Materials for electronic devices

Abstract

This application relates to amine compounds suitable for use in electronic devices, particularly organic electroluminescent devices (OLEDs). It also relates to electronic devices, particularly OLEDs, that include the compounds. It also relates to methods for synthesizing the amine compounds.

Description

[Technical Field]

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

[0002] In the context of this application, the term "electronic device" is understood to mean a so-called organic electronic device that contains an organic semiconductor material as a functional material. More specifically, the term "electronic device" is understood to mean an OLED.

[0003] The use of organic compounds as functional materials in OLEDs is common knowledge in the prior art. Generally, the term OLED is understood to mean an electronic device having one or more layers containing organic compounds that emits light when a voltage is applied.

[0004] In electronic devices, particularly OLEDs, there is strong interest in improving performance data, especially lifespan, efficiency, and operating voltage. However, no completely satisfactory solution has yet been found in these areas.

[0005] Layers with hole transport properties, such as hole injection layers, hole transport layers, electron blocking layers, and light-emitting layers, significantly impact the performance data of electronic devices. New materials with hole transport properties are continuously being sought for use in these layers.

[0006] In the course of the present invention, it has been discovered that amine compounds having a spirobifluorene group, a group derived from spirobifluorene, or a fluorene group, and being completely or partially deuterated in the manner described in detail below, are very well suited for use as materials having hole transport properties, particularly as materials for hole transport layers, electron blocking layers and / or light-emitting layers, and more specifically for use in hole transport layers and / or electron blocking layers. In this context, the electron blocking layer is understood to be a layer that is directly adjacent to the light-emitting layer on the anode side and functions to prevent electrons present in the light-emitting layer from entering the hole transport layer of the OLED.

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

[0008] Therefore, this application is based on formula (I) or (II)

[0009] [ka]

[0010] (In the formula, the following applies to the variable group: G is given by equation (G-1) or (G-2)

[0011] [ka]

[0012] It is a base by, In the formulas, the dotted line is a connection to the remainder of formula (I) or (II), and the dotted line is a connection at one of the positions marked with # in formulas (G-1) and (G-2), with base R 1 However, they are bonded to all free positions on the aromatic rings of formulas (G-1) and (G-2); Each of the benzene rings in formulas (G-1) and (G-2) is ring Aa to Ai:

[0013] [Chemical Formula]

[0014] (wherein, * The marked position is a bonding point to the remainder of the group in formula (G-1) or (G-2), W 1 represents C(R 1 )2, Si(R 1 )2, N(R 1 ), S, O, Se or C=O; V 1 represents CR 1 or N; R 11 ~R 18 is optionally exchanged with one of those defined as R 1 ; and is optionally exchanged with one of those defined as R L 1 is an aromatic ring system having 6 to 40 aromatic ring atoms substituted with the group R 2 , or a heteroaromatic ring system having 5 to 40 aromatic ring atoms substituted with the group R 2 ; Ar 1 is, in each occurrence, the same or different, and is selected from an aromatic ring system having 6 to 4 aromatic ring atoms substituted with the group R 3 , and a heteroaromatic ring system having 5 to 40 aromatic ring atoms substituted with the group R 3 ; Ar 2 is, in each occurrence, the same or different, and is selected from an aromatic ring system having 6 to 40 aromatic ring atoms substituted with the group R 3 , and a heteroaromatic ring system having 5 to 40 aromatic ring atoms substituted with the group R 3 ; E is a single bond, or C(R 4 )2, Si(R 4 )2, NR 4It is a divalent group selected from O and S; T is identical or different in each occurrence, either as a single bond or C(R) 4 )2, Si(R 4 )2, NR 4 It is a divalent group selected from O and S; n is either 0 or 1, where n=0, base L 1 It does not exist, and the G group and N atom are directly linked; R 0 In each occurrence, H, D, F, Cl, Br, I, C(=O)R appear identically or differently. 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 Selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two radicals R 0 These may be linked to each other to form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are radicals R 5 The group is substituted by, and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups are, in each case, -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), may be replaced by -O-, -S-, SO or SO2; R 1 In each occurrence, H, D, F, Cl, Br, I, C(=O)R appear identically or differently.5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 Selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two or more radicals R 1 These may be linked to each other to form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are radicals R 5 The group is substituted by, and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups are, in each case, -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), may be replaced by -O-, -S-, SO or SO2; R 2 In each occurrence, H, D, F, Cl, Br, I, C(=O)R appear identically or differently. 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5Selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two or more radicals R 2 These may be linked to each other to form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are radicals R 5 The group is substituted by, and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups are, in each case, -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), may be replaced by -O-, -S-, SO or SO2; R 3 In each occurrence, H, D, F, Cl, Br, I, C(=O)R appear identically or differently. 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 Selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two or more radicals R 3 These may be linked to each other to form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are radicals R 5is replaced, and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups are each -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 )2, -O-, -S-, SO or SO2 may be replaced; R 4 is in each occurrence the same or different and is H, D, F, Cl, Br, I, C(=O)R 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 , 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; where two or more radicals R 4 may be linked to each other to form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups, and the aromatic and heteroaromatic ring systems are substituted by the radical R 5 , and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups are each -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 )2, -O-, -S-, SO or SO2 may be replaced; R 5In each occurrence, H, D, F, Cl, Br, I, C(=O)R appear identically or differently. 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 Selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two or more radicals R 5 These may be linked to each other to form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are radicals R 6 The group is substituted by, and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups are, 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 -, NR 6 , P(=O)(R 6 ), may be replaced by -O-, -S-, SO or SO2; R 6 The radicals are selected, identically or differently in their respective appearances, from H, D, F, Cl, Br, I, CN, alkyl groups having 1 to 20 carbon atoms, aromatic ring systems having 6 to 40 carbon atoms, or heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 6 These may be linked to each other to form a ring; the alkyl group, aromatic ring system and heteroaromatic ring system may be substituted with one or more radicals selected from F and CN; Here, in equation (I), three groups -Ar 1 ,-Ar 1and -[L 1 ] n Each of -G contains at least one D atom bonded to an aromatic or heteroaromatic ring; Here, in equation (II), the three groups -Ar 2 ,-Ar 2 and -[L 1 ] n (Each of the G atoms contains at least one D atom bonded to an aromatic or heteroaromatic ring.) Regarding the compounds.

[0015] In this application, "D atom" or "D" means a deuterium atom.

[0016] The definitions below apply as general definitions to the chemical groups used. They apply unless more specific definitions are provided.

[0017] Here, the aryl group is interpreted as meaning any single aromatic ring, such as benzene, or a fused aromatic polycyclic ring, such as naphthalene, phenanthrene, or anthracene. A fused aromatic polycyclic ring in the sense of this application consists of two or more single aromatic rings that are fused to each other. An aryl group in the sense of this invention contains 6 to 40 aromatic ring atoms. An aryl group contains only carbon atoms and no heteroatoms as aromatic ring atoms.

[0018] Here, the heteroaryl group is interpreted to mean any single heteroaromatic ring, such as pyridine, pyrimidine, or thiophene, or a fused heteroaromatic polycyclic ring, such as quinoline or carbazole. A fused heteroaromatic polycyclic ring in the sense of this application consists of two or more single aromatic or heteroaromatic rings that are fused to each other, 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 this invention contains 5 to 40 aromatic ring atoms, of which at least one is a heteroatom. The heteroatom is preferably selected from N, O, and S.

[0019] The aryl or heteroaryl group may be substituted with the radicals mentioned above in each case, particularly benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluorantene, benzoanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoin Dol, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthidine, 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, benzooxa Zole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyrizine, azacarbazole, benzocarbolin, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole This is interpreted to mean groups derived from 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purines, pteridines, indidines, and benzothiadiazoles.

[0020] In the sense of the present invention, an aromatic ring system does not necessarily contain only aryl groups, but may additionally contain one or more non-aromatic rings fused with at least one aryl group. Such non-aromatic rings contain only carbon atoms as ring atoms. Examples of groups encompassed in this 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. In the sense of the present invention, an aromatic ring system contains 6 to 40 carbon 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.

[0021] A heteroaromatic ring system is defined similarly to an aromatic ring system, but differs in that it must contain at least one heteroatom as one of the ring atoms. Similar to aromatic ring systems, it does not necessarily contain only aryl and heteroaryl groups, but may also contain one or more nonaromatic rings fused with at least one aryl or heteroaryl group. The nonaromatic ring may contain only carbon atoms as ring atoms, or may contain one or more additional 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 linked to each other via single bonds, such as 4,6-diphenyl-2-triazinyl. A heteroaromatic ring system in the sense of the present invention contains 5 to 40 ring atoms selected from carbon and heteroatoms, where at least one of the ring atoms is a heteroatom. The heteroatoms are preferably selected from N, O, or S.

[0022] The terms “heteroaromatic ring system” and “aromatic ring system” as defined in this application differ from each other in that an aromatic ring system cannot contain any heteroatoms as ring atoms, while a heteroaromatic ring system must contain at least one heteroatom as a ring atom. Such a heteroatom may exist as a ring atom of a nonaromatic heterocyclic ring in the system, or as a ring atom of an aromatic heterocyclic ring in the system.

[0023] According to the above, all aryl groups as defined above are included in the term "aromatic ring system" as defined above, and all heteroaryl groups as defined above are included in the term "heteroaromatic ring system" as defined above.

[0024] Aromatic ring systems having 6 to 40 aromatic ring atoms, or heteroaromatic ring systems having 5 to 40 aromatic ring atoms, are in particular groups derived from the aforementioned aryl or heteroaryl groups, or from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, torxene, isotorxene, spirotorxene, spiroisotorxene, and indenocarbazole, or combinations thereof.

[0025] For the purposes of the present invention, a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms may also be substituted with any individual H atom or CH2 group as previously mentioned under the definition of a radical, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl This is interpreted as meaning 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, ethinyl, propynyl, butynyl, pentynyl, hexynyl, or octinyl radical.

[0026] The alkoxy or thioalkyl group having 1 to 20 carbon atoms is 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-pentoxy This is interpreted to mean tilthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, etenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethinylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio, or octinylthio.

[0027] The phrase "two or more radicals may be linked together to form a ring" is naturally understood to include cases where two radicals are linked by a chemical bond. In addition, this phrase is naturally understood to include cases where one of the two radicals is H, and this radical H is removed, and the other of the two radicals is linked to the position where this radical H was originally bonded, thereby forming a ring.

[0028] Of formulas (I) and (II), formula (I) is preferred over formula (II).

[0029] One of the compounds of formula (I) and (II) is preferably a monoamine. A monoamine is understood to be a compound having only one triarylamine group, preferably a compound having only one amine group.

[0030] Furthermore, it is preferable that the compound according to either formula (I) or (II) contains one or more deuterium atoms and does not contain hydrogen atoms, i.e., is completely deuterated.

[0031] Preferably, none of the benzene rings in groups (G-1) to (G-2) are exchanged with one of the groups Aa to Aj mentioned earlier.

[0032] In a preferred embodiment, G is a group according to formula (G-1). Particularly preferably, formula (G-1) is formula (G-1-1).

[0033] [ka]

[0034] (In the formulas, the dotted line is a connection to the remainder of formula (I) or (II), and the dotted line is a connection at one of the positions marked with # in formula (G-1-1), and the base R 1 (However, it is bonded to all free positions on the aromatic ring of formula (G-1-1).) It matches. Preferably, these groups R 1 All of them are D.

[0035] Most preferably, G is given by formula (G-1-1-1)

[0036] [ka]

[0037] (In the formulas, the dotted line represents the bond to the remainder of formula (I) or (II), and the base R 1 (However, it is bonded to all free positions on the aromatic ring of formula (G-1-1-1)). It matches. Preferably, these groups R 1 All of them are D.

[0038] T is preferably a single bond, O, or S, and is particularly preferably a single bond, and is the same or different in each case.

[0039] L 1 Preferably, radical R 2 A radical R is substituted, selected from benzene, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, more preferably a radical R 2 Selected from divalent groups derived from benzene, biphenyl, naphthalene, and fluorene, which are substituted with R. Preferably, these groups R 2 All of them are D.

[0040] Particularly preferred base L 1 The following is based on:

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] (In the formulas, the dotted lines indicate bonds to the remainder of formula (I) or (II), and the group is radical R at all free positions.) 2 (It has been replaced with) Selected from these groups R 2 All of these are D. Among the above groups, groups L1-1 to L1-9, L1-79 and L1-82 are preferred, and in particular groups L1-1, L1-4, L1-79 and L1-82, and more specifically groups L1-79 and L1-82 are preferred.

[0048] Preferably, n is 0. This is based on the base L 1 This means that no such linkage exists, and the G group and N atom are directly linked.

[0049] Preferred base: Ar 1 The monovalent groups are selected, either identically or differently, from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, particularly 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, 9-sila-fluorene, particularly 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 monovalent groups is a radical R 3 It is replaced by. According to an alternative preferred embodiment, the base Ar 1The group is selected, either identically or differently, from 2 to 4 groups, preferably a combination of 2 groups, derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, particularly 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, 9-sila-fluorene, particularly 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 groups is a radical R 3 It has been replaced with.

[0050] Particularly preferred base: Ar 1 These are selected, either identically or differently, from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, particularly 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, where these groups are each radical R 3 It has been replaced with.

[0051] Base Ar 1 Preferred embodiments are shown below:

[0052] [ka]

[0053]

change

[0054]

change

[0055]

change

[0056]

change

[0057]

change

[0058]

change

[0059]

change

[0060]

change

[0061]

change

[0062]

change

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] (In the formula, the dotted line represents a bond to the nitrogen atom, and the compound has R in all free positions) 3 (It has been replaced with...)

[0069] Preferably, these groups R 3 All of these are D. Of the above formulas, the most preferred are Ar-1 to Ar-5, Ar-48, Ar-49, Ar-78, Ar-89, Ar-107, Ar-139, and Ar-242.

[0070] Particularly preferred group in formula (I)

[0071] [ka]

[0072] The following base A-1 to A-63 is selected, where base Ar 1 The following are selected as shown in the table:

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] Group E is preferably a single bond or C(R 4 )2.

[0080] Base Ar 2 Preferably, in each case, the same or different, selected from phenyl, biphenyl, and fluorenyl, each of which is a radical R 3 They are substituted with. Preferably, all of these radicals are D.

[0081] Preferably, the base of formula (II)

[0082] [ka]

[0083] The formula is as follows:

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] (In the formula, the dotted line represents bonding to the remainder of formula (II), and the group is preferably completely deuterated.) Selected from.

[0088] R 1 Preferably, H, D, F, CN, Si(R 5 )3, N(R 5 )2, selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where the alkyl and alkoxy groups, as well as the aromatic and heteroaromatic ring systems, are radical R 5 The groups are substituted by -C≡C- and -R in each case, one or more CH2 groups in the alkyl and alkoxy groups are -C≡C- and -R 5 C=CR 5 -, Si(R 5 )2, C=O, C=NR 5 , -NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR 5 - may be replaced by R. Particularly preferred, 1 These are selected identically or differently from H, D, F, CN, linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl groups, as well as the aromatic and heteroaromatic ring systems, are radical R5 It is replaced by R. Most preferably, 1 Is it D, or R 1 It is completely deuterated, and it is R 1 This means that it does not contain hydrogen atoms.

[0089] R 0 Preferably, F, CN, Si(R) are the same or different. 5 )3, selected from linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl groups, as well as the aromatic and heteroaromatic ring systems, are radical R 5 It is replaced by R. 0 The alkyl groups are selected, either identically or differently, from linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl groups, as well as the aromatic and heteroaromatic ring systems, are radical R 5 It is replaced by R. Particularly preferably, 0 It is completely deuterated, and it is R 0 This means that it does not contain hydrogen atoms.

[0090] R 2 Preferably, H, D, F, CN, Si(R 5 )3, N(R 5 )2, selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where the alkyl and alkoxy groups, as well as the aromatic and heteroaromatic ring systems, are radical R 5 The groups are substituted by -C≡C- and -R in each case, one or more CH2 groups in the alkyl and alkoxy groups are -C≡C- and -R5 C=CR 5 -, Si(R 5 )2, C=O, C=NR 5 , -NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR 5 - may be replaced by R. Particularly preferred, 2 These are selected identically or differently from H, D, F, CN, linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl groups, as well as the aromatic and heteroaromatic ring systems, are radical R 5 It is replaced by R. Most preferably, 2 Is it D, or R 2 It is completely deuterated, and it is R 2 This means that it does not contain hydrogen atoms.

[0091] R 3 Preferably, H, D, F, CN, Si(R 5 )3, N(R 5 )2, selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where the alkyl and alkoxy groups, as well as the aromatic and heteroaromatic ring systems, are radical R 5 The groups are substituted by -C≡C- and -R in each case, one or more CH2 groups in the alkyl and alkoxy groups are -C≡C- and -R 5 C=CR 5 -, Si(R 5 )2, C=O, C=NR 5 , -NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR 5 - may be replaced by R. Particularly preferred, 3These are selected identically or differently from H, D, F, CN, linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl groups, as well as the aromatic and heteroaromatic ring systems, are radical R 5 It is replaced by R. Most preferably, 3 Is it D, or R 2 It is completely deuterated, and it is R 2 This means that it does not contain hydrogen atoms.

[0092] R 4 Preferably, the alkyl groups are selected, either identically or differently, from a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where the alkyl groups, as well as the aromatic and heteroaromatic ring systems, are radical R 5 It is replaced by R. 4 It is completely deuterated, and it is R 4 This means that it does not contain hydrogen atoms.

[0093] R 5 Preferably, H, D, F, CN, Si(R 6 )3, N(R 6 )2, selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where the alkyl and alkoxy groups, as well as the aromatic and heteroaromatic ring systems, are radical R 6 The groups are substituted by -C≡C- and -R in each case, one or more CH2 groups in the alkyl and alkoxy groups are -C≡C- and -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 - may be replaced by R. Particularly preferred, 5 These are selected identically or differently from H, D, F, CN, linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl groups, as well as the aromatic and heteroaromatic ring systems, are radical R 6 It is replaced by R. Most preferably, 5 Is it D, or R 5 It is completely deuterated, and it is R 5 This means that it does not contain hydrogen atoms.

[0094] In a preferred embodiment, formulas (I) and (II) are formulas (I-1) and (II-1)

[0095] [ka]

[0096] (In the formula, the variable group is as defined above, preferably conforming to the preferred embodiments thereof mentioned above, the amine group is bonded at one of the #-marked positions on the spirobifluorene, and all free positions on the spirobifluorene are preferably D or fully deuterated groups R) 5 (It has been replaced with) It matches.

[0097] Equation (I-1) is preferable to equation (II-1).

[0098] In a preferred embodiment, formulas (I) and (II) are (I-1-1) and (II-1-1)

[0099] [ka]

[0100] (In the formula, the variable group is as defined above, preferably conforming to the preferred embodiments thereof mentioned above, and all free positions on the spirobifluorene are preferably groups D or fully deuterated groups R) 5 (It has been replaced with) It matches.

[0101] Equation (I-1-1) is preferable to equation (II-1-1).

[0102] A further object of the present application is a material comprising a compound according to one of formulas (I) and (II), characterized in that the compound of formula (I) or (II) is present in the material with a purity of more than 90% by weight, more preferably more than 95% by weight, even more preferably more than 99% by weight, and most preferably more than 99.9% by weight.

[0103] The following are preferred compounds based on formulas (I) to (II), where all hydrogen atoms are replaced by deuterium atoms:

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109]

change

[0110]

change

[0111]

change

[0112]

change

[0113]

change

[0114]

change

[0115]

change

[0116]

change

[0117]

change

[0118]

change

[0119]

change

[0120]

change

[0121]

change

[0122]

change

[0123]

change

[0124]

change

[0125]

change

[0126]

change

[0127]

change

[0128]

change

[0129]

change

[0130]

Chem.

[0131]

Chem.

[0132]

Chem.

[0133] The compounds according to the present application can be prepared by those skilled in the art of organic synthesis using methods and types of reactions known in organic chemistry.

[0134] According to a preferred method for preparing the compound of formula (I) or (II), a non-deuterated compound having one or more hydrogen atoms is reacted with D2O and toluene-d8 in the presence of dry platinum-supported carbon as a catalyst. See the detailed reaction in Scheme 1.

[0135]

Chem.

[0136] In this scheme, the variable groups are as defined above. The subscript x is the number of hydrogen atoms present in the starting material. The subscript y is equal to the number of deuterium atoms present in the resulting material. Preferably, (x - y) / x = 0.1 to 0, more preferably 0.05 to 0, and most preferably 0. This means that all the hydrogen atoms present in the starting material have been exchanged with deuterium atoms during the reaction and the compound is completely deuterated.

[0137] Therefore, the object of the present application is a method for preparing a deuterated arylamine, a deuterated heteroarylamine, or a deuterated carbazole, characterized in that the arylamine, heteroarylamine, or carbazole undergoes an exchange of one or more H atoms for D atoms by treatment using a platinum catalyst and a deuterium source. The "deuterium source" means any compound containing one or more D atoms that can release them under appropriate conditions.

[0138] The platinum catalyst is preferably dry platinum-supported carbon, and more preferably 5% dry platinum-supported carbon. The deuterium source is preferably D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, more preferably D2O, and more preferably a combination of D2O and a completely deuterated organic solvent, most preferably D2O and toluene-d8. The reaction is preferably carried out under heating, more preferably under heating at 100°C to 200°C. Furthermore, the reaction is preferably carried out under pressure.

[0139] Compounds according to this application, particularly those substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid, or boronic acid esters, can find applications as monomers for producing corresponding oligomers, dendrimers, or polymers. Suitable reactive leaving groups include, for example, bromine, iodine, chlorine, boronic acid, boronic acid esters, amines, alkenyl or alkynyl groups having terminal CC double or CC triple bonds, oxiranes, oxetanes, groups involved in cyclic addition, such as 1,3-dipolar cyclic addition, such as dienes or azides, carboxylic acid derivatives, alcohols, and silanes.

[0140] Therefore, the present invention relates to an oligomer, polymer, or dendrimer containing one or more compounds of formula (I) to (II), wherein the bond to the polymer, oligomer, or dendrimer is R in formula (I). 0 , R 1 , R 2 , R 3 or R4 Further, we provide oligomers, polymers, or dendrimers which may be localized at any desired position substituted by the compound. Depending on the bonding of the compound, the compound may become part of the side chain or part of the main chain of the oligomer or polymer. In the context of the present invention, an oligomer is understood to mean a compound formed from at least three monomer units. In the context of the present invention, a polymer is understood to mean a compound formed from at least ten monomer units. The polymers, oligomers, or dendrimers of the present invention may be conjugated, partially conjugated, or unconjugated. The oligomers or polymers of the present invention may be linear, branched, or dendritic. In a linear structure, the units of the formula may be directly bonded to each other, or bonded to each other via divalent groups, for example, via substituted or unsubstituted alkylene groups, via heteroatoms, or via divalent aromatic or heteroaromatic groups. In branched and dendritic structures, for example, three or more units of the formula may be bonded via trivalent or higher valency groups, for example, via trivalent or higher valency aromatic or heteroaromatic groups, resulting in a branched or dendritic oligomer or polymer.

[0141] The same priority trends described earlier for compounds of the above formula apply to the repeating units of oligomers, dendrimers, and polymers.

[0142] For the production of 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, ketones, phenanthrene, or a plurality of these units. Polymers, oligomers, and dendrimers typically contain further units, such as luminescent (fluorescent or phosphorescent) units, such as vinyl triarylamines or phosphorescent metal complexes, and / or charge transport units, particularly those based on triarylamines.

[0143] The polymers and oligomers of the present invention are generally prepared by polymerization of one or more monomers, of which at least one monomer provides the polymer with repeating units of the above formula. Suitable polymerization reactions are known to those skilled in the art and are described in the literature. Particularly preferred polymerization reactions that result in the formation of CC or CN bonds are Suzuki polymerization, Yamamoto polymerization, Still polymerization, and Hartwig-Buchwald polymerization.

[0144] To treat the compounds according to this application from a liquid phase, for example by spin coating or printing, a preparation of the compounds according to this application is required. These preparations may be, for example, solutions, dispersions, or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable preferred solvents include, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fencone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidine, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexano These are cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indan, methyl benzoate, NMP, p-cymene, phenethole, 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.

[0145] Accordingly, the present invention further provides preparations, in particular solutions, dispersions, or emulsions comprising at least one compound according to the present application and at least one solvent, preferably an organic solvent. Methods for preparing such solutions are known to those skilled in the art and are described, for example, in WO2002 / 072714, WO2003 / 019694 and the literature cited herein.

[0146] The compounds according to this application are suitable for use in electronic devices, particularly organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds can be used in a variety of functions and layers.

[0147] Accordingly, the present invention further provides the use of compounds in electronic devices. These electronic devices are preferably selected from the group consisting of organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quenched devices (OFQDs), organic light-emitting electrochemical cells (OLECs), and organic laser diodes (O-lasers), and more preferably organic electroluminescent devices (OLEDs).

[0148] As previously described, the present invention further provides an electronic device comprising at least one compound according to this application. This electronic device is preferably selected from the above-described devices.

[0149] More preferably, the organic electroluminescent device (OLED) comprises an anode, a cathode, and at least one light-emitting layer, wherein the light-emitting layer, a hole transport layer, or another layer, preferably the light-emitting layer or the hole transport layer, particularly preferably the hole transport layer, contains at least one compound according to the present application.

[0150] In addition to the cathode, anode, and light-emitting layer, the organic electroluminescent device may also include further layers. These are selected, for example, in each case from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, charge generation layers, and / or organic or inorganic p / n junctions.

[0151] The arrangement of layers in an organic electroluminescent device containing the compound of the above formula is preferably as follows: Anode - Hole injection layer - Hole transport layer - Optional further hole transport layer - Optional electron blocking layer - Emitting layer - Optional hole blocking layer - Electron transport layer - Electron injection layer - Cathode. In addition, further layers may be present in the OLED.

[0152] The organic electroluminescent device of the present invention may contain two or more light-emitting layers. More preferably, these light-emitting layers in this case have several emission maxima in the range of 380 nm to 750 nm as a whole, producing white light emission as a whole; in other words, various light-emitting compounds that can emit fluorescence or phosphorescence and emit blue, green, yellow, orange, or red light are used for the light-emitting layers. Particularly preferred is a three-layer system, i.e., a system having three light-emitting layers, the three layers exhibiting blue, green, and orange or red light emission. The compounds according to this application are preferably present in the hole transport layer, hole injection layer, electron blocking layer, and light-emitting layer. When the compounds are present in the light-emitting layer, they are preferably present as a host material.

[0153] According to the present invention, it is preferable that the compound according to this application be used in an electronic device containing one or more phosphorescent compounds. In this case, the compounds may be present in different layers, preferably in a hole transport layer, an electron blocking layer, a hole injection layer, or an emissive layer.

[0154] The term "phosphorescent compound" typically encompasses compounds in which light emission occurs due to spin-forbidden transitions, such as transitions from an excited triplet state or a state with a higher spin quantum number, such as a quintet state.

[0155] A suitable phosphorescent compound (=triplet emitter) is, in particular, a compound that, when properly excited, preferably emits light in the visible region and also contains at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, and more preferably greater than 56 and less than 80. It is preferable to use compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium as the phosphorescent compound, and especially compounds containing iridium, platinum, or copper. In the context of the present invention, all luminescent iridium, platinum, or copper complexes are considered phosphorescent compounds. Generally, all phosphorescent complexes used in phosphorescent OLEDs according to the prior art and known to those skilled in the art in the field of organic electroluminescent devices are suitable. Those skilled in the art may also use further phosphorescent complexes in combination with the compounds of the present invention in organic electroluminescent devices without employing inventive techniques. Further examples are listed in the table below.

[0156] According to the present invention, the compound according to this application can also be used in an electronic device that includes one or more fluorescent compounds.

[0157] In a preferred embodiment of the present invention, the compound according to this application is used as a hole transporting material. In this case, the compound is preferably present in a hole transport layer, an electron blocking layer, or a hole injection layer. It is particularly preferred to use it in an electron blocking layer or a hole transport layer.

[0158] The hole transport layer according to this invention is a layer having hole transport functionality located between the anode and the light-emitting layer.

[0159] In the context of this application, hole injection layers and electron blocking layers are understood to be specific embodiments of hole transport layers. A 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. An 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, of which at least one preferably contains the compound according to this application, and more preferably strictly one or two contain such a compound.

[0160] When the compounds according to this application are used as hole transport materials in hole transport layers, hole injection layers, or electron blocking layers, the compounds may be used as pure materials, i.e., in 100% proportions, in the hole transport layer, or in combination with one or more further compounds. In a preferred embodiment, the organic layer containing one of the compounds of the above formula further 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.

[0161] Particularly preferred p-dopants are quinodimethane compounds, azaindenofluoradione, azaphenalene, azatriphenylene, I2, metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or a metal of group 3, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd, and Pt having ligands containing at least one oxygen atom as a binding site. Further preferred dopants are transition metal oxides, preferably oxides of rhenium, molybdenum, and tungsten, more preferably Re2O7, MoO3, WO3, and ReO3. Even more preferred p-dopants are selected from Bi(III)-containing metal complexes, particularly Bi(III) complexes of benzoic acid or benzoic acid derivatives.

[0162] The p-dopant is preferably distributed substantially uniformly in the p-doped layer. This can be achieved, for example, by the simultaneous deposition of the p-dopant and the hole transport material matrix.

[0163] Preferred p-dopants include, in particular, the following compounds:

[0164] [ka]

[0165] [ka]

[0166] In a further preferred embodiment of the present invention, the compound is used as a hole transport material in a hole transport layer, and a layer (called a hole injection layer) exists between the anode and this hole transport layer, which contains an electron-accepting material. Preferably, this electron-accepting material is selected from the class of compounds previously mentioned with respect to use as p-dopants, particularly preferably from the compounds (D-1) to (D-14) mentioned earlier, and most preferably from compounds (D-6), (D-7) and (D-14). Preferably, the hole injection layer contains one of the above compounds in an undoped form, not mixed with other compounds. Most preferably, it consists of only one of the above compounds and does not contain other compounds.

[0167] In 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, and more specifically from the compounds listed below as preferred hole transport compounds. If 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, and preferably at least 20% by volume.

[0168] In this application, proportions are given in volume percentages. When a mixture is provided from a solution, this corresponds to a mass percentage.

[0169] The above mixed layer preferably contains one or more compounds according to the present invention.

[0170] In a further embodiment of the present invention, the compound is used as a matrix material in the light-emitting layer in combination with one or more light-emitting compounds, preferably phosphorescent compounds.

[0171] In this case, the proportion of matrix material in the light-emitting layer is 50.0% to 99.9% by volume, preferably 80.0% to 99.5% by volume, and more preferably 92.0% to 99.5% by volume, in the case of a fluorescent light-emitting layer, and 85.0% to 97.0% by volume, in the case of a phosphorescent light-emitting layer.

[0172] Accordingly, the proportion of the luminescent compound is 0.1% to 50.0% by volume, preferably 0.5% to 20.0% by volume, and more preferably 0.5% to 8.0% by volume, in the case of the fluorescent luminescent layer, and 3.0% to 15.0% by volume, in the case of the phosphorescent luminescent layer.

[0173] The light-emitting layer of an organic electroluminescent device may also include a system comprising multiple matrix materials (a mixed matrix system) and / or multiple light-emitting compounds. In this case as well, the light-emitting compounds are generally the compounds that make up the lower proportion in the system, and the matrix materials are the compounds that make up 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.

[0174] It is preferable that the compound be used as a component of the 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 having hole transport properties, and the other material is a material having electron transport properties. The compound is preferably a matrix material having hole transport properties. However, the desired electron transport and hole transport properties of the mixed matrix components may also be primarily or completely possessed by a single mixed matrix component, in which case the additional mixed matrix components perform other functions. The two different matrix materials may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, and most preferably 1:4 to 1:1. It is preferable to use a mixed matrix system in phosphorescent organic electroluminescent devices.

[0175] The mixed matrix system may contain one or more luminescent compounds, preferably one or more phosphorescent compounds. Generally, the mixed matrix system is preferably used in phosphorescent organic electroluminescent devices.

[0176] Particularly suitable matrix materials that can be used as matrix components in combination with the compounds of this invention are selected from the preferred matrix materials for phosphorescent compounds or preferred matrix materials for fluorescent compounds as defined below, depending on the type of luminescent compound used in the mixed matrix system.

[0177] Preferred phosphorescent compounds for use in mixed matrix systems are generally the same as those previously described in detail as preferred phosphorescent materials.

[0178] Preferred embodiments of various functional materials in electronic devices are listed below.

[0179] Preferred phosphorescent compounds are as follows:

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185]

change

[0186]

change

[0187]

change

[0188]

change

[0189]

change

[0190]

change

[0191] Preferred fluorescent compounds are selected from the class of arylamines. In the context of the present invention, arylamine or aromatic amine is understood to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, and more preferably, has at least 14 aromatic ring atoms. These preferred examples are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines, or aromatic chrysendiamines. Aromatic anthraceneamines are understood to mean compounds in which a diarylamino group is directly bonded to an anthracene group, preferably at position 9. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are directly bonded to an anthracene group, preferably at positions 9 and 10. Aromatic pyreneamines, pyrenediamines, chrysenamines, and chrysendiamines are similarly defined, where the diarylamino group is bonded to pyrene, preferably at position 1 or 1,6. Further preferred luminescent compounds are indenofluorenamine and fluororangeamine, benzoindenofluorenamine and fluororangeamine, dibenzoindenofluorenamine and diamine, and indenofluorene derivatives having a condensed aryl group. Equally preferred are pyrenearylamines. Equally preferred are benzoindenofluorenamine, benzofluorenamine, extended benzoindenofluorene, phenoxazine, and fluorene derivatives bonded to a furan unit or a thiophene unit.

[0192] Various material classes are suitable as matrix materials, preferably useful for fluorescent compounds. Preferred matrix materials are selected from the classes of oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene or dinaphthylanthracene), oligoarylenes containing condensed aromatic groups in particular, oligoarylenevinylenes (e.g., DPVBi or spiro-DPVBi), multi-legged metal complexes, hole-conducting compounds, electron-conducting compounds, particularly ketones, phosphine oxides and sulfoxides, as well as atropisomers, boronic acid derivatives or benzoanthracenes. 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, including anthracene, benzoanthracene, benzophenanthrene and / or pyrene, or atropisomers of these compounds. In the context of the present invention, oligoarylene is naturally understood to mean a compound in which at least three aryl or arylene groups are bonded to one another.

[0193] Preferred matrix materials for phosphorescent compounds, in addition to the compounds of this application, include 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, azabolol or boronic acid esters, triazine derivatives, zinc complexes, diazasilol or tetraazalol derivatives, diazaphosphorol derivatives, crosslinked carbazole derivatives, triphenylene derivatives, or lactams.

[0194] Suitable charge transport materials that can be used in the hole injection or hole transport layer or electron blocking layer, or in the electron transport layer, of the electronic devices of the present invention include, in addition to the compounds of this application, compounds disclosed in, for example, Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials used in these layers according to the prior art. Materials preferred for use in the hole transport layer of the OLED of the present invention are selected from indenofluorenamine derivatives, hexaazatriphenylene derivatives, amine derivatives including condensed aromatics, monobenzoindenofluorenamine, dibenzoindenofluorenamine, spirobifluorenamine, fluorenamine, spirodibenzopyranamine, dihydroacridine derivatives, spirodibenzofuran and spirodibenzothiophene, phenantrediarylamine, spirotribenzotropolone, spirobifluorene having a metaphenyldiamine group, spirobisacridine, xanthenediarylamine, and 9,10-dihydroanthracenylo compounds having a diarylamino group.

[0195] Preferred compounds having hole-transporting properties, preferably used as a hole injection layer, hole transport layer, electron blocking layer, and / or as a matrix material in the light-emitting layer of an OLED, preferably a phosphorescent layer, other than the compounds of this application are listed below. The compounds are non-deuterated compounds, as indicated by their structure.

[0196] [ka]

[0197] [ka]

[0198] [ka]

[0199] [ka]

[0200]

change

[0201]

change

[0202]

change

[0203]

change

[0204]

change

[0205]

change

[0206]

change

[0207]

change

[0208]

change

[0209]

change

[0210] [ka]

[0211] [ka]

[0212] [ka]

[0213] [ka]

[0214] Compounds HT-1 to HT-110 are well-suited not only for use in OLEDs according to the present invention but also for the aforementioned applications in OLEDs of any type or stack design. Compounds HT-1 to HT-110 can be synthesized as disclosed in the published patent applications mentioned below for each compound. Further information regarding the use and properties of the compounds can also be found disclosed in these patent applications. When used in OLEDs, compounds HT-1 to HT-110 exhibit excellent performance, particularly outstanding lifetime and efficiency.

[0215] Preferably, the OLED of the present invention comprises two or more different hole-transporting layers. Here, the compounds according to the present application may be used in one or more or all of the hole-transporting layers.

[0216] The material used in the electron transport layer may be any material used as an electron transport material in the electron transport layer according to the prior art. Particularly preferred are aluminum complexes, e.g., Alq3; zirconium complexes, e.g., Zrq4; lithium complexes, e.g., 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.

[0217] A preferred cathode for electronic devices is a multilayer structure composed of a metal, metal alloy, or various metals with a low work function, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also preferred are alloys composed of alkali metals or alkaline earth metals with silver, such as magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, further metals with relatively high work functions, such as Ag or Al, may also be used, in which case combinations of metals such as Ca / Ag, Mg / Ag, or Ba / Ag are commonly used. It may also be preferable to introduce a thin interlayer of a material with a high dielectric constant between the metallic cathode and the organic semiconductor. Examples of materials useful for this purpose include alkali metal or alkaline earth metal fluorides, as well as their corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Lithium quinolinate (LiQ) can also be used for this purpose. The thickness of this layer is preferably 0.5 to 5 nm.

[0218] A preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, metals with a high redox potential are suitable for this purpose, such as Ag, Pt, or Au. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are suitable. x Al / PtO x) may also be preferred. Depending on the application, at least one of the electrodes needs to be transparent or partially transparent to allow irradiation of organic materials (organic solar cells) or emission of light (OLED, O-laser). Here, preferred anode materials are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Furthermore, conductive doped organic materials, in particular 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.

[0219] The device is properly structured (depending on the application), its contacts are connected, and it is finally sealed to eliminate the damaging effects of water and air.

[0220] In a preferred embodiment, the electronic device is characterized by having one or more layers coated by sublimation. In this case, the material is subjected to a vacuum sublimation system. -5 Less than mbar, preferably 10 -6 The initial pressure is applied by deposition at a pressure of less than mbar. However, in this case, the initial pressure can be further reduced, for example, 10 -7 It is also possible to set it to less than mbar.

[0221] Similarly, electronic devices are preferred in which one or more layers are coated by OVPD (organic vapor deposition) or with the help of carrier gas sublimation. In this case, the material is 10 -5 The material is applied at a pressure of mbar to 1 bar. A special case of this method is OVJP (organic vapor jet printing), in which the material is applied directly by the nozzle and thus structured (e.g., MSArnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0222] In addition, an electronic device is preferred in which one or more layers are produced from a solution, for example by spin coating, or by any printing method, such as screen printing, flexographic printing, nozzle printing, or offset printing, more preferably by LITI (photo-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, a soluble compound is required. High solubility can be achieved by suitable substitution of the compound.

[0223] The electronic device of the present invention is more preferably manufactured by applying one or more layers from a solution and one or more layers by sublimation.

[0224] According to the present invention, an electronic device comprising one or more compounds according to the present application can be used in a display as a light source for illumination applications, and as a light source for medical and / or cosmetic applications.

[0225] [example] A) Synthesis example General deuteration protocol The compound is dissolved in a mixture of heavy water (99% deuterium atoms) and toluene-d8 (99% deuterium atoms), and heated under pressure at 160°C for 96 hours in the presence of dry platinum-supported carbon (5%) as a catalyst. After the reaction mixture is cooled, the phases are separated, and the aqueous phase is extracted twice with a mixture of tetrahydrofuran and toluene. The reassembled organic phase is washed with sodium chloride solution, dried over sodium sulfate, and filtered. The solvent is removed under vacuum to obtain the crude deuterated compound as a solid. The compound is further purified by extraction, crystallization, and sublimation.

[0226] Example 1. N-[(2,2',3,3',4',5,5',6,6'- 2 H9)-[1,1'-biphenyl]-4-yl]-N-{4-[(3,4,5,10,11,12,13- 2 H7)-8-Oxatricyclo[7.4.0.0 2,7]Trideca-1(13),2(7),3,5,9,11-Hexaen-6-yl](2,3,5,6- 2 H4)phenyl}(1,1',2,2',3,3',4,4',5,5',6,6',7,7',8'- 2 H15)-9,9'-spirobi[fluorene]-8-amine

[0227] [ka]

[0228] Following a general deuteration protocol, N-{[1,1'-biphenyl]-4-yl}-N-(4-{8-oxatricyclo[7.4.0.0 2 From [,7]trideca-1(13),2(7),3,5,9,11-hexaen-6-yl}phenyl)-9,9'-spirobi[fluorene]-8-amine (23.1 g, 31.8 mmol), toluene-D8 (231 g, 2.31 mol), heavy water (1300 g, 64.9 mol), and dry platinum-supported carbon (5%) (30 g), 23.5 g of crude product is prepared. The crude product is further purified by two extractions with a mixture of heptane and toluene (4:1) and two sublimations to obtain 5.3 g of the title compound with a purity of over 99.9%. The substance is confirmed by HPLC-MS.

[0229] Example 2. N,N-bis[(2,2',3,3',4',5,5',6,6'- 2 H9)-[1,1'-biphenyl]-4-yl](1,1',2,2',3,3',4,4',5,5',6,6',7,7',8'- 2 H15)-9,9'-spirobi[fluorene]-8-amine

[0230] [ka]

[0231] Following a standard deuteration protocol, 20.8 g of crude product was obtained from N,N-bis({[1,1'-biphenyl]-4-yl})-9,9'-spirobi[fluorene]-8-amine (25.0 g, 39.3 mmol), toluene-D8 (250 g, 2.50 mol), heavy water (1230 g, 61.4 mol), and dry platinum-supported carbon (5%) (30 g). The crude product was extracted with a mixture of heptane and toluene (3:2), crystallized from toluene, and further purified by two sublimations to obtain 7.4 g of the title compound with a purity exceeding 99.9%. The compound was confirmed by HPLC-MS.

[0232] Example 3. N-{4-[(3,4,5,10,11,12,13- 2 H7)-8-Oxatricyclo[7.4.0.0 2 ,7]Trideca-1(13),2,4,6,9,11-Hexaen-6-yl](2,3,5,6- 2 H4)phenyl}-N-{4-[(3,4,5,10,11,12,13- 2 H7)-8-Oxatricyclo[7.4.0.0 2 ,7]Trideca-1(9),2(7),3,5,10,12-Hexaen-6-yl](2,3,5,6- 2 H4)phenyl}(1,1',2,2',3,3',4,4',5,5',6,6',7,7',8'- 2 H15)-9,9'-spirobi[fluorene]-8-amine

[0233] [ka]

[0234] Following a general deuteration protocol, N-(4-{8-oxatricyclo[7.4.0.0 2 [7]Trideca-1(13),2,4,6,9,11-Hexaen-6-yl}phenyl)-N-(4-{8-Oxatricyclo[7.4.0.0 2From [,7]trideca-1(9),2(7),3,5,10,12-hexaen-6-yl}phenyl)-9,9'-spirobi[fluorene]-8-amine (19.9 g, 24.4 mmol), toluene-D8 (200 g, 2.00 mol), heavy water (2020 g, 100.9 mol), and dry platinum-supported carbon (5%) (25 g), 19.5 g of crude product is prepared. The crude product is extracted with a mixture of heptane and toluene (4:1), crystallized from heptane, crystallized twice from ethyl acetate, crystallized from toluene, and finally further purified by four sublimations under high vacuum to obtain 5.7 g of the title compound with a purity of over 99.9%. The substance is confirmed by HPLC-MS.

[0235] Further deuterated spiro-bisarylamine derivatives can be synthesized in a similar manner. The yield is 40% to 90% in all cases.

[0236] [ka]

[0237] [ka]

[0238] [ka]

[0239] [ka]

[0240] [ka]

[0241] [ka]

[0242] [ka]

[0243] [ka]

[0244] [ka]

[0245] [ka]

[0246] [ka]

[0247] [ka]

[0248] [ka]

[0249] [ka]

[0250] [ka]

[0251] [ka]

[0252] B) Device examples B-1) General manufacturing and characterization methods An OLED containing the compound according to this application is prepared by the following general method: The substrate used is a glass plate coated with a 50 nm thick structured ITO (indium tin oxide). 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 cathode. The cathode is formed by a 100 nm thick aluminum layer. Specific device settings for the OLED are shown in Table 1, and the materials for various layers of the OLED are shown in Table 3.

[0253] All materials are applied by thermal deposition in a vacuum chamber. Here, the luminescent layer always consists of at least one matrix material (host material) and a luminescent dopant (luminescent material) that is co-deposited with the matrix material or multiple matrix materials in a specific volume ratio. Here, for example, an expression such as H:SEB(5%) means that material H is present in the layer at a volume ratio of 95% and SEB is present at a volume ratio of 5%. Similarly, other layers may also consist of mixtures of two or more materials.

[0254] OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, the external quantum efficiency (EQE, measured in percent) as a function of luminous flux 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 This expression means 10mA / cm 2 This represents the external quantum efficiency at the operating current density of LT80@60mA / cm². 2 It achieves 60 mA / cm² without using any acceleration factors. 2 At a current density of, for example, 5000 cd / m², the OLED can achieve a current density of 5000 cd / m². 2 From the initial brightness to 80% of the initial intensity, i.e., 4000 cd / m² 2 This is the lifespan until the quality declines to that point.

[0255] B-2) Use of compounds in EBL for blue fluorescent OLEDs Compounds HTM-1 to HTM-3 according to this application are used in the EBL of a blue fluorescent OLED stack, as shown in Table 1 below.

[0256] [Table 1]

[0257] In this device configuration, very good results in terms of EQE, lifetime, and voltage can be obtained using the compound, as shown in the table below.

[0258] [Table 2]

[0259] Similar results can be obtained by using the compounds according to this invention in other stack designs, such as stacks containing a green or red phosphorescent layer.

[0260] [Table 3-1]

[0261] [Table 3-2]

Claims

1. Formula (I) or (II) 【Chemistry 1】 (In the formula, the following applies to the variable group: G is given by equation (G-1) or (G-2) 【Chemistry 2】 It is a base by, In the formulas, the dotted line is a connection to the remainder of formula (I) or (II), and the dotted line is connected at one of the positions marked with # in formulas (G-1) and (G-2), and the base R １ However, they are bonded to all free positions on the aromatic rings of formulas (G-1) and (G-2); L １ is, base R ２ Aromatic ring systems having 6 to 40 aromatic ring atoms, or the group R, which are substituted with ２ A heteroaromatic ring system having 5 to 40 aromatic ring atoms that are substituted with; Ar １ In each occurrence, the base R is identical or different. ３ Aromatic ring systems having 6 to 40 aromatic ring atoms, which are substituted with the group R ３ Selected from heteroaromatic ring systems having 5 to 40 aromatic ring atoms that are substituted; Ar ２ is, in each occurrence, the same or different and is selected from an aromatic ring system having 6 to 40 aromatic ring atoms substituted with a group R ３ and a heteroaromatic ring system having 5 to 40 aromatic ring atoms substituted with a group R ３ ; E is a single bond, or C(R) ４ ) ２ , Si(R ４ ) ２ , NR ４ It is a divalent group selected from O and S; T is identical or different in each occurrence, a single bond, or C(R) ４ ) ２ , Si(R ４ ) ２ , NR ４ It is a divalent group selected from O and S; n is either 0 or 1, where n = 0, base L １ It does not exist, and the G group and N atom are directly linked; R ０ In each occurrence, H, D, F, Cl, Br, I, C(=O)R appear identically or differently. ５ , CN, Si(R ５ ) ３ , N(R ５ ) ２ , P(=O)(R ５ ) ２ , OR ５ , S(=O)R ５ , S (=O) ２ R ５ Selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two radicals R ０ These may be linked to each other to form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are radicals R ５ Substituted by one or more CH groups in the alkyl, alkoxy, alkenyl and alkynyl groups. ２ The base is -R in each case. ５ C=CR ５ -, -C≡C-, Si(R ５ ) ２ C=O, C=NR ５ , -C(=O)O-, -C(=O)NR ５ -, NR ５ , P(=O)(R ５ ), -O-, -S-, SO or SO ２ It may be replaced by; R １ In each occurrence, H, D, F, Cl, Br, I, C(=O)R appear identically or differently. ５ , CN, Si(R ５ ) ３ , N(R ５ ) ２ , P(=O)(R ５ ) ２ , OR ５ , S(=O)R ５ , S (=O) ２ R ５ Selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two or more radicals R １ These may be linked to each other to form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are radicals R ５ Substituted by one or more CH groups in the alkyl, alkoxy, alkenyl and alkynyl groups. ２ The base is -R in each case. ５ C=CR ５ -, -C≡C-, Si(R ５ ) ２ C=O, C=NR ５ , -C(=O)O-, -C(=O)NR ５ -, NR ５ , P(=O)(R ５ ), -O-, -S-, SO or SO ２ It may be replaced by; R ２ is, in each occurrence, the same or different and is H, D, F, Cl, Br, I, C(=O)R ５ , CN, Si(R ５ ), ３ , N(R ５ ), ２ , P(=O)(R ５ ), ２ , OR ５ , S(=O)R ５ , S(=O) ２ R ５ , a linear alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more radicals R ２ may be linked to each other to form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups, and the aromatic and heteroaromatic ring systems are substituted by the radical R ５ , and one or more CH ２ groups in the alkyl, alkoxy, alkenyl and alkynyl groups are, in each case, -R ５ C=CR ５ -, -C≡C-, Si(R ５ ), ２ , C=O, C=NR ５ , -C(=O)O-, -C(=O)NR ５ -, NR ５ , P(=O)(R ５ ), -O-, -S-, SO or SO ２ and may be replaced by; R ３ is, in each occurrence, the same or different, H, D, F, Cl, Br, I, C(=O)R ５ , CN, Si(R ５ ), ３ , N(R ５ ), ２ , P(=O)(R ５ ), ２ , OR ５ , S(=O)R ５ , S(=O) ２ R ５ , 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; where two or more radicals R ３ may be linked to each other to form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups, and the aromatic and heteroaromatic ring systems are substituted by a radical R ５ , and one or more CH ２ groups in the alkyl, alkoxy, alkenyl and alkynyl groups are, in each case, -R ５ C=CR ５ -, -C≡C-, Si(R ５ ), ２ , C=O, C=NR ５ , -C(=O)O-, -C(=O)NR ５ -, NR ５ , P(=O)(R ５ ), -O-, -S-, SO or SO ２ may be replaced; R ４ In each occurrence, H, D, F, Cl, Br, I, C(=O)R appear identically or differently. ５ , CN, Si(R ５ ) ３ , N(R ５ ) ２ , P(=O)(R ５ ) ２ , OR ５ , S(=O)R ５ , S (=O) ２ R ５ Selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two or more radicals R ４ These may be linked to each other to form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are radicals R ５ Substituted by one or more CH groups in the alkyl, alkoxy, alkenyl and alkynyl groups. ２ The base is -R in each case. ５ C=CR ５ -, -C≡C-, Si(R ５ ) ２ C=O, C=NR ５ , -C(=O)O-, -C(=O)NR ５ -, NR ５ , P(=O)(R ５ ), -O-, -S-, SO or SO ２ It may be replaced by; R ５ In each occurrence, H, D, F, Cl, Br, I, C(=O)R appear identically or differently. 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 Selected from a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two or more radicals R ５ These may be linked to each other to form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are radicals R ６ Substituted by one or more CH groups in the alkyl, alkoxy, alkenyl and alkynyl groups. ２ The base is -R in each case. 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 SO ２ It may be replaced by; R ６ R is selected, identically or differently in each occurrence, from H, D, F, Cl, Br, I, CN, alkyl groups having 1 to 20 carbon atoms, aromatic ring systems having 6 to 40 carbon atoms, or heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R ６ These may be linked to each other to form a ring; the alkyl group, aromatic ring system and heteroaromatic ring system may be substituted with one or more radicals selected from F and CN; Here, in equation (I), the three groups -Ar １ ,-Ar １ and -[L １ ] ｎ Each of the -G groups contains at least one D atom bonded to an aromatic or heteroaromatic ring; where, in formula (II), the three groups -Ar ２ ,-Ar ２ and -[L １ ] ｎ (Each of the G atoms contains at least one D atom bonded to an aromatic or heteroaromatic ring.) A compound of [this].

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

3. The compound according to claim 1 or 2, characterized in that G is a group according to formula (G-1).

4. (G-1) is formula (G-1-1-1) 【Transformation 3】 (In the formulas, the dotted line represents the connection to the remainder of formula (I) or (II), and base R １ However, it is bonded to all free positions on the aromatic ring of formula (G-1-1-1). The compound according to claim 3, characterized by conforming to the following.

5. R １ The compound according to claim 4, characterized in that it is D.

6. L １ However, Radical R ２ The compound according to any one of claims 1 to 5, characterized in that it is substituted with a divalent group selected from benzene, biphenyl, naphthalene, and fluorene.

7. A compound according to any one of claims 1 to 6, characterized in that n is 0.

8. Base Ar １ However, identically or differently, selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, particularly 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, where the group is a radical R ３ The compound according to any one of claims 1 to 7, characterized in that it is substituted with

9. The basis of equation (II) 【Chemistry 4】 However, the following formula: 【Chemistry 5-1】 【Chemistry 5-2】 【Chemistry 5-3】 (In the equation, the dotted line represents the connection to the remainder of equation (II).) A compound according to any one of claims 1 to 8, characterized in that it is selected from among the following.

10. R １ Is it D, or R １ The fact that it is completely deuterated, and / or R ２ The compound according to any one of claims 1 to 9, characterized in that is D.

11. Equations (I) and (II) are given by equations (I-1-1) and (II-1-1). 【Transformation 6】 (In the formula, the variable group is as defined in claim 1, and all free positions on spirobifluorene are substituted with group R1.) A compound according to any one of claims 1 to 10, characterized by conforming to the above.

12. R ３ A compound according to any one of claims 1 to 11, characterized in that is D.

13. The compound according to any one of claims 1 to 12, characterized in that the compound is completely deuterated.

14. A material characterized in that a compound described in any one of claims 1 to 13 is present in the material with a purity of more than 90% by weight.

15. A preparation comprising at least one compound according to any one of claims 1 to 13 and at least one solvent.

16. An electronic device comprising at least one compound as described in any one of claims 1 to 13.

17. The electronic device according to claim 16, 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 transport layer, an electron blocking layer, or a hole injection layer, comprises the at least one compound.

18. Use of the compound according to any one of claims 1 to 13 in an electronic device.

Images