generally used in prior art electronic devices.A wide variety of suitable organic functional materials are known to those skilled in the art of electronic devices.Therefore, the present invention further provides a composition comprising one or more compounds of formula (I) or one or more polymers, oligomers or dendrimers containing one or more compounds of formula (I), and at least one other organic functional material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, electron blocking materials, hole blocking materials, wide band gap materials, delayed fluorescent emitters and delayed fluorescent hosts.

[0235] Delayed fluorescent emitters and delayed fluorescent hosts are well known in the art and are disclosed, for example, in Ye Tao et al., Adv. Mater. 2014, 26, 7931-7958, MY Wong et al., Adv. Mater. 2017, 29, 1605444, WO2011 / 070963, WO2012 / 133188, WO2015 / 022974 and WO2015 / 098975. Typically, delayed fluorescent materials (emitters and / or hosts) are characterized by a fairly small gap between their singlet energy (S1) and triplet energy (T1). Preferably, ΔE ST is less than or equal to 0.5 eV, very preferably less than or equal to 0.3 eV, particularly preferably less than or equal to 0.2 eV, and most preferably less than or equal to 0.1 eV, where ΔE ST represents the difference between the singlet energy (S1) and the triplet energy (T1).

[0236] Within the scope of the present invention, wide bandgap materials are understood to mean materials such as those disclosed in US Pat. No. 7,294,849, which are characterized by a bandgap of at least 3 eV, preferably at least 3.5 eV, and very preferably at least 4.0 eV, where the term "bandgap" refers to the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Such systems exhibit particularly advantageous performance characteristics in electroluminescent devices.

[0237] Processing the compounds and compositions of the present invention from a liquid phase, for example by spin-coating or printing, requires a formulation of the compounds and compositions of the present invention. 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 and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 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, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanoic acid, cyclohexanone ... Examples of suitable solvents include methyl benzoate, 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.

[0238] Therefore, the present invention further provides a formulation, in particular a solution, dispersion or emulsion, comprising at least one compound of formula (I), or an oligomer, polymer or dendrimer containing one or more compounds of formula (I), or at least one composition comprising one or more compounds of formula (I), at least one additional organic functional material as described above, and at least one solvent, preferably an organic solvent. Methods for preparing such solutions are known to those skilled in the art and are described, for example, in WO2002 / 072714, WO2003 / 019694 and the documents cited therein.

[0239] The compounds of the present invention are suitable for use in electronic devices, especially organic electroluminescent devices, such as OLEDs. Depending on the substitution, the compounds are used in different functions and layers.

[0240] Therefore, the present invention further provides the use of a compound of formula (I), or an oligomer, polymer, or dendrimer containing one or more compounds of formula (I), or a composition comprising one or more compounds of formula (I) and at least one additional organic functional material as described above, in an electronic device. The electronic device is preferably selected from the group consisting of organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, and more preferably organic electroluminescent devices (EL devices). Preferred EL devices are organic light-emitting transistors (OLETs), organic field-quenched devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs), of which OLEDs are most preferred.

[0241] The present invention further provides an electronic device comprising at least one compound of formula (I), as already mentioned above, said electronic device preferably being selected from the devices described above.

[0242] Particularly preferably, the electronic device is an organic light-emitting diode (OLED) comprising an anode, a cathode and at least one light-emitting layer, characterized in that at least one organic layer, which may be the light-emitting layer, a hole-transporting layer or another layer, preferably the light-emitting layer or the hole-transporting layer, particularly preferably the hole-transporting layer, comprises at least one compound of formula (I).

[0243] Within the scope of the present invention, the term "organic layer" is understood to mean any layer of an electronic device that contains one or more organic compounds as functional materials.

[0244] In addition to the cathode, anode, and light-emitting layer, organic light-emitting diodes may also comprise further layers, for example, selected in each case from 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 (IDMC2003, Taiwan; Session 21 OLED(5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and / or organic or inorganic p / n junctions.

[0245] The layer order of an organic light-emitting diode comprising a compound of formula (I) is preferably as follows: anode - hole injection layer - hole transport layer - optional further hole transport layer - optional electron blocking layer - light-emitting layer - optional hole blocking layer - electron transport layer - electron injection layer - cathode. In addition, further layers may be present in the OLED.

[0246] The organic light-emitting diode of the present invention may contain two or more light-emitting layers. More preferably, these light-emitting layers have several emission maxima between 380 nm and 750 nm, resulting in a white light emission overall; in other words, various light-emitting compounds, which may be fluorescent or phosphorescent and emit blue, green, yellow, orange, or red light, are used in the light-emitting layers. Particularly preferred are three-layer systems, i.e., systems with three light-emitting layers, which emit blue, green, and orange or red light (see, for example, WO2005 / 011013 for basic structures). The compound of the present invention is preferably present in a hole-transporting layer, a hole-injecting layer, or an electron-blocking layer, most preferably in an electron-blocking layer.

[0247] According to the present invention, the compounds of formula (I) are preferably used in electronic devices comprising one or more phosphorescent compounds, in which case the compounds may be present in different layers, preferably in a hole transport layer, an electron blocking layer, a hole injection layer or an emissive layer.

[0248] The term "phosphorescent compound" typically includes compounds in which emission occurs through a spin-forbidden transition, e.g., a transition from an excited triplet state or a state with a higher spin quantum number, e.g., a quintet state.

[0249] Suitable phosphorescent compounds (= triplet emitters) are, in particular, compounds that, when appropriately excited, preferably emit light in the visible range, and further 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 compounds, it is preferred to use compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium, platinum or copper. In the context of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent compounds.

[0250] Examples of the above-mentioned light-emitting compounds can be found in the applications WO00 / 70655, WO01 / 41512, WO02 / 02714, WO02 / 15645, EP1191613, EP1191612, EP1191614, WO05 / 033244, WO05 / 019373 and US2005 / 0258742.Generally, all phosphorescent complexes that are used in phosphorescent OLEDs according to the prior art and known to those skilled in the art of organic electroluminescent devices are suitable.Those skilled in the art can also use other phosphorescent complexes in combination with the compound of formula (I) in organic electroluminescent devices without exerting inventive skills.Further examples are listed in the following table.

[0251] In accordance with the present invention, the compounds of formula (I) may also be used in electronic devices that include one or more fluorescent light-emitting compounds.

[0252] In a preferred embodiment of the present invention, the compound of formula (I) is used as a hole transport material. In that case, the compound is preferably present in a hole transport layer, an electron blocking layer or a hole injection layer. Use in an electron blocking layer is particularly preferred.

[0253] The hole transport layer according to the present invention is a layer having a hole transport function between the anode and the light emitting layer.

[0254] In the context of this application, the hole injection layer and the electron blocking layer are understood to be specific embodiments of the hole transport layer.The hole injection layer is a hole transport layer that is directly adjacent to the anode or separated from the anode by only a single coating of the anode when there are multiple hole transport layers between the anode and the light emitting layer.The electron blocking layer is a hole transport layer that is directly adjacent to the light emitting layer on the anode side when there are multiple hole transport layers between the anode and the light emitting layer.Preferably, the OLED of the present invention comprises two, three, or four hole transport layers between the anode and the light emitting layer, at least one of which preferably contains a compound of formula (I), and more preferably, exactly one or two of which contain a compound of formula (I).

[0255] When the compound of formula (I) is used as a hole transport material in a hole transport layer, a hole injection layer, or an electron blocking layer, the compound can be used as a pure material, i.e., 100% in the hole transport layer, or can be used in combination with one or more additional compounds.In this case, in a preferred embodiment, the organic layer containing the compound of formula (I) additionally contains one or more p-dopants.The p-dopants used in the present invention are preferably organic electron acceptor compounds that can oxidize one or more other compounds in the mixture.

[0256] Particularly preferred embodiments of p-dopants are the compounds disclosed in WO2011 / 073149, EP1968131, EP2276085, EP2213662, EP1722602, EP2045848, DE102007031220, US8044390, US8057712, WO2009 / 003455, WO2010 / 094378, WO2011 / 120709, US2010 / 0096600, WO2012 / 095143 and DE102012209523.

[0257] 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 of the third main group, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd, and Pt with a ligand containing at least one oxygen atom as a bonding site. Transition metal oxides are also preferred as dopants, preferably oxides of rhenium, molybdenum, and tungsten, more preferably Re2O7, MoO3, WO3, and ReO3.

[0258] The p-dopant is preferably substantially uniformly distributed in the p-doped layer, which can be achieved, for example, by co-evaporation of the p-dopant and the hole transport material matrix.

[0259] Preferred p-dopants are especially the following compounds:

[0260] [ka]

[0261] In a further preferred embodiment of the present invention, the compounds of formula (I) are used as hole transport materials in combination with hexaazatriphenylene derivatives as described in US 2007 / 0092755, where it is particularly preferred to use the hexaazatriphenylene derivatives in a separate layer.

[0262] Additional hole transport materials that can be used in any layer requiring a material with hole transport capability, such as a hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), or light emitting layer (EML), are listed in the table below. The compounds can be readily prepared according to the disclosures cited for each of the compounds. Compounds (1)-(22) exhibit excellent stability, and electronic devices containing the compounds exhibit high efficiency, low voltage, and improved lifetime.

[0263] [ka]

[0264] [ka]

[0265] [ka]

[0266] In a further embodiment of the present invention, the compounds of formula (I) are used in an emissive layer as matrix material in combination with one or more emissive compounds, preferably phosphorescent emissive compounds.

[0267] 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 92.0% to 99.5% by volume for a fluorescent light-emitting layer, and 85.0% to 97.0% by volume for a phosphorescent light-emitting layer.

[0268] Accordingly, the proportion of the luminescent compound is 0.1% to 50.0% by volume, preferably 0.5% to 20.0% by volume, more preferably 0.5% to 8.0% by volume for the fluorescent luminescent layer, and 3.0% to 15.0% by volume for the phosphorescent luminescent layer.

[0269] The light-emitting layer of an organic light-emitting diode 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 the lower proportion in the system, and the matrix material is the compound with the 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.

[0270] The compound of formula (I) is preferably used as a component of a mixed matrix system. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Preferably, one of the two materials has hole-transporting properties, and the other has electron-transporting properties. The compound of formula (I) is preferably a matrix material with hole-transporting properties. However, the desired electron-transporting and hole-transporting properties of the mixed matrix component may be primarily or completely possessed by a single mixed matrix component, in which case an additional mixed matrix component performs another function. 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. The use of a mixed matrix system for phosphorescent organic light-emitting diodes is preferred. One source of more detailed information on mixed matrix systems is application WO2010 / 108579.

[0271] The mixed matrix system may comprise one or more light-emitting compounds, preferably one or more phosphorescent light-emitting compounds. Generally, the mixed matrix system is preferably used in phosphorescent organic light-emitting diodes.

[0272] Particularly suitable matrix materials that can be used in combination with the compounds of the present invention as matrix components in a mixed matrix system are selected from the preferred matrix materials for phosphorescent compounds or preferred matrix materials for fluorescent compounds listed below, depending on what type of luminescent compound is used in the mixed matrix system.

[0273] Preferred phosphorescent compounds for use in mixed matrix systems are generally the same as those detailed above as preferred phosphorescent materials.

[0274] Preferred embodiments of various functional materials in electronic devices are listed below.

[0275] Preferred phosphorescent compounds are:

[0276] [ka]

[0277] [ka]

[0278] [ka]

[0279] [ka]

[0280] [ka]

[0281]

change

[0282]

change

[0283]

change

[0284]

change

[0285]

change

[0286] Preferred fluorescent compounds are selected from the arylamine class. In the context of the present invention, arylamine or aromatic amine refers to 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 refer to compounds in which a diarylamino group is directly bonded to an anthracene group, preferably at the 9-position. Aromatic anthracenediamines refer to 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, in which the diarylamino group is bonded to the pyrene group, preferably at the 1- or 1- and 6-positions. Further preferred light-emitting compounds are indenofluoreneamines or -fluorenediamines, for example according to WO 2006 / 108497 or WO 2006 / 122630, benzoindenofluoreneamines or -fluorenediamines, for example according to WO 2008 / 006449, and dibenzoindenofluoreneamines or -diamines, for example according to WO 2007 / 140847, as well as indenofluorene derivatives with fused aryl groups, as disclosed in WO 2010 / 012328. Also preferred are pyrenearylamines, as disclosed in WO 2012 / 048780 and WO 2013 / 185871.Also preferred are the benzoindenofluorene amines disclosed in WO2014 / 037077, the benzofluorene amines disclosed in WO2014 / 106522, the extended benzoindenofluorenes disclosed in WO2014 / 111269 and WO2017 / 036574, the phenoxazines disclosed in WO2017 / 028940 and WO2017 / 028941, and fluorene derivatives linked to furan or thiophene units disclosed in WO2016 / 150544.

[0287] Matrix materials that are preferably useful for fluorescent light-emitting compounds include materials from various substance classes. Preferred matrix materials are oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461, or dinaphthylanthracene), especially oligoarylenes containing fused aromatic groups, oligoarylenevinylenes (e.g., DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (e.g., according to WO 2004 / 081017), hole-conducting compounds (e.g., The matrix materials are selected from the classes of oligoarylenes, oligoarylenevinylenes, ketones, phosphine oxides, sulfoxides, etc. (e.g., according to WO 2004 / 058911), electron-conducting compounds, especially ketones, phosphine oxides, sulfoxides, etc. (e.g., according to WO 2005 / 084081 and WO 2005 / 084082), atropisomers (e.g., according to WO 2006 / 048268), boronic acid derivatives (e.g., according to WO 2006 / 117052), or benzanthracenes (e.g., according to WO 2008 / 145239). Particularly preferred matrix materials are selected from the classes of oligoarylenes, oligoarylenevinylenes, ketones, phosphine oxides, and sulfoxides, including naphthalene, anthracene, benzanthracene, and / or pyrene, or atropisomers of these compounds. Very particularly preferred matrix materials are selected from the class of oligoarylenes, which include 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 bonded to one another.Furthermore, anthracene derivatives disclosed in WO2006 / 097208, WO2006 / 131192, WO2007 / 065550, WO2007 / 110129, WO2007 / 065678, WO2008 / 145239, WO2009 / 100925, WO2011 / 054442 and EP1553154, pyrene compounds disclosed in EP1749809, EP1905754 and US2012 / 0187826, benzanthracenylanthracene compounds disclosed in WO2015 / 158409, indenobenzofurans disclosed in WO2017 / 025165, and phenanthrylanthracenes disclosed in WO2017 / 036573 are preferred.

[0288] Preferred matrix materials for phosphorescent compounds, 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), according to, for example, WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, or compounds such as, for example, benzophenone (BBP), N,N-biscarbazolylbiphenyl (BBP), N ... carbazole derivatives disclosed in WO 2004 / 288381, EP 1205527 or WO 2008 / 086851, for example indolocarbazole derivatives according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives according to WO 2010 / 136109, W2011 / 000455 or W2013 / 041176, azacarbazole derivatives according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, azole derivatives, for example bipolar matrix materials according to WO 2007 / 137725, silanes, for example, according to WO 2005 / 111172, azaboroles or boronic esters, for example, according to WO 2006 / 117052, triazine derivatives, for example, according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes, for example, according to EP 652273 or WO 2009 / 062578, diazabicyclo[4.2.1]c acid, for example, according to WO 2010 / 054729 ol or tetraazasilol derivatives, for example diazaphosphole derivatives according to WO 2010 / 054730, bridged carbazole derivatives, for example according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107, WO 2011 / 088877 or WO 2012 / 143080, triphenylene derivatives, for example according to WO 2012 / 048781, or lactams, for example according to WO 2011 / 116865 or WO 2011 / 137951.

[0289] Suitable charge transport materials that can be used in the hole-injection or hole-transport layer or electron-blocking layer, or in the electron-transport layer, of the electronic device of the present invention are, in addition to the compounds of formula (I), 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.

[0290] Preferably, the OLED of the present invention comprises two or more different hole transport layers.Here, the compound of formula (I) may be used in one or more or all of the hole transport layers.In a preferred embodiment, the compound of formula (I) is used in exactly one or exactly two hole transport layers, and other compounds, preferably aromatic amine compounds, are used in the other hole transport layers that exist.The other compounds that are preferably used in the hole transport layer of the OLED of the present invention together with the compound of formula (I) include, inter alia, indenofluorene amine derivatives (for example, according to WO06 / 122630 or WO06 / 100896), amine derivatives disclosed in EP1661888, hexaazatriphenylene derivatives (for example, according to WO01 / 049806), amine derivatives with condensed aromatic rings (for example, according to US5,061,569), and the amine derivatives disclosed in WO95 / 09 147, monobenzoindenofluoreneamines (e.g., according to WO 08 / 006449), dibenzoindenofluoreneamines (e.g., according to WO 07 / 140847), spirobifluoreneamines (e.g., according to WO 2012 / 034627 or WO 2013 / 120577), fluoreneamines (e.g., according to WO 2014 / 015937, WO 2014 / 015938, WO 2014 / 015935 and WO 2 015 / 082056), spirodibenzopyranamines (e.g. according to WO2013 / 083216), dihydroacridine derivatives (e.g. according to WO2012 / 150001), for example spirodibenzofurans and spirodibenzothiophenes according to WO2015 / 022051, W2016 / 102048 and W2016 / 131521, phenanthrediarylamines, for example according to WO2015 / 131976, Examples include spirotribenzotropolones according to WO2016 / 087017, spirobifluorenes having a meta-phenyldiamine group according to WO2016 / 078738, spirobisacridines according to WO2015 / 158411, xanthenediarylamines according to WO2014 / 072017, and 9,10-dihydroanthracene spiro compounds having a diarylamino group according to WO2015 / 086108.

[0291] Very particular preference is given to the use as hole-transporting compounds of spirobifluorenes substituted in the 4-position by a diarylamino group, in particular the use of the compounds claimed and disclosed in WO2013 / 120577, and to the use as hole-transporting compounds of spirobifluorenes substituted in the 2-position by a diarylamino group, in particular the use of the compounds claimed and disclosed in WO2012 / 034627.

[0292] The material used in the electron transport layer may be any material that is used as an electron transport material in the electron transport layer according to the prior art. Particularly suitable 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. Further suitable materials are derivatives of the above compounds, as disclosed in JP2000 / 053957, WO2003 / 060956, WO2004 / 028217, WO2004 / 080975, and WO2010 / 072300.

[0293] Preferred cathodes for electronic devices are metals, metal alloys, or multilayer structures composed of various metals, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.), with low work functions. Additionally, alloys composed of alkali metals or alkaline earth metals and silver, such as alloys composed of magnesium and silver, are suitable. 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 also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between the metal 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.

[0294] Preferred anodes are materials with a high work function. Preferably, the anode has a work function greater 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 / NiOx, Al / PtOx) may be preferred. Depending on the application, at least one of the electrodes must be transparent or partially transparent to allow irradiation of the organic material (organic solar cells) or for 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 consist of two or more layers, such as an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide, or vanadium oxide.

[0295] The device is appropriately structured (depending on the application), contacted and finally sealed to eliminate the damaging effects of water and air.

[0296] In a preferred embodiment, the electronic device is characterized in that one or more layers are coated by a sublimation process, in which case the material is deposited in a vacuum sublimation system for 10 -5 less than mbar, preferably 10 -6 The deposition is carried out at an initial pressure of less than 10 mbar. However, in this case the initial pressure may be even lower, for example 10 -7 It is also possible to have a pressure below mbar.

[0297] Likewise preferred are electronic devices 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 -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 from a nozzle and is therefore structured (for example, M.S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0298] 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.

[0299] 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.

[0300] 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 (e.g., phototherapy).

[0301] The compound according to the invention and the electronic device according to the invention, respectively, exhibit the following surprising beneficial effects compared to the prior art: 1. The compounds according to the invention are particularly suitable as hole transport materials in electron blocking layers of electronic devices, such as electroluminescent devices, due in particular to the very good electron blocking and hole conducting properties of the compounds.

[0302] 2. The compounds according to the invention are characterized by a low sublimation temperature, high thermal stability, high oxidative stability, high glass transition temperature and high solubility, which are advantageous in terms of processability of the compounds, e.g. from the liquid or gas phase, making the compounds particularly suitable for use in electronic devices.

[0303] 3. When used in electronic devices, especially as hole transport materials, the compounds according to the invention provide excellent results in terms of device lifetime, operating voltage and quantum efficiency.

[0304] 4. Compounds containing deuterium are more thermally stable and devices containing them exhibit longer lifetimes and improved efficiency.

[0305] The invention is explained in more detail below with the help of examples, which should not be considered as limiting the scope of the invention.

[0306] [example] A) Synthesis example The following syntheses are carried out under a protective gas atmosphere unless otherwise indicated. The starting materials can be purchased from Aldrich or ABCR. For starting materials known from the literature, the numbers in brackets are the corresponding CAS numbers.

[0307] Example 1 Synthesis of 2-{[1,1'-biphenyl]-2-yl}-5-bromobenzoate methyl ester 1a

[0308] [ka]

[0309] 2.9 g (14.9 mmol) of (1,1'-biphenyl)-2-yl-boronic acid, 4.6 g (13.6 mmol) of methyl 5-bromo-2-iodobenzoate, 314 mg (0.3 mmol, 0.02 equiv.) of Pd(P(Ph3))4, and 5.6 g (40.7 mmol, 3 equiv.) of Na2CO3 are dissolved in 7 mL of water and 30 mL of toluene. The reaction mixture is stirred at 85 °C and shaken under argon for 12 hours. After cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo, and the residue is purified by chromatography (heptane / AcOEt mixture). The product is isolated in the form of an off-white solid (4.5 g, 91% of theory).

[0310] Further derivatives are synthesized in a similar manner:

[0311] [ka]

[0312] [ka]

[0313] [ka]

[0314] Synthesis of 2-(2-{[1,1'-biphenyl]-2-yl}-5-bromophenyl)propan-2-ol 2a

[0315] [ka]

[0316] A solution of 2-{[1,1'-biphenyl]-2-yl}-5-bromobenzoate methyl ester (3 g, 8.2 mmol) in THF (30 ml) is treated with 16 mL of MeMgCl (3 M in THF, 49 mmol, 6 equivalents) at −10° C. under argon. The reaction is allowed to proceed for 30 min at −10° C. and then stirred overnight at room temperature. The reaction is quenched with saturated NH4Cl solution and the mixture is extracted with EtOAc. The organic phase is dried over MgSO4 and concentrated to dryness. The residue is purified by chromatography (heptane / AcOEt mixtures) to isolate pure 2a (1.8 g, 61% of theory).

[0317] The following compounds are similarly synthesized:

[0318] [ka]

[0319] [ka]

[0320] [ka]

[0321] [ka]

[0322] Synthesis of 2-bromo-9,9-dimethyl-5-phenyl-9H-fluorene 3a

[0323] [ka]

[0324] A solution of 2-(2-{[1,1'-biphenyl]-2-yl}-5-bromophenyl)propan-2-ol (1.3 g, 3.5 mmol) in CHCl (26 mL) is treated with 0.54 mL of BF.EtO (4.6 mmol, 1.3 equiv.) under argon at 0 °C. The mixture is stirred for 30 min. The reaction is stirred at room temperature for 2 h. The reaction is quenched with saturated NaHCO solution and the mixture is extracted with CHCl. ​​The organic phase is dried over MgSO and concentrated to dryness. The residue is purified by chromatography (heptane / AcOEt mixtures) to isolate pure 3a (0.9 g, 72% of theory).

[0325] The following compounds are similarly synthesized:

[0326] [ka]

[0327] [ka]

[0328] [ka]

[0329] [ka]

[0330] Synthesis of N-{[1,1'-biphenyl]-4-yl}-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-5-phenyl-9H-fluoren-2-amine 4a

[0331] [ka]

[0332] S-Phos (1.06 g, 2.6 mmol), Pd2(dba)3 (1.18 g, 1.29 mmol), and sodium tert-butoxide (48.3 g, 85.9 mmol) were added to a degassed toluene (200 ml) solution of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (15.5 g, 42.9 mmol) and 2-bromo-9,9-dimethyl-5-phenyl-9H-fluorene (15 g, 42.9 mmol), and the mixture was heated under reflux for 10 h. The reaction mixture was cooled to room temperature, diluted with toluene, and filtered through Celite. The filtrate was evaporated in vacuo, and the residue was crystallized from toluene / heptane. The crude product was extracted with a Soxhlet extractor (toluene) and purified twice by zone sublimation in vacuo. The product is isolated in the form of an off-white solid (12 g, 45% of theory).

[0333] Similarly, the following compounds are obtained:

[0334] [ka]

[0335] [ka]

[0336] [ka]

[0337] [ka]

[0338] [ka]

[0339] [ka]

[0340] [ka]

[0341] [ka]

[0342] [ka]

[0343] [ka]

[0344] [ka]

[0345] [ka]

[0346] Synthesis of N-{[1,1'-biphenyl]-4-yl}-N-[4-(9,9-dimethyl-5-phenyl-9H-fluoren-2-yl)phenyl]-9,9-dimethyl-9H-fluoren-2-amine 5a

[0347] [ka]

[0348] 59.1 g (101.8 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl)amine, 35.5 g (101.8 mmol) of 2-bromo-9,9-dimethyl-5-phenyl-9H-fluorene, 3.88 g (5.14 mmol) of PdCl(Cy), 31.2 g (205.6 mmol) of ) of cesium fluoride is dissolved in 800 mL of toluene. The reaction mixture is refluxed and shaken under argon for 12 hours, and after cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo and the residue is crystallized from heptane. The crude product is extracted with a Soxhlet extractor (toluene) and purified twice by zone sublimation in vacuo. The product is isolated in the form of a white solid (42 g, 59% of theory).

[0349] The following compounds are similarly synthesized:

[0350] [ka]

[0351] [ka]

[0352] [ka]

[0353] [ka]

[0354] Synthesis of 5-bromo-2-chloro-9,9-diphenyl-9H-fluorene 6a

[0355] [ka]

[0356] A solution of 2,2'-dibromo-4-chloro-biphenyl (84 g, 239 mmol) in THF (200 ml) is treated with 109 ml of n-BuLi (2.2 M in hexane, 239 mmol) under argon at -78 °C. The mixture is stirred for 30 minutes. A solution of benzophenone (43.5 g, 239 mmol) in 150 ml of THF is added dropwise. The reaction is allowed to proceed for 30 minutes at -78 °C and then stirred overnight at room temperature. The reaction is quenched with water and the solid is filtered. Without further purification, a solution of this alcohol in 966 ml of toluene and 2.9 g of p-toluenesulfonic acid is refluxed overnight. After cooling, the organic phase is washed with water and the solvent is removed under vacuum. The product is isolated in the form of a white solid (60 g, 90% of theory).

[0357] The synthesis of further halogenated fluorene derivatives is carried out similarly:

[0358] [ka]

[0359] [ka]

[0360] [ka]

[0361] Synthesis of 2-chloro-5,9,9-triphenyl-9H-fluorene 7a

[0362] [ka]

[0363] 31.5 g (251 mmol) of phenylboronic acid, 108.4 g (251 mmol) of 5-bromo-2-chloro-9,9-diphenyl-9H-fluorene, 9.9 g (8.5 mmol) of Pd(P(Ph3))4, and 66.8 g (627 mmol) of Na2CO3 are dissolved in 903 mL of water, 278 mL of ethanol, and 1.9 L of toluene. The reaction mixture is refluxed and shaken under argon for 12 hours. After cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallized from heptane. The product is isolated in the form of an off-white solid (100 g, 93% of theory).

[0364] The following compounds are similarly synthesized:

[0365] [ka]

[0366] [ka]

[0367] B) OLED manufacturing The OLEDs according to the invention and the prior art OLEDs are produced by the general methods according to WO2004 / 058911, but the methods are adapted to the circumstances (eg materials) described therein.

[0368] Data for various OLEDs are presented in the following examples (see Tables 1 to 7). The substrate used is a glass plate coated with a structured ITO (indium tin oxide) layer 50 nm thick. The 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 aluminum layer. The materials required for the production of the OLED are listed in Table 7.

[0369] All materials are applied by thermal evaporation in a vacuum chamber. The emissive layer here always consists of at least one matrix material (host material) and a light-emitting dopant (emitter), which is mixed into the matrix material in a certain volumetric proportion by co-evaporation. Here, the expression, for example, H1:SEB(5%), means that the material H1 is present in the layer in a volumetric proportion of 95% and the material SEB is present in the layer in a volumetric proportion of 5%. Similarly, other layers may consist of a mixture of two or more materials.

[0370] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, the external quantum efficiency (EQE, measured in percent) as a function of luminous density calculated from the current / voltage / luminous flux density characteristic line (IUL characteristic line) assuming Lambertian emission characteristics, and the lifetime are determined. EQE @ 10 mA / cm 2 The expression is 10mA / cm 2 LT80@60mA / cm 2 indicates that the OLED achieves an initial luminance of 5000 cd / m without the use of any promoter. 2 to 80% of the initial intensity, i.e., 4000 cd / m 2 The data for various OLEDs containing the materials of the present invention are summarized in Tables 2-6. Use of the compounds according to the invention in fluorescent and phosphorescent OLEDs In particular, the compounds according to the present invention are suitable as HILs, HTLs, EBLs in OLEDs or as matrix materials in EMLs, and are suitable not only for use as a single layer but also as a mixed component as a HIL, HTL, EBL or as a mixed component in an EML.

[0371] OLED devices having this structure are shown below in Tables 1, 3, 4 and 5. Tables 2 and 6 provide device data.

[0372] OLEDs E1 to E27 are OLEDs according to the present application, containing compounds HTM-1 to HTM-14 of the present application as the HTL and EBL, respectively. COMP-1 and COMP-2 are comparative examples. OLEDs E1 to E27 according to the present application all exhibit long lifetimes, low voltages, and good efficiency in singlet blue devices and even triplet green devices. In particular, compared to the comparative examples, the examples according to the present application clearly demonstrate statistically and physically significant improvements in efficiency.

[0373] [Table 1]

[0374] [Table 2]

[0375] Tables 3-6 summarize additional device data for OLEDs containing compounds HTM-10-HTM-14 of the present invention.

[0376] [Table 3]

[0377] [Table 4]

[0378] [Table 5]

[0379] [Table 6]

[0380] [Table 7-1]

[0381] Table 7-2

Claims

1. Formula (I) 【Chemistry 1】 wherein the variables are defined as follows: Z １ is the same or different for each occurrence, and CR １ , C.R. ２ and N; Z ２ is the same or different for each occurrence, and CR ２ and N; Ar Ｌ is an aromatic ring system having 6 to 40 aromatic ring atoms (which may be linked to one or more radicals R ４ and heteroaromatic ring systems having 5 to 40 aromatic ring atoms (which may be substituted by one or more radicals R ４ and optionally substituted by Ar １ , Ar ２ are identical or different aromatic ring systems having 6 to 40 aromatic ring atoms (which are substituted by one or more radicals R ４ and heteroaromatic ring systems having 5 to 40 aromatic ring atoms (which may be substituted by one or more radicals R ４ and optionally substituted by E is a single bond or —C(R ４ ) ２ -, -N(R ４ ) is a divalent group selected from —, —O—, and —S—; R １ are the same or different in each occurrence, and Si(R ５ ) ３ , linear alkyl, alkoxy or thioalkyl groups having 1 to 20 C atoms, branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, wherein said alkyl, alkoxy and thioalkyl groups, and said aromatic and heteroaromatic ring systems, are in each case selected from one or more radicals R ５ may be substituted by R ２ are the same or different at each occurrence, and are H, D, F, Cl, Br, I, C(=O)R ５ , CN, Si(R ５ ) ３ , N(R ５ ) ２ , P(=O)(R ５ ) ２ , OR ５ , S(=O)R ５ , S(=O) ２ R ５ , SCN, SF ５ , a linear alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C 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 two or more radicals R ２ may be linked to each other to form a ring; said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems may in each case be linked to one or more radicals R ５ and one or more of the alkyl, alkoxy, alkenyl and alkynyl groups may be substituted by ２ The group is in each case -R ５ C=CR ５ -, -C≡C-, Si(R ５ ) ２ , C=O, C=S, C=NR ５ , -C(=O)O-, -C(=O)NR ５ -, NR ５ , P(=O)(R ５ ), —O—, —S—, SO or SO ２ R ３ are the same or different at each occurrence, and are H, D, F, Cl, Br, I, C(=O)R ４ , CN, Si(R ４ ) ３ , NO ２ , P(=O)(R ４ ) ２ , S(=O)R ４ , S(=O) ２ R ４ , a linear alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl and alkynyl groups are in each case independently selected from one or more radicals R ５ and one or more of the alkyl, alkoxy, thioalkyl, alkenyl and alkynyl groups may be substituted by ２ The group is in each case -R ５ C=CR ５ -, -C≡C-, Si(R ５ ) ２ , C=O, C=S, C=NR ５ , -C(=O)O-, -C(=O)NR ５ -, NR ５ , P(=O)(R ５ ), —O—, —S—, SO or SO ２ and in said alkyl, alkoxy, thioalkyl, alkenyl and alkynyl groups one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ２ or aromatic or heteroaromatic ring systems having 6 to 30 aromatic ring atoms, wherein said aromatic and heteroaromatic ring systems are in each case replaced by one or more radicals R ５ or an aryloxy group having 5 to 60 aromatic ring atoms or an arylalkyl group having 5 to 60 aromatic ring atoms, wherein the aryloxy and arylalkyl groups are in each case optionally substituted by one or more radicals R ５ and wherein the two radicals R ３ may be linked together to form a ring, thereby constructing a spiro compound at the 9-position of the fluorene group, in which case spirobifluorenes are excluded; R ４ are the same or different at each occurrence, and are H, D, F, C(=O)R ５ , CN, Si(R ５ ) ３ , N(R ５ ) ２ , P(=O)(R ５ ) ２ , OR ５ , S(=O)R ５ , S(=O) ２ R ５ , a linear alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C 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 two or more radicals R ４ may be linked to each other to form a ring; said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems may in each case be linked to one or more radicals R ５ and one or more of the alkyl, alkoxy, alkenyl and alkynyl groups may be substituted by ２ The group is in each case -R ５ C=CR ５ -, -C≡C-, Si(R ５ ) ２ , C=O, C=S, C=NR ５ , -C(=O)O-, -C(=O)NR ５ -, NR ５ , P(=O)(R ５ ), —O—, —S—, SO or SO ２ may be replaced by; R ５ are the same or different in each occurrence and are H, D, F, C(=O)R ６ , CN, Si(R ６ ) ３ , N(R ６ ) ２ , P(=O)(R ６ ) ２ , OR ６ , S(=O)R ６ , S(=O) ２ R ６ , a linear alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C 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 two or more radicals R ５ may be linked to each other to form a ring; said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems may in each case be linked to one or more radicals R ６ and one or more of the alkyl, alkoxy, alkenyl and alkynyl groups may be substituted by ２ The group is in each case -R ６ C=CR ６ -, -C≡C-, Si(R ６ ) ２ , C=O, C=S, C=NR ６ , -C(=O)O-, -C(=O)NR ６ -, NR ６ , P(=O)(R ６ ), —O—, —S—, SO or SO ２ may be replaced by; R ６ are identical or different in each occurrence and are selected from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 C atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R ６ may be linked together to form a ring; said alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by F and CN; m is 0 or 1, where when m=0, the group E is absent and the group Ar １ and Ar ２ are not connected; n is 0 or 1; where, when n=0, the group Ar Ｌ does not exist, and the nitrogen atom and the fluorene group are directly linked) and wherein the compound is １ At least one of the following is CR １ A compound characterized in that:

2. Group Ar Ｌ is selected from divalent radicals derived from benzene, biphenyl, terphenyl, naphthyl, fluorenyl, indenofluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl, each of which is selected from one or more radicals R ４ 2. The compound according to claim 1, wherein the compound is optionally substituted by:

3. Group Ar １ and Ar ２ is selected from a radical containing at least two rings selected from aromatic and heteroaromatic rings, and the radical is selected from one or more R ４ 3. A compound according to claim 1 or 2, characterised in that it is optionally substituted by

4. In the radical, two aromatic or heteroaromatic rings are fused together or are joined by a -C(R ４ ) ２ -, -N(R ４ 4. The compound according to claim 3, wherein the rings are linked to each other via a divalent group selected from ———, —O—, and —S—.

5. 5. A compound according to claim 3 or 4, characterized in that the radical contains at least two aromatic rings.

6. Group Ar １ and Ar ２ are selected from radicals each containing at least two rings that are the same or different and are selected from aromatic and heteroaromatic rings, each of which contains one or more R ４ 4. The compound according to claim 1, wherein the compound is optionally substituted with:

7. In at least one of the radicals, two aromatic or heteroaromatic rings are fused together or are —C(R ４ ) ２ -, -N(R ４ 7. The compound according to claim 6, wherein the rings are linked to each other via a divalent group selected from ———, —O—, and —S—.

8. In both of the radicals, the two aromatic or heteroaromatic rings are fused together or are joined by a -C(R ４ ) ２ -, -N(R ４ 8. The compound according to claim 6 or 7, wherein the rings are linked to each other via a divalent group selected from ———, —O—, and —S—.

9. 9. A compound according to any one of claims 6 to 8, characterized in that the radical contains at least two aromatic rings.

10. Group Ar １ and Ar ２ are the same or different and are selected from phenyl, naphthyl-substituted phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, pyridyl, phenyl-substituted pyridyl, pyrimidyl, pyrazinyl, pyridazinyl and triazinyl, each of which is selected from one or more radicals R ４ 10. The compound according to claim 1, optionally substituted by

11. A compound according to any one of claims 1 to 10, characterized in that m=0.

12. Formulas (IA) to (IG) 【Chemistry 2】 wherein the variable groups occurring are as defined in any one of claims 1 to 11.

12. A compound according to any one of claims 1 to 11, characterized in that it meets one of the following criteria:

13. Formulas (IA-1) to (IG-1) 【Transformation 3】 wherein the variable groups occurring are as defined in any one of claims 1 to 12.

13. The compound according to any one of claims 1 to 12, characterized in that it meets one of the following criteria:

14. Formulae (IA-2) to (I-K-2) 【Chemistry 4-1】 【Chemistry 4-2】 wherein the variable groups occurring are as defined in any one of claims 1 to 13.

14. The compound according to any one of claims 1 to 13, characterized in that it meets one of the following criteria:

15. The following formula 【Chemistry 5-1】 【Chemistry 5-2】 (wherein the variable groups appearing are as defined in any one of claims 1 to 14, and in formulas (IA-2-1) and (I-H-2-1), A Ｌ is selected from divalent radicals derived from benzene, biphenyl, terphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, each of which is substituted with one or more radicals R ４ and optionally substituted by 15. The compound according to any one of claims 1 to 14, characterized in that it meets one of the following criteria:

16. R １ are the same or different at each occurrence, 【Transformation 6】 wherein m is 1 and E is a single bond, an aromatic ring system having 6 to 30 aromatic ring atoms, and a heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein the aromatic and heteroaromatic ring systems are in each case bound to one or more radicals R ５ and optionally substituted by 16. The compound according to any one of claims 1 to 15, characterized in that it is selected from:

17. R １ are the same or different at each occurrence, 【Transformation 7】 wherein m is 1 and E is a single bond, phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, 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, each of which may be selected from the group consisting of one or more radicals R ５ and optionally substituted with 17. The compound according to any one of claims 1 to 16, characterized in that it is selected from:

18. R ３ are identical or different in each occurrence and are a linear alkyl group having 1 to 20 C atoms or a cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl group or the cyclic alkyl group is selected from the group consisting of one or more radicals R ５ or aromatic or heteroaromatic ring systems having 6 to 30 aromatic ring atoms, wherein said aromatic and heteroaromatic ring systems are in each case substituted by one or more radicals R ５ and wherein the two radicals R ３ may be linked to each other to form a ring, thereby constructing a spiro compound at the 9-position of the fluorene group, in which case spirobifluorene is excluded.

19. R ３ are identical or different in each occurrence and are linear alkyl groups having 1 to 10 C atoms, wherein said alkyl groups are each independently selected from one or more radicals R ５ or an aromatic ring system having 6 to 24 aromatic ring atoms, wherein said aromatic ring system is in each case substituted by one or more radicals R ５ and wherein the two radicals R ３ may be linked to each other to form a ring, thereby constructing a spiro compound at the 9-position of the fluorene group, in which case spirobifluorene is excluded.

20. A process for producing a compound of formula (I) according to any one of claims 1 to 19, comprising introducing a diarylamino group by a C-N coupling reaction between a fluorene derivative halogenated at the 2-position and a diarylamine derivative.

21. 20. A process for preparing a compound of formula (I) according to any one of claims 1 to 19, characterized in that the compound is prepared by reacting an alkyl 5-halo-2-iodobenzoate with an aryl boronic acid.

22. a) General formula (II) 【Transformation 8】 and methyl 5-halo-2-iodobenzoate of the formula (III-1) to (III-8) 【Chemistry 9】 (In the formula, R １ are identical or different on each occurrence and are as defined in any one of claims 1 to 19, but are preferably selected from phenyl, biphenyl, terphenyl or quaterphenyl, each of which may be selected from one or more radicals R as defined above. ５ may be optionally substituted by X is Cl or Br. to obtain a 5-halobenzoate methyl ester derivative, and thereafter b) a reaction step of converting said ester derivative into a tertiary alcohol by using an alkyl or aryl magnesium halide, preferably methyl or phenyl magnesium chloride, and then c) carrying out an acid-catalyzed cyclization to obtain a fluorene derivative halogenated at the 2-position, and then d) a reaction step of reacting the fluorene derivative with a diarylamine derivative to obtain the compound of formula (I).

22. The method of claim 21, comprising:

23. Formulas (IV-A) to (IV-Is) 【Chemistry 10-1】 【Chemistry 10-2】 (In the formula, R １ are the same or different at each occurrence and are selected from phenyl, biphenyl, terphenyl or quaterphenyl, each of which is selected from one or more radicals R as defined above. ５ may be optionally substituted by R ３ are identical or different at each occurrence and are selected from methyl and phenyl, each of which is selected from one or more radicals R as defined above. ５ may be optionally substituted by X is Cl or Br. A compound characterized by meeting one of the following criteria:

24. 24. A compound according to claim 23, obtained or obtainable in reaction step c) of claim 22.

25. 20. An oligomer, polymer or dendrimer comprising one or more compounds of formula (I) according to any one of claims 1 to 19, wherein the bond to the polymer, oligomer or dendrimer is R １ ~R ６ The oligomer, polymer or dendrimer of formula (I) substituted by

26. A composition comprising one or more compounds of formula (I) according to any one of claims 1 to 19, or one or more polymers, oligomers, or dendrimers according to claim 25, and at least one further organic functional material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, electron blocking materials, hole blocking materials, wide band gap materials, delayed fluorescent emitters, and delayed fluorescent hosts.

27. 27. A formulation comprising at least one compound of formula (I) according to any one of claims 1 to 19, or at least one polymer, oligomer or dendrimer according to claim 25, or at least one composition according to claim 26, and at least one solvent.

28. 27. An electronic device comprising at least one compound according to any one of claims 1 to 19, or at least one polymer, oligomer or dendrimer according to claim 25, or at least one composition according to claim 26.

29. 29. An organic electroluminescent device comprising an anode, a cathode and at least one light-emitting layer, wherein at least one organic layer of the device is a light-emitting layer, a hole-transporting layer, an electron-blocking layer or a hole-injecting layer, characterized in that it comprises the at least one compound of formula (I) according to any one of claims 1 to 19, or the at least one polymer, oligomer or dendrimer according to claim 25, or the at least one composition according to claim 26.

30. Use of a compound according to any one of claims 1 to 19, or a polymer, oligomer or dendrimer according to claim 25, or a composition according to claim 26 in an electronic device.

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