Material for electronic device

Abstract

To provide: a compound for use in an electronic device; a method for preparing the compound; and an electronic device including the compound.SOLUTION: There is provided a compound having the following structure.SELECTED DRAWING: None

Description

[Technical field]

[0001] This application relates to fluorene amine compounds suitable for use in electronic devices, particularly organic electroluminescent devices (OLEDs).

[0002] Electronic devices in the context of the present application are understood to mean so-called organic electronic devices which contain organic semiconducting materials as functional materials, more particularly these are understood to mean OLEDs.

[0003] The construction of OLEDs, in which organic compounds are used as functional materials, is common knowledge in the prior art. In general, the term OLED is understood to mean an electronic device that has one or more layers containing organic compounds and emits light upon application of a voltage.

[0004] In electronic devices, and in particular in OLEDs, there is a strong interest in improving performance data, especially lifetime, efficiency and operating voltage, aspects which still do not provide any completely satisfactory solutions.

[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 data of electronic devices. New materials with hole transport properties are continually being sought for use in these layers.

[0006] In the course of the present invention, it has been found that fluorene amine compounds having dibenzofuran or similar groups bonded to bridgehead positions of fluorene via spacer groups are very well suited for use as materials with hole transport function, in particular for use as materials of hole transport layer, electron blocking layer and / or emitting layer, more particularly for use in hole transport layer and / or electron blocking layer.In this context, electron blocking layer is understood to be a layer that is directly adjacent to the emitting layer on the anode side and functions to block the electrons present in the emitting layer from entering the hole transport layer of OLED.

[0007] When used in electronic devices, especially OLEDs, they provide excellent results in terms of device lifetime, operating voltage and quantum efficiency.The compounds also feature very good hole-conducting properties, very good electron-blocking properties, high glass transition temperature, high oxidation stability, good solubility, high thermal stability and low sublimation temperature.

[0008] Thus, the present application relates to a compound of formula (I)

[0009] [ka]

[0010] wherein the following applies to the variables: Z is a group -[Ar 2 ] n -A is C when attached thereto; Z is a group -[Ar 2 ] n If -A is not attached thereto, then in each occurrence, identically or differently, CR 1 and N; Y is a group Ar 1 is bonded thereto, is C; Y is a group Ar 1 If no CR is attached to it, each occurrence may be the same or different. 3 and N; X is O or S; Ar 1 may be identically or differently in each occurrence a radical R 4 and an aromatic ring system having 6 to 40 aromatic ring atoms, substituted by the radical R 4 a heteroaromatic ring system having 5 to 40 aromatic ring atoms, substituted by Ar 2 may be identically or differently in each occurrence a radical R 5 and an aromatic ring system having 6 to 40 aromatic ring atoms, substituted by the radical R 5a heteroaromatic ring system having 5 to 40 aromatic ring atoms, substituted by A is a compound of the following formula bonded via a dotted line

[0011] [ka]

[0012] Corresponding to; Ar 3 and Ar 4 may be identically or differently in each occurrence a radical R 5 and an aromatic ring system having 6 to 40 aromatic ring atoms, substituted by the radical R 5 a heteroaromatic ring system having 5 to 40 aromatic ring atoms, substituted by T is a single bond or C(R 5 )2, Si(R 5 )2, N(R 5 ), O, and S; k is 0 or 1, where k=0 means that T does not occur and the group Ar 3 and Ar 4 means that it is not connected; R 1 are each independently H, D, F, Cl, Br, I, 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 , 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 1may be linked together to form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems, can in each case be linked together with the radical R 6 and one or more CH groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted in each case by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), -O-, -S-, SO or SO2; R 2 are each independently or differently H, D, F, Cl, Br, I, CN, Si(R 6 )3, N(R 6 2) selected from 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 the alkyl, alkoxy, alkenyl and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are in each case selected from the radical R 6 and one or more CH groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted in each case by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), -O-, -S-, SO or SO2; R 3 are each independently H, D, F, Cl, Br, I, 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 , 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 3 may be linked together to form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems, can in each case be linked together with the radical R 6 and one or more CH groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted in each case by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), -O-, -S-, SO or SO2; R 4 are each independently H, D, F, Cl, Br, I, 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, 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 4 may be linked together to form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems, can in each case be linked together with the radical R 6 and one or more CH groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted in each case by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), -O-, -S-, SO or SO2; R 5 are each independently H, D, F, Cl, Br, I, 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 , 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 5 may be linked together to form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems, can in each case be linked together with the radical R 6and one or more CH groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted in each case by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), -O-, -S-, SO or SO2; R 6 are each independently H, D, F, Cl, Br, I, C(=O)R, 7 , CN, Si(R 7 )3, N(R 7 )2, P(=O)(R 7 )2, OR 7 , S(=O)R 7 , S(=O)2R 7 , 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 6 may be linked together to form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems, can in each case be linked together with the radical R 7 and one or more CH groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted in each case by -R 7 C=CR 7 -, -C≡C-, Si(R 7 )2, C=O, C=NR 7 , -C(=O)O-, -C(=O)NR 7 -, NR 7 , P(=O)(R 7 ), -O-, -S-, SO or SO2; R 7are identically or differently selected at each occurrence from H, D, F, Cl, Br, I, CN, an alkyl group having 1 to 20 C atoms, an aromatic ring system having 6 to 40 C atoms, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein said alkyl group, aromatic ring system and heteroaromatic ring system may be substituted by one or more radicals selected from F and CN; m is 1, 2, 3, or 4; n is 0, 1, 2, 3, or 4) The present invention relates to a compound of the formula:

[0013] The following definitions apply as general definitions to the chemical groups used. They apply unless a more specific definition is given.

[0014] An aryl group is understood here to mean either a single 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 single aromatic rings fused together. An aryl group in the sense of the present invention contains 6 to 40 aromatic ring atoms, none of which are heteroatoms.

[0015] Here, a heteroaryl group is understood to mean either a single heteroaromatic ring, such as pyridine, pyrimidine or thiophene, or a fused heteroaromatic polycycle, such as quinoline or carbazole. A fused heteroaromatic polycycle in the sense of the present application consists of two or more single aromatic or heteroaromatic rings fused together, where at least one of the two or more single aromatic or heteroaromatic rings is a heteroaromatic ring. 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.

[0016] The aryl or heteroaryl groups may in each case be substituted by the abovementioned radicals, in particular benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzoanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, Dole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, benzimidazolo[1,2-a]benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, oxazole, benzoxa azole, 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 , 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.

[0017] An aromatic ring system in the sense of the present invention is a system which does not necessarily contain only aryl groups, but may additionally contain one or more non-aromatic rings fused to at least one aryl group. Such non-aromatic rings contain only carbon atoms as ring atoms. Examples of groups encompassed by such definition are tetrahydronaphthalene, fluorene, and spirobifluorene. Furthermore, the term aromatic ring system is understood to include systems consisting of two or more aromatic ring systems linked to each other via single bonds, such as biphenyl, terphenyl, 7-phenyl-2-fluorenyl, and quaterphenyl. An aromatic ring system in the sense of the present invention contains 6 to 40 C atoms as ring atoms of the ring system and does not contain heteroatoms. An aromatic ring system in the sense of the present application does not include any heteroaryl groups as defined above.

[0018] Heteroaromatic ring systems are defined similarly to the aromatic ring systems described above, with the difference that they must have at least one heteroatom as one of the ring atoms. As in the case of aromatic ring systems, they do not necessarily contain only aryl and heteroaryl groups, but may additionally contain one or more non-aromatic rings fused to at least one aryl or heteroaryl group. The non-aromatic ring may contain only carbon atoms as ring atoms, or may additionally contain one or more heteroatoms, where the heteroatoms are preferably selected from N, O and S. An example of such a heteroaromatic ring system is benzopyranyl. Furthermore, the term heteroaromatic ring system is understood to include systems consisting of two or more aromatic or heteroaromatic ring systems connected to each other via single bonds, such as 4,6-diphenyl-2-triazinyl. Heteroaromatic ring systems in the sense of the present invention contain 5 to 40 ring atoms selected from carbon and heteroatoms, where at least one of the ring atoms is a heteroatom. The heteroatom is preferably selected from N, O or S.

[0019] The terms "heteroaromatic ring system" and "aromatic ring system" as defined herein differ from each other by the fact that an aromatic ring system cannot contain any heteroatoms as ring atoms, whereas a heteroaromatic ring system must contain at least one heteroatom as a ring atom. Such a heteroatom may be present as a ring atom of a non-aromatic heterocyclic ring of the system or as a ring atom of an aromatic heterocyclic ring of the system.

[0020] According to the above, any aryl group as defined above is encompassed by the term "aromatic ring system" as defined above, and any heteroaryl group as defined above is encompassed by the term "heteroaromatic ring system" as defined above.

[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 radicals mentioned above or from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene and indenocarbazole or from a combination of these radicals.

[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 may in addition be substituted at individual H atoms or CH2 groups by the groups mentioned above under the definition of the radicals, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl ... i-propyl, s-butyl, cyclopentyl, neopentyl, ethyl, n-propyl, i-propyl, i-propyl, i-propyl, s-butyl, cyclopentyl, neopentyl, ethyl, n-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl, i-propyl This is taken to mean the radicals: 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.

[0023] Alkoxy or thioalkyl groups having 1 to 20 C 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 ... This is taken to mean ethylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0024] The phrase "two or more radicals may be linked together to form a ring" is understood to include the case where two radicals are linked by a chemical bond. In addition, this phrase is understood to include the case where one of the two radicals is H, the H radical is removed, and the other of the two radicals is linked to the position where the H radical was originally attached to form a ring. In addition, this phrase is understood to include the case where both of the two radicals are H, both of them are removed, and the positions where the two H radicals were attached are linked by a single bond to form a ring.

[0025] For purposes of this application, when a group is depicted as being attached to a ring having multiple attachment points, and the group has a subscript that is an integer, this means that the respective group is present multiple times on the ring. For example, the group -[R 1 ]4 is shown in the formula, this means that all four positions on the aromatic ring are R 1 This means that it is replaced by

[0026] The compounds according to formula (I) are preferably monoamines, which are understood to be compounds which have only one triarylamine group, preferably only one amine group.

[0027] Group - [Ar 2 ] n -A can be attached at any of the 1, 2, 3 and 4 positions on the fluorene moiety of formula (I), preferably at the 2 or 4 position, more preferably at the 2 position.

[0028] The positions on the fluorene moiety of formula (I) are numbered as follows:

[0029] [ka]

[0030] Group of formula (I)

[0031] [ka]

[0032] is preferably attached to the remainder of formula (I) at the following position:

[0033] [ka]

[0034] where the bond shown with a dotted line is the bond connecting the group to the remainder of the formula.

[0035] According to a preferred embodiment, Z is a group -[Ar 2 ] n -A is C when attached thereto; Z is a group -[Ar 2 ] n -If A is not bound to it, CR 1 It is.

[0036] According to a preferred embodiment, Y is a group Ar 1 is attached thereto, is C; Z is a group Ar 1 If CR is not bound to it, 1 It is.

[0037] According to a preferred embodiment, X is O.

[0038] According to a preferred embodiment, Ar 1 is one or more radicals R 4 and more preferably one or more radicals R 4 and most preferably selected from 1,2-phenylene, 1,3-phenylene and 1,4-phenylene, of which 1,4-phenylene is preferred, in which the phenylene group is optionally substituted with one or more radicals R 4 It may be optionally substituted with, and is preferably unsubstituted.

[0039] The index m is preferably 1 or 2, most preferably 1.

[0040] Preferred group when m=1 is -[Ar 1 ] m - is the radical R 4and more preferably selected from divalent radicals derived from phenyl, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which is substituted with 4 and most preferably selected from 1,2-phenylene, 1,3-phenylene and 1,4-phenylene, of which 1,4-phenylene is preferred, where the phenylene group is selected from the divalent radicals derived from phenyl, biphenyl and fluorene, substituted with the radical R 4 In such cases, the radical R 4 is preferably H.

[0041] Preferred groups Ar 2 is the radical R 5 and more preferably selected from divalent radicals derived from phenyl, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which is substituted with a radical R 5 The divalent radicals are selected from divalent radicals derived from phenyl, biphenyl and fluorene, each substituted with

[0042] According to a preferred embodiment, the index n is 0, so that the group Ar 2 is not present and the fluorene moiety and the amine nitrogen in formula (I) are directly linked to each other.

[0043] According to an alternative preferred embodiment, the index n is 1 or 2, preferably 1.

[0044] Preferred group when n=1 is -[Ar 2 ] n - is the radical R 5and more preferably selected from divalent radicals derived from phenyl, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which is substituted with a radical R 5 The divalent radicals are selected from divalent radicals derived from phenyl, naphthyl, biphenyl and fluorene, each substituted with

[0045] Particularly preferred groups when n=1 are -[Ar 2 ] n - is the following group

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] in which the bond shown by the dotted line is the bond to the remainder of formula (I) and the group is linked at all free positions to the radical R 5 (replaced with is selected from.

[0053] Among the above groups, the formula (Ar 2 -1), (Ar 2 -2), (Ar 2 -3), (Ar 2 -4), (Ar 2 -15), (Ar 2 -20), (Ar 2 -25) and (Ar 2 Particularly preferred are radicals according to the formula:-36).

[0054] According to a preferred embodiment of the present invention, the group Ar 3 and Ar 4 are not linked to each other by the group T, ie, k is 0.

[0055] According to another preferred embodiment, the group Ar 3 and Ar 4 are linked to each other by the group T, i.e. k is 1. In this case, T is preferably a single bond. Preferred embodiments of the group A when k=1 are shown below:

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] where the dotted line is the bond to the remainder of formula (I).

[0060] According to a preferred embodiment, Ar 3 and Ar 4are identically or differently selected from monovalent radicals derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, in particular 9,9′-dimethylfluorene and 9,9′-diphenylfluorene, 9-sila-fluorene, in particular 9,9′-dimethyl-9-silafluorene and 9,9′-diphenyl-9-silafluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, where each of said monovalent radicals is selected from the group consisting of the radicals R 5 According to an alternative preferred embodiment, the group Ar 3 and Ar 4 are identically or differently selected from a combination of two to four radicals, preferably two radicals, derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, in particular 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, 9-sila-fluorene, in particular 9,9'-dimethyl-9-silafluorene and 9,9'-diphenyl-9-silafluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, where each of these radicals is selected from the group consisting of the radical R 5 has been replaced with.

[0061] Particularly preferred groups Ar 3 and Ar 4are identically or differently selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, in particular 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophene-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl and triazinyl-substituted phenyl, where these groups can each be selected from the radical R 5 has been replaced with.

[0062] Ar group 3 and Ar 4 Preferred embodiments of the invention are shown below:

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068]

change

[0069]

change

[0070]

change

[0071]

change

[0072]

change

[0073]

change

[0074]

change

[0075]

change

[0076]

change

[0077]

change

[0078]

change

[0079] [ka]

[0080] (wherein the dotted line is the bond to the nitrogen atom of group A).

[0081] Among the above formulae, particularly preferred are the formulae Ar-1, Ar-2, Ar-4, Ar-5, Ar-50, Ar-74, Ar-78, Ar-82, Ar-107, Ar-108, Ar-117, Ar-134, Ar-139, Ar-150, and Ar-172.

[0082] Preferably, R 1 are the same or different, H, D, F, CN, Si(R 6 )3, N(R 6 2) selected from linear alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy 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 the alkyl and alkoxy groups, as well as the aromatic and heteroaromatic ring systems, are selected from the radical R 6 and one or more CH groups in said alkyl and alkoxy groups are in each case substituted by -C≡C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 -. Preferably, R 1 is N(R 6 )2. Particularly preferably, R 1 does not contain any amine groups. More preferably, R 1 are the same or different, H, D, F, CN, Si(R 6)3, selected from linear alkyl groups having 1 to 20 C atoms, which are optionally deuterated and / or fluorinated, branched or cyclic alkyl groups having 3 to 20 C atoms, which are optionally deuterated and / or fluorinated, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein said alkyl groups, as well as said aromatic and heteroaromatic ring systems, are selected from the radical R 6 Most preferably, R 1 is H.

[0083] R 1 A preferred embodiment of the present invention is the following group:

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] wherein the bond shown with a dotted line is the bond to the remainder of formula (I). is selected from.

[0095] Preferably, R 2 is F, Si(R 6 ) 3, a linear alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein said alkyl group and said aromatic or heteroaromatic ring system are each independently selected from the radicals R 6 More preferably, R 2 is the radical R 6 Most preferably, R is an aromatic ring system having 6 to 40 aromatic ring atoms substituted with 2 is phenyl, biphenyl, terphenyl, phenyl substituted with dibenzofuran, or phenyl substituted with dibenzothiophene, where each of these groups can be represented by the radical R 6 and is substituted with the radical R 6 In this case, R is preferably H. 2 is the radical R 6 Most preferably, the radical R 6 In this case, is preferably H.

[0096] Further preferably, R 2is selected from the following group:

[0097] [ka]

[0098] (wherein the bond shown with a dotted line represents the bond to the remainder of the formula).

[0099] Preferably, R 3 are the same or different, H, D, F, CN, Si(R 6 )3, N(R 6 2) selected from linear alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy 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 the alkyl and alkoxy groups, as well as the aromatic and heteroaromatic ring systems, are selected from the radical R 6 and one or more CH groups in said alkyl and alkoxy groups are in each case substituted by -C≡C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 More preferably, R 3 are the same or different, H, D, 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; wherein said alkyl groups, as well as said aromatic and heteroaromatic ring systems, are selected from the radical R 6 Most preferably, R 3 is H.

[0100] Preferably, R 4are the same or different, H, D, F, CN, Si(R 6 )3, N(R 6 2) selected from linear alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy 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 the alkyl and alkoxy groups, as well as the aromatic and heteroaromatic ring systems, are selected from the radical R 6 and one or more CH groups in said alkyl and alkoxy groups are in each case substituted by -C≡C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 More preferably, R 4 are the same or different, H, D, 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; wherein said alkyl groups, as well as said aromatic and heteroaromatic ring systems, are selected from the radical R 6 Most preferably, R 4 are identically or differently H, alkyl groups having 1 to 10 C atoms, preferably methyl, isopropyl and tert-butyl, and radicals R 6 Preferably, the aromatic ring system is selected from aromatic ring systems having 6 to 40 aromatic ring atoms, each of which is substituted with phenyl.

[0101] Preferably, R 5 are the same or different, H, D, F, CN, Si(R 6 )3, N(R 62) selected from linear alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy 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 the alkyl and alkoxy groups, as well as the aromatic and heteroaromatic ring systems, are selected from the radical R 6 and one or more CH groups in said alkyl and alkoxy groups are in each case substituted by -C≡C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 More preferably, R 5 are the same or different, H, D, 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; wherein said alkyl groups, as well as said aromatic and heteroaromatic ring systems, are selected from the radical R 6 Most preferably, R 5 are identically or differently H, alkyl groups having 1 to 10 C atoms, preferably methyl, isopropyl and tert-butyl, and radicals R 6 Preferably, the aromatic ring system is selected from aromatic ring systems having 6 to 40 aromatic ring atoms, each of which is substituted with phenyl.

[0102] Preferably, R 6 are the same or different, H, D, F, CN, Si(R 7 )3, N(R 72) selected from linear alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy 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 the alkyl and alkoxy groups, as well as the aromatic and heteroaromatic ring systems, are selected from the radical R 7 and one or more CH groups in said alkyl and alkoxy groups are in each case substituted by -C≡C-, -R 7 C=CR 7 -, Si(R 7 )2, C=O, C=NR 7 , -NR 7 -, -O-, -S-, -C(=O)O- or -C(=O)NR 7 More preferably, R 6 are the same or different, H, D, F, CN, Si(R 7 ) 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; wherein said alkyl groups, as well as said aromatic and heteroaromatic ring systems, are selected from the radical R 7 has been replaced by

[0103] Preferably, R 7 is H.

[0104] A preferred embodiment according to formula (I) is represented by the following formulae (IA) to (IH):

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] wherein the variables and subscripts are as defined above, preferably in accordance with their preferred embodiments set forth above. Matches

[0110] Particularly preferred is the moiety -[Ar 1 ] m - is phenylene, preferably p-phenylene, or biphenylene, preferably parabiphenylene, each of which is a radical R 4 and is substituted with the radical R 4 is preferably H. Most preferably, -[Ar 1 ] m - is phenylene, preferably p-phenylene, each of which is a radical R 4 and is substituted by the radical R 4 is preferably H.

[0111] Among the above formulae, formulae (IA) to (ID), particularly formulae (IB) and (ID), are preferred, and formula (IB) is the most preferred.

[0112] In the case of formulas (IE) to (IH), Ar 3 and Ar 4 are preferably, identically or differently, selected from phenyl, fluorenyl, carbazolyl, dibenzofuranyl and dibenzothiophenyl, each of which is a radical R 5 In addition, the group Ar 3 and Ar 4are preferably linked by a single bond in the ortho position relative to the bond to the amine nitrogen, so that a five-membered ring containing a nitrogen atom is formed. Particularly preferably, a combination of the two embodiments occurs, so that carbazole, indenocarbazole, indolocarbazole, benzofuran-fused carbazole or benzothiophene-fused carbazole is represented by the group

[0113] [ka]

[0114] It is formed by:

[0115] Preferably, R 2 is expressed by the above formula (R 2 -1)~(R 2 -4).

[0116] Furthermore, a preferred embodiment of formula (I) is

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] wherein X is the same or different and is selected from O and S, X is preferably O, and further variables and subscripts are as defined above, preferably according to their preferred embodiments. 2 But radical R 5and more preferably selected from divalent radicals derived from phenyl, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which is substituted with a radical R 5 Preferably, the divalent radicals are selected from the divalent radicals derived from phenyl, naphthyl, biphenyl and fluorene, each of which is substituted with the group Ar 2 Alternatively, the amine nitrogen is preferably attached to the 2- or 4-position of the fluorene moiety, preferably to the 2-position. 2 is expressed by the above formula (R 2 -1)~(R 2 -4).

[0121] A particularly preferred embodiment of formula (I) is

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] (wherein the variables and subscripts are as defined above, preferably in accordance with the preferred embodiments thereof mentioned above). X, identically or differently, is O or S. Particularly preferably, the subscript n is 0 or the subscript n is 1. When the subscript n is 1, -[Ar 2 ] n - but radical R 5 and more preferably selected from divalent radicals derived from phenyl, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which is substituted with a radical R 5 It is preferred that X is selected from divalent radicals derived from phenyl, naphthyl, biphenyl and fluorene, each of which is substituted with X. It is further preferred that X is O.

[0129] Preferred embodiments of the compounds according to formula (I) are shown below:

[0130] [ka]

[0131] [ka]

[0132] [ka]

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] Compounds according to formula (I) are synthetically accessible to one skilled in the art based on the information below.

[0142] A preferred synthetic method for preparing compounds according to formula (I) is shown below in Scheme 1. Although not shown in the scheme for simplicity reasons, the structures may be substituted with organic radicals.

[0143] [ka]

[0144] V 1 = halogen, preferably Br or I V 2 = reactive group, preferably Cl or Br V 3 = reactive group, preferably a boronic acid or boronic ester Ar=aromatic group HetAr = optionally substituted dibenzofuran or dibenzothiophene R=an organic radical, preferably an alkyl or aromatic ring system T=a single bond or an organic linking group, preferably O, S, CR2 or SiR2 k=0 or 1, where, when k=0, the groups Ar are not bonded to each other. In the first step, a reactive group V is attached to the linking bond between the two phenyl groups. 1 and a further reactive group V 2 Biphenyl compounds substituted with the group V 1 The metallation reaction is preferably a lithiation reaction or a Grignard reaction. The metallated intermediate is then reacted with a carbonyl derivative having a dibenzofuran or dibenzothiophene group attached via a spacer. The resulting tertiary alcohol is cyclized to the fluorene under acidic and / or Lewis acidic conditions. The resulting fluorene having the attached reactive group V is then reacted with a carbonyl derivative having a dibenzofuran or dibenzothiophene group attached via a spacer. The resulting tertiary alcohol is then cyclized to the fluorene under acidic and / or Lewis acidic conditions. 2 The fluorene derivatives having the above group V can be further reacted in a Buchwald reaction to give the corresponding amine or carbazolyl derivatives of fluorene, or in a Suzuki reaction to give the corresponding amine or carbazolyl derivatives of fluorene, having an aromatic group as a spacer between the amine nitrogen and the fluorene. 3 Instead of the Suzuki reaction with -Ar-NAr2, the group V 3 -Ar-V 4 A Suzuki reaction with a group H-NAr2 followed by a Buchwald reaction with a group H-NAr2 can be carried out.

[0145] The present application therefore relates to a method for preparing a compound according to formula (I), characterized in that it comprises metalating a biphenyl derivative substituted with two reactive groups, at least one of which is ortho to the phenyl-phenyl bond of the biphenyl derivative. The metallation reaction is preferably a lithiation reaction or a Grignard reaction. Then, in a second step, the metallated biphenyl derivative is added to a carbonyl derivative having a dibenzofuran or dibenzothiophene group linked to the carbonyl group via a spacer. In a third step, the resulting intermediate is cyclized to a fluorene derivative. The cyclization reaction is preferably carried out under acidic and / or Lewis acidic conditions, most preferably by the addition of a strong organic acid, such as paratoluenesulfonic acid. In a fourth step, the fluorene derivative is further reacted in a Buchwald or Suzuki reaction.

[0146] The above first to fourth steps are preferably consecutive, which means that there are no intermediate steps between the first and second, the second and third, and the third and fourth steps.

[0147] The compounds according to the present application, especially those substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acids or boronic esters, can find use as monomers for preparing corresponding oligomers, dendrimers or polymers. Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boronic acids, boronic esters, amines, alkenyl or alkynyl groups with terminal CC double or CC triple bonds, oxiranes, oxetanes, groups involved in cycloaddition reactions, for example 1,3-dipolar cycloaddition reactions, such as dienes or azides, carboxylic acid derivatives, alcohols and silanes.

[0148] Thus, the present invention provides an oligomer, polymer or dendrimer containing one or more compounds of formula (I), wherein the bond to the polymer, oligomer or dendrimer is represented by the formula R 1 , R 2 , R 3, R 4 or R 5 The present invention further provides an oligomer, polymer or dendrimer, which may be located at any desired position substituted by. Depending on the attachment of the compound, the compound becomes part of the side chain or part of the backbone of the oligomer or polymer. An oligomer in the context of the present invention is understood to mean a compound formed from at least three monomer units. A polymer in the context of the present invention is understood to mean a compound formed from at least 10 monomer units. The polymer, oligomer or dendrimer of the present invention may be conjugated, partially conjugated or non-conjugated. The oligomer or polymer of the present invention may be linear, branched or dendritic. In structures with linear bonds, the units of the above formula may be directly bonded to each other, or may be bonded 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 the above formula may be bonded to each other via a trivalent or higher valent group, for example via a trivalent or higher valent aromatic or heteroaromatic group, resulting in a branched or dendritic oligomer or polymer.

[0149] For repeating units of the above formula in oligomers, dendrimers and polymers the same preferences apply as described above for compounds of the above formula.

[0150] To prepare oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with further monomers.Suitable preferred comonomers are selected from fluorene, spirobifluorene, paraphenylene, carbazole, thiophene, dihydrophenanthrene, cis- and trans-indenofluorene, ketone, phenanthrene, or a plurality of these units.Polymers, oligomers and dendrimers typically contain further units, such as luminescent (fluorescent or phosphorescent) units, such as vinyltriarylamine or phosphorescent metal complexes, and / or charge transport units, especially those based on triarylamine.

[0151] The polymers and oligomers of the present invention are generally prepared by polymerization of one or more monomers, at least one of which provides the repeating unit of the above formula in the polymer.Suitable polymerization reactions are known to those skilled in the art and described in the literature.Particularly suitable preferred polymerization reactions that provide the formation of CC or CN bonds are Suzuki polymerization, Yamamoto polymerization, Stille polymerization and Hartwig-Buchwald polymerization.

[0152] Processing the compounds according to the present application from a liquid phase, for example by spin-coating or printing methods, requires formulations of the compounds according to the present application. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use mixtures of two or more solvents. Suitable preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanoate, cyclohexanol ... The solvents include, for example, benzene, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or mixtures of these solvents.

[0153] Thus, the present invention further provides a formulation, in particular a solution, dispersion or emulsion, comprising at least one compound according to the present application and at least one solvent, preferably an organic solvent. Methods by which such solutions can be prepared are known to those skilled in the art and are described, for example, in WO2002 / 072714, WO2003 / 019694 and the documents cited therein.

[0154] The compounds according to the present application are suitable for use in electronic devices, especially organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds are used in different functions and layers.

[0155] Therefore, the present invention further provides the use of the compound in an electronic device, which is preferably selected from the group consisting of organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic light emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field quenching devices (OFQDs), organic light emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), and more preferably organic electroluminescent devices (OLEDs).

[0156] The present invention further provides an electronic device comprising at least one compound according to the present application, as already described above, said electronic device being preferably selected from the devices described above.

[0157] More preferably, it is an organic electroluminescent device (OLED) comprising an anode, a cathode and at least one light-emitting layer, characterized in that at least one organic layer, which may be a light-emitting layer, a hole-transporting layer or another layer, preferably a light-emitting layer or a hole-transporting layer, particularly preferably a hole-transporting layer, comprises at least one compound according to the present application.

[0158] Besides the cathode, the anode and the light-emitting layer, the organic electroluminescent device may also comprise further layers, for example selected from in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, charge generation layers, and / or organic or inorganic p / n junctions.

[0159] The layer arrangement of an organic electroluminescent device comprising a compound of the above formula is preferably as follows: Anode-hole injection layer-hole transport layer-optionally further hole transport layer-optionally electron blocking layer-light emitting layer-optionally hole blocking layer-electron transport layer-electron injection layer-cathode. In addition, further layers can also be present in the OLED.

[0160] The organic electroluminescent device 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 in total, resulting in a total white emission; in other words, various light-emitting compounds that can fluoresce or phosphoresce 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 show blue, green and orange or red emission. The compound according to the present application is preferably present in the hole transport layer, the hole injection layer, the electron blocking layer and the light-emitting layer. When the compound is present in the light-emitting layer, it is preferably present as a host material.

[0161] According to the invention, the compounds according to the present application are preferably used in electronic devices comprising one or more phosphorescent emitting 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 in an emitting layer.

[0162] The term "phosphorescent compound" typically encompasses compounds in which light emission occurs via a spin-forbidden transition, such as a transition from an excited triplet state or a state having a higher spin quantum number, such as a quintet state.

[0163] Suitable phosphorescent compounds (= triplet emitters) are especially compounds that, when appropriately excited, preferably emit light in the visible range and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. As phosphorescent compounds, it is preferred to use compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium, platinum or copper. In the context of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent compounds. In general, 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. It is also possible for a person skilled in the art to use further phosphorescent complexes in combination with the compounds according to the present application in organic electroluminescent devices without the need for inventive techniques. Further examples are listed in the table that follows below.

[0164] According to the present invention, the compounds according to the present application can also be used in electronic devices that contain one or more fluorescent emitting compounds.

[0165] In a preferred embodiment of the present invention, the compounds according to the present application are used as hole transporting materials. In that case, the compounds are preferably present in a hole transporting layer, an electron blocking layer or a hole injection layer. The use in an electron blocking layer or a hole transporting layer is particularly preferred.

[0166] 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.

[0167] In the context of this application, hole injection layer and electron blocking layer are understood to be specific embodiments of hole transport layer. 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. 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 according to the present application, more preferably exactly one or two of which contain such a compound.

[0168] When the compounds according to the present application are used as hole transport materials in hole transport layers, hole injection layers or electron blocking layers, they can be used as pure materials, i.e. in the proportion of 100%, in the hole transport layer, or in combination with one or more further compounds.In a preferred embodiment, the organic layer that contains one compound of the above formula additionally contains one or more p-dopants.The p-dopants used according to the present invention are preferably organic electron acceptor compounds that can oxidize one or more other compounds in the mixture.Such p-dopants are preferably present in the hole injection layer and / or hole transport layer of the device.The electron blocking layer preferably does not contain any p-dopants.

[0169] 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 ligands containing at least one oxygen atom as a binding site. Further preferred as dopants are transition metal oxides, preferably oxides of rhenium, molybdenum and tungsten, more preferably Re2O7, MoO3, WO3 and ReO3. Further preferred p-dopants are selected from Bi(III)-containing metal complexes, in particular Bi(III) complexes of benzoic acid or benzoic acid derivatives.

[0170] 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 with the hole transport material matrix.

[0171] Preferred p-dopants are especially the following compounds:

[0172] [ka]

[0173] In a further preferred embodiment of the invention, the compound is used as a hole transport material in a hole transport layer, and between the anode and this hole transport layer there is a layer (called hole injection layer) which comprises an electron accepting material. Preferably, this electron accepting material is selected from the classes of compounds mentioned above for use as p-dopants, particularly preferably from the compounds (D-1) to (D-14) mentioned above, most preferably from the compounds (D-6), (D-7) and (D-14). Preferably, the hole injection layer comprises one of the above compounds in undoped form and not mixed with other compounds. Most preferably, it consists of only one of the above compounds and does not contain other compounds.

[0174] According to a preferred embodiment, the hole transport layer or hole injection layer of the device comprises two or more, preferably two different hole transport materials (mixed layer). In such a case, the two or more different hole transport materials are preferably selected from triarylamine compounds, particularly preferably from monotriarylamine compounds, more particularly from the compounds listed below as preferred hole transport compounds. When two or more different compounds are present in the layer, each of them is preferably present in a proportion of at least 10% by volume, preferably in a proportion of at least 20% by volume.

[0175] In this application, the percentages are given in volume percent. If the mixture is applied from a solution, this corresponds to a weight percent.

[0176] The mixed layer preferably comprises one or more compounds according to the present application.

[0177] In a further embodiment of the invention the compounds are used as matrix materials in the light-emitting layer in combination with one or more light-emitting compounds, preferably phosphorescent light-emitting compounds.

[0178] In this case, the ratio of the matrix material in the light-emitting layer is 50.0% to 99.9% by volume in the case of a fluorescent light-emitting layer, preferably 80.0% to 99.5% by volume, and more preferably 92.0% to 99.5% by volume, and in the case of a phosphorescent light-emitting layer, 85.0% to 97.0% by volume.

[0179] Correspondingly, the proportion of the emissive compound is 0.1% to 50.0% by volume for the fluorescent emissive layer, preferably 0.5% to 20.0% by volume, more preferably 0.5% to 8.0% by volume, and 3.0% to 15.0% by volume for the phosphorescent emissive layer.

[0180] The light-emitting layer of an organic electroluminescent device may also comprise a system containing several matrix materials (mixed matrix system) and / or several light-emitting compounds. In this case, too, 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.

[0181] The compound 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, in this case, one of the two materials is a material with hole transport properties and the other material is a material with electron transport properties. The compound is preferably a matrix material with hole transport properties. However, the desired electron transport and hole transport properties of the mixed matrix component may also be mainly or completely combined in a single mixed matrix component, in which case a further 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, most preferably 1:4 to 1:1. For phosphorescent organic electroluminescent devices, mixed matrix systems are preferably used.

[0182] 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 electroluminescent devices.

[0183] Particularly suitable matrix materials which can be used as matrix components of a mixed matrix system in combination with the compounds according to the present application are selected from the preferred matrix materials for phosphorescent compounds or the preferred matrix materials for fluorescent compounds defined below, depending on the type of emissive compound used in the mixed matrix system.

[0184] Preferred phosphorescent compounds for use in the mixed matrix systems are generally the same as those detailed above as preferred phosphorescent materials.

[0185] Preferred embodiments of various functional materials in electronic devices are listed below.

[0186] Preferred phosphorescent compounds are:

[0187] [ka]

[0188] [ka]

[0189] [ka]

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193] [ka]

[0194] [ka]

[0195]

change

[0196]

change

[0197]

change

[0198] Preferred fluorescent compounds are selected from the class of arylamines. Arylamines or aromatic amines in the context of the present invention are understood to mean compounds 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 or aromatic chrysenediamines. Aromatic anthracenamines are understood to mean compounds in which a diarylamino group is directly bonded to an anthracene group, preferably in the 9-position. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are directly bonded to an anthracene group, preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are similarly defined, in which the diarylamino group is directly bonded to the pyrene, preferably in the 1-position or the 1,6-position. Further preferred luminescent compounds are indenofluorene amines and fluorene diamines, benzoindenofluorene amines and fluorene diamines, dibenzoindenofluorene amines and diamines, and indenofluorene derivatives with condensed aryl groups.Also preferred are pyrene arylamines.Also preferred are benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives that are linked to furan or thiophene units.

[0199] Matrix materials preferably useful for fluorescent compounds include materials from various substance classes.Preferred matrix materials are selected from the classes of oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobifluorene or dinaphthylanthracene), especially oligoarylenes containing fused aromatic groups, oligoarylenevinylenes (e.g. DPVBi or spiro-DPVBi), multipodal metal complexes, hole-conducting compounds, electron-conducting compounds, especially ketones, phosphine oxides and sulfoxides, and atropisomers, boronic acid derivatives or benzoanthracene.Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzoanthracene and / or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the class of oligoarylenes comprising anthracene, benzoanthracene, benzophenanthrene and / or pyrene or the atropisomers of these compounds. Oligoarylenes in the context of the present invention are of course understood to mean compounds in which at least three aryl or arylene groups are bonded to one another.

[0200] Preferred matrix materials for phosphorescent compounds are, in addition to the compounds of the present application, aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, such as CBP (N,N-biscarbazolylbiphenyl) or carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, silanes, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasiloles or tetraazasilol derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or lactams.

[0201] Suitable charge transporting materials which can be used in the hole-injecting or hole-transporting layers or electron-blocking layers or in the electron-transporting layers of the electronic devices of the invention are, in addition to the compounds of the present application, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials as used in these layers according to the prior art.

[0202] Particularly preferred materials for use in the hole transport layer of an OLED are listed below:

[0203] [ka]

[0204] [ka]

[0205] [ka]

[0206] [ka]

[0207] [ka]

[0208] Preferably, the OLED of the present invention comprises two or more different hole transport layers. Here, the compound according to the present application may be used in one or more or all of the hole transport layers. In a preferred embodiment, the compound is used in exactly one or exactly two hole transport layers, and another compound, preferably an aromatic amine compound, is used in the additional hole transport layers present. Further compounds which are preferably used in conjunction with the compounds according to the present application in a hole-transporting layer of an OLED according to the present invention are, inter alia, indenofluorene amine derivatives, hexaazatriphenylene derivatives, amine derivatives containing condensed aromatic groups, monobenzoindenofluorene amines, dibenzoindenofluorene amines, spirobifluorene amines, fluorene amines, spirodibenzopyran amines, dihydroacridine derivatives, spirodibenzofurans and spirodibenzothiophenes, phenanthredialylamines, spirotribenzotropolones, spirobifluorenes with metaphenyldiamine groups, spirobisacridines, xanthenediarylamines and 9,10-dihydroanthracenespiro compounds with diarylamino groups.

[0209] Very particular preference is given to the use as hole-transporting compounds of spirobifluorenes which are substituted in the 4-position by a diarylamino group, and to the use as hole-transporting compounds of spirobifluorenes which are substituted in the 2-position by a diarylamino group.

[0210] 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.

[0211] Particularly preferred electron-transporting materials for use in OLEDs are listed below:

[0212] [ka]

[0213] [ka]

[0214] [ka]

[0215] A preferred cathode for electronic devices is a metal, metal alloy, or multilayer structure 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 a low work function. Also suitable are alloys composed of alkali metals or alkaline earth metals and silver, such as alloys composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, it is also possible to use further metals with relatively high work functions, such as Ag or Al, in which case metal combinations such as Ca / Ag, Mg / Ag or Ba / Ag are commonly used. It may be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between the metallic cathode and the organic semiconductor. Examples of materials useful for this purpose are 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.). It is also possible to use lithium quinolinate (LiQ) for this purpose. The thickness of this layer is preferably 0.5 to 5 nm.

[0216] Preferred anodes are materials with a high work function. Preferably, the anode has a work function of more than 4.5 eV vs. vacuum. Firstly, metals with high redox potentials are suitable for this purpose, such as Ag, Pt or Au. Secondly, metal / metal oxide electrodes (e.g. Al / Ni / NiO x , Al / PtO x ) may be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to allow irradiation of the organic material (organic solar cells) or emission of light (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Furthermore, conductive doped organic materials, especially conductive doped polymers, are preferred. In addition, the anode may also consist of two or more layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0217] The device is then appropriately structured (depending on the application), the contacts are connected and finally sealed to eliminate the damaging effects of water and air.

[0218] In a preferred embodiment, the electronic device is characterized in that one or more layers are coated by sublimation. In this case, the material is deposited in a vacuum sublimation system at 10 -5 Less than mbar, preferably less than 10 -6 It is applied by evaporation at an initial pressure of less than 10 mbar. However, in this case, the initial pressure can be lowered, for example to 10 -7 It is also possible to go below mbar.

[0219] 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 preferably 10 -5It is applied at a pressure of between mbar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly by a nozzle and thus structured (eg MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0220] In addition, electronic devices are preferred, characterized in that one or more layers are produced from 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, soluble compounds are required. High solubility can be achieved by suitable substitution of the compounds.

[0221] More preferably, the electronic devices of the present invention are fabricated by applying one or more layers from solution and applying one or more layers by sublimation.

[0222] According to the present invention, electronic devices comprising one or more compounds according to the present application can be used in displays, as light sources in lighting applications, and as light sources in medical and / or cosmetic applications.

[0223] [example] A) Synthesis example The following syntheses are carried out under a protective gas atmosphere unless otherwise indicated. The starting materials are commercially available. The numbers in brackets for the starting materials known from the literature are the corresponding CAS numbers.

[0224] 6-[4-(2-chloro-9-phenyl-9H-fluoren-9-yl)phenyl]-8-oxatricyclo[7.4.0.0 2,7 Synthesis of ]trideca-1(13),2,4,6,9,11-hexaene 2a

[0225] [ka]

[0226] 6-(4-benzoylphenyl)-8-oxatricyclo[7.4.0.0 2,7 Synthesis of ]trideca-1(13),2,4,6,9,11-hexaene 1a

[0227] [ka]

[0228] 50 g (191.5 mmol) of (4-bromo-phenyl)-phenyl-methanone and 50.7 g (239.4 mmol) of dibenzofuran-4-yl-boronic acid, 26.5 g (23 mmol, 0.12 eq.) of Pd(P(Ph3))4 and 680 mL of a 2 M solution of Na2CO3 (1365 mmol, 7 eq.) are dissolved in 1300 mL of ethylene glycol diethyl ether. The reaction mixture is stirred under reflux and rocked under an argon atmosphere for 12 hours. After cooling to room temperature, the mixture is extracted with ethyl acetate. The organic phase is dried over Na2SO4, the filtrate is evaporated in a vacuum and the residue is purified by chromatography (heptane / AcOEt mixture). The product is isolated in the form of an off-white solid (46 g, 68% of theory).

[0229] The synthesis of further derivatives is carried out in a similar manner.

[0230] [ka]

[0231] [ka]

[0232] [ka]

[0233] 6-[4-(2-chloro-9-phenyl-9H-fluoren-9-yl)phenyl]-8-oxatricyclo[7.4.0.0 2,7 Synthesis of ]trideca-1(13),2,4,6,9,11-hexaene 2a

[0234] [ka]

[0235] A solution of 2-bromo-4'-chloro-biphenyl (43 g, 158 mmol) in THF (465 ml) is treated with 58 mL of n-BuLi (2.2 M in hexane, 144 mmol) at -78°C under argon. The mixture is stirred for 30 min. A solution of 1a (50 g, 144 mmol) in 230 mL of THF is added dropwise. The reaction is allowed to proceed for 30 min 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 700 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 (55 g, 74% of theory).

[0236] The following compounds are similarly synthesized:

[0237] [ka]

[0238] [ka]

[0239] [ka]

[0240] N-{[1,1'-biphenyl]-4-yl}-N-(9,9-dimethyl-9H-fluoren-2-yl)-9-(4-{8-oxatricyclo[7.4.0.02,7 Synthesis of ]trideca-1(9),2,4,6,10,12-hexaen-6-yl}phenyl)-9-phenyl-9H-fluoren-2-amine 4a

[0241] [ka]

[0242] S-Phos (0.645 g, 1.6 mmol), Pd2(dba)3 (0.72 g, 0.8 mmol) and sodium tert-butoxide (5 g, 52.4 mmol) are added to a solution of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-amine (9.5 g, 26.2 mmol) and fluorene 3a (9.5 g, 26.2 mmol) in degassed toluene (140 ml) and the mixture is heated under reflux for 10 h. The reaction mixture is cooled to room temperature, weighed down with toluene and filtered through Celite. The filtrate is evaporated in vacuum and the residue is crystallized from toluene / heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified twice by zone sublimation in vacuum. The product is isolated in the form of an off-white solid (11 g, 40% of theory).

[0243] The following compounds can be obtained similarly:

[0244] [ka]

[0245] [ka]

[0246] [ka]

[0247] [ka]

[0248] [ka]

[0249] [ka]

[0250] [ka]

[0251] [ka]

[0252] [ka]

[0253] [ka]

[0254] N-{[1,1'-biphenyl]-4-yl}-9,9-dimethyl-N-{4-[9-(4-{8-oxatricyclo[7.4.0.0 2,7 Synthesis of ]trideca-1(13),2(7),3,5,9,11-hexaen-6-yl}phenyl)-9-phenyl-9H-fluoren-2-yl]phenyl}-9H-fluoren-2-amine 5a

[0255] [ka]

[0256] 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, 52.8 g (101.8 mmol) of fluorene 3a, 3.88 g (5.14 mmol) of PdCl2(Cy)3, 31.2 g (205.6 mmol) of cesium fluoride are dissolved in 800 mL of toluene. The reaction mixture is rocked at reflux under an argon atmosphere for 12 hours and, after cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in a vacuum and the residue is crystallized from heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified twice by zone sublimation in a vacuum. The product is isolated in the form of a white solid (46 g, 50% of theory).

[0257] The following compounds are similarly synthesized:

[0258] [ka]

[0259] [ka]

[0260] [ka]

[0261] [ka]

[0262] [ka]

[0263] [ka]

[0264] B) Device example B-1) General manufacturing and characterization methods The OLEDs containing the compounds according to the present application are prepared by the following general method: the substrate used is a glass plate coated with a structured ITO (indium tin oxide) with a thickness of 50 nm. The OLED 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 specific device settings of the OLED are shown in Tables 1a-1c and the materials of the various layers of the OLED are shown in Table 3.

[0265] All materials are applied by thermal evaporation in a vacuum chamber. Here, the emitting layer always consists of at least one matrix material (host material) and a emitting dopant (emitter) mixed with the matrix material or materials in a certain volume percentage by co-evaporation. Here, an expression such as H:SEB(5%) means that the material H is present in the layer in a volume percentage of 95% and the material SEB is present in the layer in a volume percentage of 5%. Similarly, the other layers may also consist of a mixture of two or more materials.

[0266] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum and 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@10mA / cm 2 The expression is 10mA / cm 2 This represents the external quantum efficiency at the operating current density of LT80@60mA / cm 2 is 60mA / cm without the use of any acceleration factor. 2 At a current density of, say, 5000cd / m 2 From the initial luminance of 4000cd / m to 80% of the initial intensity, i.e. 2 This is the lifespan until the material deteriorates to

[0267] B-2) Use of the compound in EBL of blue fluorescent OLED Compounds HTM-1 to HTM-3 according to the present application are used in the EBL of a blue fluorescent OLED stack as shown in Table 1a below.

[0268] [Table 1]

[0269] In such a device setup, very good results in terms of EQE, lifetime and voltage are obtained with the compounds, as shown in the table below.

[0270] [Table 2]

[0271] B-3) Use of the compound in EBL of green phosphorescent OLED Compounds HTM-1 to HTM-4 according to the present application are used in the EBL of a blue fluorescent OLED stack as shown in Table 1b below.

[0272] [Table 3]

[0273] In such a device setup, very good results in terms of EQE, lifetime and voltage are obtained with the compounds, as shown in the table below.

[0274] [Table 4]

[0275] B-4) Use of the compound in HTL of blue fluorescent OLED Compounds HTM-2 and HTM-3 according to the present application are used in the HTL of a blue fluorescent OLED stack as shown in Table 1c below.

[0276] [Table 5]

[0277] In such a device setup, very good results in terms of EQE, lifetime and voltage are obtained with the compounds, as shown in the table below.

[0278] [Table 6]

[0279] [Table 7-1]

[0280] [Table 7-2]

Claims

1. Formula (I) 【Chemistry 1】 wherein the following applies to the variables: Z is a group -[Ar ２ ] ｎ -A is C when attached thereto; Z is a group -[Ar ２ ] ｎ -CR, identically or differently in each occurrence when A is not attached thereto. １ and N; Y is a group Ar １ is attached thereto; Y is a group Ar １ When is not bound to it, each occurrence may be identical or different, ３ and N; X is O or S; Ar １ is, identically or differently, in each occurrence a radical R ４ and an aromatic ring system having 6 to 40 aromatic ring atoms, substituted by a radical R ４ a heteroaromatic ring system having 5 to 40 aromatic ring atoms, substituted by Ar ２ is, identically or differently, in each occurrence a radical R ５ and an aromatic ring system having 6 to 40 aromatic ring atoms, substituted by a radical R ５ a heteroaromatic ring system having 5 to 40 aromatic ring atoms, substituted by A is a group represented by the following formula bonded via a dotted line: 【Chemistry 2】 Corresponding to; Ar ３ and Ar ４ is, identically or differently, in each occurrence a radical R ５ and an aromatic ring system having 6 to 40 aromatic ring atoms, substituted by a radical R ５ a heteroaromatic ring system having 5 to 40 aromatic ring atoms, substituted by T is a single bond or C(R ５ ) ２ , Si(R ５ ) ２ , N(R ５ ), O, and S; k is 0 or 1, where k=0 means that T does not occur and the group Ar ３ and Ar ４ means that it is not connected; R １ is, identically or differently, H, D, F, Cl, Br, I, 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; １ may be linked together to form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems, can in each case be linked to the radical R ６ and one or more of the alkyl, alkoxy, alkenyl and alkynyl groups are substituted by ２ The group is in each case -R ６ C=CR ６ -, -C≡C-, Si(R ６ ) ２ , C=O, C=NR ６ , -C(=O)O-, -C(=O)NR ６ -, N.R. ６ , P(=O)(R ６ ), —O—, —S—, SO or SO ２ may be replaced by; R ２ are each independently or differently H, D, F, Cl, Br, I, CN, Si(R ６ ) ３ , N(R ６ ) ２ , 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 said alkyl, alkoxy, alkenyl and alkynyl groups, as well as said aromatic and heteroaromatic ring systems, are in each case selected from the radical R ６ and one or more of the alkyl, alkoxy, alkenyl and alkynyl groups are substituted by ２ The group is in each case -R ６ C=CR ６ -, -C≡C-, Si(R ６ ) ２ , C=O, C=NR ６ , -C(=O)O-, -C(=O)NR ６ -, N.R. ６ , P(=O)(R ６ ), —O—, —S—, SO or SO ２ may be replaced by; R ３ is, identically or differently, H, D, F, Cl, Br, I, 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; ３ may be linked together to form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems, can in each case be linked to the radical R ６ and one or more of the alkyl, alkoxy, alkenyl and alkynyl groups are substituted by ２ The group is in each case -R ６ C=CR ６ -, -C≡C-, Si(R ６ ) ２ , C=O, C=NR ６ , -C(=O)O-, -C(=O)NR ６ -, N.R. ６ , P(=O)(R ６ ), —O—, —S—, SO or SO ２ may be replaced by; R ４ is, identically or differently, H, D, F, Cl, Br, I, 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; ４ may be linked together to form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems, can in each case be linked to the radical R ６ and one or more of the alkyl, alkoxy, alkenyl and alkynyl groups are substituted by ２ The group is in each case -R ６ C=CR ６ -, -C≡C-, Si(R ６ ) ２ , C=O, C=NR ６ , -C(=O)O-, -C(=O)NR ６ -, N.R. ６ , P(=O)(R ６ ), —O—, —S—, SO or SO ２ may be replaced by; R ５ is, identically or differently, H, D, F, Cl, Br, I, 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; ５ may be linked together to form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems, can in each case be linked to the radical R ６ and one or more of the alkyl, alkoxy, alkenyl and alkynyl groups are substituted by ２ The group is in each case -R ６ C=CR ６ -, -C≡C-, Si(R ６ ) ２ , C=O, C=NR ６ , -C(=O)O-, -C(=O)NR ６ -, N.R. ６ , P(=O)(R ６ ), —O—, —S—, SO or SO ２ may be replaced by; R ６ is, identically or differently, H, D, F, Cl, Br, I, C(=O)R ７ , CN, Si(R ７ ) ３ , N(R ７ ) ２ , P(=O)(R ７ ) ２ , OR ７ , S(=O)R ７ , S(=O) ２ R ７ , 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; ６ may be linked together to form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups, and said aromatic and heteroaromatic ring systems, can in each case be linked to the radical R ７ and one or more of the alkyl, alkoxy, alkenyl and alkynyl groups are substituted by ２ The group is in each case -R ７ C=CR ７ -, -C≡C-, Si(R ７ ) ２ , C=O, C=NR ７ , -C(=O)O-, -C(=O)NR ７ -, N.R. ７ , P(=O)(R ７ ), —O—, —S—, SO or SO ２ may be replaced by; R ７ are identically or differently selected at each occurrence from H, D, F, Cl, Br, I, CN, an alkyl group having 1 to 20 C atoms, an aromatic ring system having 6 to 40 C atoms, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein said alkyl group, aromatic ring system and heteroaromatic ring system may be substituted by one or more radicals selected from F and CN; m is 1, 2, 3, or 4; n is 0, 1, 2, 3, or 4. Compound.

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

3. Group -[Ar ２ ] ｎ A compound according to claim 1 or 2, characterised in that -A is attached in the 2 or 4 position on the fluorene moiety of formula (I), preferably in the 2 position.

4. A compound according to any one of claims 1 to 3, characterized in that X is O.

5. Compounds according to any one of claims 1 to 4, characterised in that m is 1 or 2, preferably 1.

6. The group -[Ar when m=1 １ ] ｍ is selected from 1,2-phenylene, 1,3-phenylene and 1,4-phenylene, of which 1,4-phenylene is preferred, where the phenylene group is the radical R ４ The compound according to any one of claims 1 to 5, characterized in that it is substituted with

7. n is 0, so that the group Ar ２ The compound according to any one of claims 1 to 6, characterized in that: is absent, and the fluorene moiety and the amine nitrogen in formula (I) are directly linked to each other.

8. A compound according to any one of claims 1 to 6, characterized in that n is 1.

9. Group -[Ar ２ ] ｎ - is the radical R ５ 9. The compound according to claim 8, characterized in that it is selected from divalent radicals derived from phenyl, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene and carbazole, substituted with

10. k=0, i.e., the group Ar in the group A ３ and Ar ４ are not linked to each other by a group T.

11. Ar ３ and Ar ４ are identically or differently selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, in particular 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophene-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl and triazinyl-substituted phenyl, in which said groups are each selected from the radical R ５ The compound according to any one of claims 1 to 10, characterized in that it is substituted with

12. - R １ are the same or different, H, D, F, CN, Si(R ６ ) ３ , N(R ６ ) ２ , linear alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy 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 and alkoxy groups, as well as said aromatic and heteroaromatic ring systems, are selected from the radical R ６ and one or more of the alkyl and alkoxy groups are substituted by ２ The group is in each case -C≡C-, -R ６ C=CR ６ -, Si(R ６ ) ２ , C=O, C=NR ６ , -NR ６ -, -O-, -S-, -C(=O)O- or -C(=O)NR ６ - may be replaced by; and - R ２ F, Si(R ６ ) ３ , a linear alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein said alkyl group and said aromatic or heteroaromatic ring system are linked by the radical R ６ is substituted with; and - R ３ are the same or different, H, D, F, CN, Si(R ６ ) ３ , N(R ６ ) ２ , linear alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy 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 and alkoxy groups, as well as said aromatic and heteroaromatic ring systems, are selected from the radical R ６ and one or more of the alkyl and alkoxy groups are substituted by ２ The group is in each case -C≡C-, -R ６ C=CR ６ -, Si(R ６ ) ２ , C=O, C=NR ６ , -NR ６ -, -O-, -S-, -C(=O)O- or -C(=O)NR ６ - may be replaced by; and - R ４ are the same or different, H, D, F, CN, Si(R ６ ) ３ , N(R ６ ) ２ , linear alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy 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 and alkoxy groups, as well as said aromatic and heteroaromatic ring systems, are selected from the radical R ６ and one or more of the alkyl and alkoxy groups are substituted by ２ The group is in each case -C≡C-, -R ６ C=CR ６ -, Si(R ６ ) ２ , C=O, C=NR ６ , -NR ６ -, -O-, -S-, -C(=O)O- or -C(=O)NR ６ - may be replaced by; and - R ５ are the same or different, H, D, F, CN, Si(R ６ ) ３ , N(R ６ ) ２ , linear alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy 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 and alkoxy groups, as well as said aromatic and heteroaromatic ring systems, are selected from the radical R ６ and one or more of the alkyl and alkoxy groups are substituted by ２ The group is in each case -C≡C-, -R ６ C=CR ６ -, Si(R ６ ) ２ , C=O, C=NR ６ , -NR ６ -, -O-, -S-, -C(=O)O- or -C(=O)NR ６ - may be replaced by; and - R ６ are the same or different, H, D, F, CN, Si(R ７ ) ３ , N(R ７ ) ２ , linear alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy 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 and alkoxy groups, as well as said aromatic and heteroaromatic ring systems, are selected from the radical R ７ and one or more of the alkyl and alkoxy groups are substituted by ２ The group is in each case -C≡C-, -R ７ C=CR ７ -, Si(R ７ ) ２ , C=O, C=NR ７ , -NR ７ -, -O-, -S-, -C(=O)O- or -C(=O)NR ７ 12. A compound according to claim 1, characterised in that it may be replaced by -.

13. R ２ However, the following base 【Chemistry 3】 (wherein the bond shown with a dotted line represents the bond to the remainder of the formula) The compound according to any one of claims 1 to 12, characterized in that it is selected from

14. The following formula 【Chemistry 4-1】 【Chemistry 4-2】 wherein X, identically or differently, is selected from O and S, X is preferably O, and further variables and subscripts are as defined in any one of claims 1 to 13. A compound according to any one of claims 1 to 13, characterized in that it meets one of the following criteria:

15. A process for preparing a compound of formula (I) according to any one of claims 1 to 14, characterized in that it comprises metallating a biphenyl derivative substituted with two reactive groups, at least one of which is in the ortho position relative to the phenyl-phenyl bond of the biphenyl derivative.

16. 15. An oligomer, polymer or dendrimer comprising one or more compounds of formula (I) according to any one of claims 1 to 14, wherein the bond to the polymer, oligomer or dendrimer is selected from the group consisting of the group represented by formula (I) R １ , R ２ , R ３ , R ４ Or R ５ The substituted aryl groups may be located at any desired position in the oligomer, polymer or dendrimer.

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

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

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

20. Use of a compound according to any one of claims 1 to 14, or a polymer, oligomer or dendrimer according to claim 16, in an electronic device.

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