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CN119894856A - Nitrogen-containing compounds for organic electroluminescent devices - Google Patents

Nitrogen-containing compounds for organic electroluminescent devices Download PDF

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Publication number
CN119894856A
CN119894856A CN202380067569.7A CN202380067569A CN119894856A CN 119894856 A CN119894856 A CN 119894856A CN 202380067569 A CN202380067569 A CN 202380067569A CN 119894856 A CN119894856 A CN 119894856A
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Prior art keywords
aromatic
occurrence
substituted
ring system
group
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CN202380067569.7A
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Chinese (zh)
Inventor
菲利普·施特塞尔
鲁文·林格
斯特凡·施拉姆
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Merck Patent GmbH
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Merck Patent GmbH
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Abstract

The present invention relates to nitrogen-containing compounds suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing these compounds.

Description

Nitrogen-containing compounds for organic electroluminescent devices
Technical Field
The present invention relates to nitrogen-containing compounds for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices, in particular organic electroluminescent devices, containing these materials.
Background
Phosphorescent organometallic complexes are often used as light-emitting materials in organic electroluminescent devices. Up to four times the energy and power efficiency can be achieved using metal-organic compounds as phosphorescent emitters for quantum mechanical reasons. In general, there remains a need for improvements in electroluminescent devices, in particular electroluminescent devices exhibiting triplet emission (phosphorescence). The characteristics of phosphorescent electroluminescent devices depend not only on the triplet emitters used. Other materials used, such as matrix materials, are also of particular importance here. Thus, improvements in these materials can also significantly improve the performance of electroluminescent devices.
In addition, many electroluminescent devices include other layers in addition to the light-emitting layer, such as one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and/or charge generation layers (charge generation layers). These layers have a significant impact on the performance of the electroluminescent device.
In particular, the above-mentioned electroluminescent device is described in document WO 2014/015938 A1.
In general, there remains a need for improvements in these materials, for example for use as host materials, particularly in terms of lifetime, but also in terms of efficiency and operating voltage of the device.
Disclosure of Invention
It is therefore an object of the present invention to provide compounds suitable for use in organic electronic devices, in particular organic electroluminescent devices, which compounds give good device performance when used in such devices, and to provide corresponding electronic devices.
In particular, it is an object of the present invention to provide a compound having a long service life, high efficiency and a low operating voltage. In particular, a hole transporting material, a hole injecting material, or an electron blocking material contributes to these characteristics. Furthermore, the nature of the host material (also referred to herein as host material) has a significant impact on the lifetime and efficiency of the organic electroluminescent device.
Furthermore, it is an object of the present invention to provide compounds characterized by a low Refractive Index (RI).
It may be a further object of the present invention to provide compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, in particular as host materials. In particular, it is an object of the present invention to provide a host material suitable for use in green or blue phosphorescent electroluminescent devices and optionally also in red or yellow phosphorescent photoinduced luminescent devices.
In addition, these compounds should give devices having excellent color purity, particularly when used as host materials, hole transport materials, hole injection materials, or electron blocking materials in organic electroluminescent devices.
Another task may be to provide electronic devices that are as cost-effective and quality stable as possible with excellent performance.
Furthermore, the electronic device should be able to be used or adapted for a variety of purposes. In particular, the performance of the electronic device should be maintained over a wide temperature range.
It has surprisingly been found that the specific compounds described in more detail below solve this problem, are very suitable for use in electroluminescent devices, and result in organic electroluminescent devices which exhibit very good properties, in particular in terms of lifetime, color purity, efficiency, operating voltage and refractive index. The subject of the invention is therefore these compounds and electronic devices, in particular organic electroluminescent devices, containing such compounds.
The subject of the invention is a compound comprising at least one structure of formula (I), preferably according to formula (I)
Wherein the symbols represent:
Z a, identically or differently at each occurrence, represents Ar, R c、L1-N(Ar)2 or L 1 -Q, preferably R c、L1-N(Ar)2 or L 1 -Q;
Ar is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which may be substituted by one or more residues R d, wherein two residues Ar bound to the same N atom may also be bridged to one another by a single bond or a bridge selected from B(Rd)、C(Rd)2、Si(Rd)2、C＝O、C＝N Rd、C＝C(Rd)2、RdC＝CRd、O、S、S＝O、SO2、N(Rd)、P(Rd)、P(＝O)Rd and an ortho-linked phenylene which may be substituted by one or more residues R d, said bridge preferably being selected from C (R d)2、O、N(Rd) and an ortho-linked phenylene which may be substituted by one or more residues R d, preferably Ar, identically or differently on each occurrence, represents an aryl or heteroaryl group having from 6 to 40 aromatic ring atoms, which may be substituted by one or more residues R, wherein two residues Ar bound to the same N atom may also be bridged to one another by a single bond or a bridge selected from B(Rd)、C(Rd)2、Si(Rd)2、C＝O、C＝N Rd、C＝C(Rd)2、RdC＝C Rd、O、S、S＝O、SO2、N(Rd)、P(Rd)、P(＝O)Rd and an ortho-linked phenylene which may be substituted by one or more residues R d, said bridge preferably being selected from C (R d)2、O、N(Rd) and an ortho-linked phenylene which may be substituted by one or more residues R d;
L 1 represents identically or differently on each occurrence a bond or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which ring system may be substituted by one or more residues R;
R a is, identically or differently on each occurrence, a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 10 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 10 carbon atoms, which in each case may be substituted by one or more residues R 2, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which in each case may be substituted by one or more residues R 2, preferably a straight-chain alkyl radical having 1 to 10 carbon atoms or a branched or cyclic alkyl radical having 3 to 10 carbon atoms, which in each case may be substituted by one or more residues R 2, or phenyl, which in each case may be substituted by one or more residues R 2, wherein two or more preferably adjacent substituents R a may form a ring system with one another;
R b is, identically or differently on each occurrence, H, D, straight-chain alkyl, alkoxy or thioalkoxy having from 1 to 10 carbon atoms, or branched or cyclic alkyl, alkoxy or thioalkoxy having from 3 to 10 carbon atoms, which in each case may be substituted by one or more residues R 2, or an aromatic or heteroaromatic ring system having from 5 to 20 aromatic ring atoms, which in each case may be substituted by one or more residues R 2, preferably H, D, straight-chain alkyl having from 1 to 10 carbon atoms, or branched or cyclic alkyl or phenyl having from 3 to 10 carbon atoms, which in each case may be substituted by one or more residues R 2, wherein two preferably adjacent substituents R b may form a ring system with one another, particularly preferably H or D;
Q, identically or differently on each occurrence, represents an electron-transporting group, preferably a nitrogen-containing heteroaryl group having 5 to 12 ring atoms, particularly preferably having 6 to 12 ring atoms, which may be substituted by one or more residues R e;
R, R c、Rd、Re is, identically or differently on each occurrence, a straight-chain alkyl, alkoxy or thioalkoxy radical of H、D、OH、F、Cl、Br、I、CN、NO2、N(Ar')2、N(R1)2、C(＝O)N(Ar')2、C(＝O)N(R1)2、C(Ar')3、C(R1)3、Si(Ar')3、Si(R1)3、B(Ar')2、B(R1)2、C(＝O)Ar'、C(＝O)R1、P(＝O)(Ar')2、P(＝O)(R1)2、P(Ar')2、P(R1)2、S(＝O)Ar'、S(＝O)R1、S(＝O)2Ar'、S(＝O)2R1、OSO2Ar'、OSO2R1、 having 1 to 40 carbon atoms, or an alkenyl or heteroaryloxy radical of 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy radical of 3 to 20 carbon atoms, where alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl radicals, respectively, may be substituted by one or more residues R 1, where one or more non-adjacent CH 2 groups may be replaced by R1C＝CR1、C≡C、Si(R1)2、C＝O、C＝S、C＝Se、C＝NR1、C(＝O)O、C(＝O)NR1-、NR1、P(＝O)(R1)、-O-、S、SO or SO 2, or an aromatic or heteroaromatic ring system of 5 to 60 aromatic ring atoms, respectively, which may be substituted by one or more residues R 1, or an aryloxy or heteroaryloxy radical of 5 to 60 aromatic ring atoms, which may be substituted by one or more residues R 1, where two residues R, R d、Re may also form a ring system with each other, or residues R, R d、Re may form a ring system with further groups, in particular residues R c;
Ar 'is identically or differently on each occurrence an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which may be substituted by one or more residues R 1, wherein the two residues Ar' bound to the same C, si, N, P or B atom may also be bridged to one another by a single bond or a bridge selected from B(R1)、C(R1)2、Si(R1)2、C＝O、C＝NR1、C＝C(R1)2、O、S、S＝O、SO2、N(R1)、P(R1) and P (=O) R 1;
R 1 is identically or differently at each occurrence a linear, alkoxy or thioalkoxy radical having from 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having from 3 to 40 carbon atoms, or an alkenyl radical having from 2 to 40 carbon atoms, which may be substituted by one or more residues R 2, respectively, wherein one or more non-adjacent CH 2 groups may be replaced by -R2C＝CR2-、C≡C-、Si(R2)2、C＝O、C＝S、C＝Se、C＝NR2、C(＝O)O-、C(＝O)NR2-、NR2、P(＝O)(R2)、-O-、S、SO or SO 2, and wherein one or more H atoms may be replaced by D, F, cl, br, I, CN or NO 2, or an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which may be substituted by one or more residues R 2, or an aryloxy or heteroaryloxy radical having from 5 to 60 aromatic ring atoms, which may be substituted by one or more residues R 2, or an aralkyl or heteroarylalkyl radical having from 5 to 60 aromatic ring atoms, which may be substituted by one or more residues R 2, or a combination of these systems, wherein two or more preferably adjacent residues R may form part of a ring with one another R 1;
Ar 'is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, which may be substituted by one or more residues R 2, wherein the two residues Ar' bound to the same C, si, N, P or B atom may also be bridged to one another by a single bond or a bridge selected from B(R2)、C(R2)2、Si(R2)2、C＝O、C＝NR2、C＝C(R2)2、O、S、S＝O、SO2、N(R2)、P(R2) and P (=O) R 2;
r 2 is selected identically or differently on each occurrence from H, D, F, CN, an aliphatic hydrocarbon residue having from 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, where one or more H atoms can be replaced by D, F, cl, br, I or CN and can be substituted by one or more alkyl groups each having from 1 to 4 carbon atoms, where two or more preferably adjacent substituents R 2 can form a ring system with one another.
Aryl groups in the sense of the present invention contain 6 to 40 carbon atoms, heteroaryl groups in the sense of the present invention contain 3 to 40 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. Herein, aryl or heteroaryl refers to a simple aromatic ring (i.e., benzene) or a simple heteroaromatic ring (e.g., pyridine, pyrimidine, thiophene, etc.), or a fused (added ring) aryl or heteroaryl, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc., for example. Aromatic compounds, such as biphenyls, which are linked to one another by single bonds, are not referred to as aryl or heteroaryl groups, but rather as aromatic ring systems.
Electron-deficient heteroaryl in the sense of the present invention means a heteroaryl group having at least one heteroaromatic six-membered ring with at least one nitrogen atom. Other aromatic or heteroaromatic five-membered rings or six-membered rings may also be fused to this six-membered ring. Examples of electron-poor heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline or quinoxaline.
An aromatic ring system in the sense of the present invention comprises 6 to 60 carbon atoms in the ring system. Heteroaromatic ring systems in the sense of the present invention contain 3 to 60 carbon atoms and at least one heteroatom in the ring system, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the sense of the present invention is understood to be a system which does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be linked by non-aromatic units such as C, N or O atoms. For example, fluorene, 9' -spirobifluorene, 9-diaryl fluorene, triarylamine, diaryl ether, stilbene, etc. systems are also understood as aromatic ring systems in the sense of the present invention, as well as systems in which two or more aryl groups are linked, for example by a short alkyl group. Preferably, the aromatic ring system is selected from fluorene, 9' -spirobifluorene, 9-diarylamine or groups in which two or more aryl and/or heteroaryl groups are linked to each other by single bonds.
In the present invention, the aliphatic hydrocarbon residue or alkyl or alkenyl or alkynyl group (which may contain 1 to 20 carbon atoms and in which a single H atom or CH 2 group may also be substituted by the above groups) is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloalkynyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. Alkoxy having 1 to 40 carbon atoms is preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octoxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2, 2-trifluoroethoxy. Thioalkyl having 1 to 40 carbon atoms is, in particular, a methylthio group, an ethylthio group, a n-propylthio group, an isopropylthio group, a n-butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a n-pentylthio group, a Zhong Wuliu-yl group, a n-hexylthio group, a cyclohexylthio group, a n-heptylthio group, a cycloheptylthio group, a n-octylthio group, a cyclooctylthio group, a 2-ethylhexyl thio group, a trifluoromethylthio group, a pentafluoroethylthio group, a2, 2-trifluoroethylthio group, a vinylthio group, a propenyl thio group, a butenylthio group, a pentenylthio group, a cyclopentenylthio group, a hexenylthio group, a cyclohexenylthio group, an ethynylthio group, a propynylthio group, a butynylthio group, a pentynylthio group, a hexynylthio group, a heptynylthio group or an alkynylthio group. In general, the alkyl, alkoxy or thioalkyl groups according to the invention may be straight-chain, branched or cyclic, in which one or more non-adjacent CH 2 groups may be replaced by the abovementioned groups, and furthermore one or more H atoms may also be replaced by D, F, cl, br, I, CN or NO 2, preferably F, cl or CN, further preferably F or CN, particularly preferably CN.
An aromatic or heteroaromatic ring system having from 5 to 60 or from 5 to 40 aromatic ring atoms, which may in each case also be substituted by the abovementioned residues and may be linked to the aromatic or heteroaromatic structure in any position, the ring system being in particular a radical derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, cis-or trans-indenocarbazole, cis-or trans-indolocarbazole, triindene, isoindene, spirotetralin, spiroisoindene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthazole, phenanthroimidazole, pyridine imidazole, pyrazinoimidazole, imidazole quinoxaline imidazole, oxazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthrooxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diazaanthracene, 2, 7-diazapyrene, 2, 3-diazapyrene, 1, 6-diazapyrene, 1, 8-diazapyrene, 4, 5-diazapyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorored, naphthyridine, azocarbazole, 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, or groups derived from combinations of these systems.
In the present specification, the expression that two or more residues may form a ring with each other means, in particular, that the two residues are linked to each other by a chemical bond while formally eliminating two hydrogen atoms. This is explained by the following formula.
Furthermore, the above expression is to be understood as meaning, for the case where one of the two residues represents hydrogen, that the second residue is bound at the position where it would otherwise be bound to a hydrogen atom, thereby forming a ring. This will be illustrated by the following formula:
in a preferred embodiment, the compounds according to the invention may preferably comprise at least one structure of the formulae (I-1) to (I-4), and particularly preferably are selected from the compounds of the formulae (I-1) to (I-4),
Wherein the symbols Ar, lr 1、Q、Ra、Rb and R c have the meanings described above in particular for formula (I).
It may also be provided that the groups Ar are, identically or differently, selected for each occurrence from phenyl, biphenyl, terphenyl, tetrabiphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, which may each be substituted by one or more residues R d, preferably phenyl, biphenyl, fluorene, dibenzofuran, triphenylene, indolocarbazole.
Preferably, it may be provided that the groups Ar are selected identically or differently on each occurrence from the structures of the formulae (Ar a -1) to (Ar a -28),
Wherein for the symbols used the following holds:
Y 2 is O, S, NR d or C (R d)2, preferably O, NR d or C (R d)2;
k is independently at each occurrence 0 or 1;
i is independently at each occurrence 0,1 or 2;
j is independently at each occurrence 0,1, 2 or 3, preferably 0,1 or 2;
h is independently at each occurrence 0, 1,2,3 or 4, preferably 0, 1 or 2;
g is independently at each occurrence 0,1, 2,3, 4 or 5, preferably 0,1 or 2;
R d has the meaning described above, in particular for formula (I), and the dotted bond marks the binding position.
The structures of the formulae (Ar a -1) to (Ar a-5)、(Ara -7) to (Ar a-13)、(Ara -18) to (Ar a-22)、(Ara-24)、(Ara -27) and (Ar a -28) are particularly preferred here, the structures of the formulae (Ar a-1)、(Ara-2)、(Ara-4)、(Ara-5)、(Ara -7) to (Ar a-9)、(Ara-12)、(Ara-13)、(Ara-19)、(Ara -21) and (Ar a -22) are particularly preferred, and the structures of the formulae (Ar a-1)、(Ara-2)、(Ara -7) to (Ar a-9)、(Ara -12) and (Ar a -13) are particularly preferred.
In a further preferred embodiment, it can be provided that the radicals L 1 represent, equally or differently, bonds or structures selected from the formulae (L 1 -1) to (L 1 -22),
Wherein for the symbols used the following holds:
Y is CR 2, O, S or NR, preferably O or NR;
j is independently at each occurrence 0,1, 2 or 3, preferably 0,1 or 2;
h is independently at each occurrence 0,1, 2,3 or 4, preferably 0,1 or 2
R has the meaning described above, in particular for formula (I), and the dashed bonds mark the binding sites.
The sum of the indices i, j, h and g in the structures of the formulae (Ar a -1) to (Ar a -28) and/or (L 1 -1) to (L 1 -22) is preferably up to 6, particularly preferably up to 4, particularly preferably up to 2.
The radicals Q, identically or differently on each occurrence, represent electron-transporting groups, where the electron-transporting groups preferably represent nitrogen-containing heteroaryl groups having 5 to 12 ring atoms, particularly preferably nitrogen-containing heteroaryl groups having 6 to 12 ring atoms, which may be substituted by one or more residues R e. The group Q preferably represents an electron-poor heteroaryl group, wherein the electron-poor heteroaryl group particularly preferably also has the properties given above and below.
Preferably, it may be provided that the group Q represents a nitrogen-containing heteroaryl group having 6 to 12 ring atoms, wherein the ring has at least two nitrogen atoms, which nitrogen-containing heteroaryl group may be substituted by one or more residues R e, wherein the carbon atoms adjacent to at least two nitrogen atoms located in the ring are not linked to a hydrogen atom.
Electron transporting groups are well known in the art and facilitate the ability of a compound to transport and/or conduct electrons. They include in particular nitrogen-containing heteroaryl groups having from 5 to 12 ring atoms, particularly preferably having from 6 to 12 ring atoms, where they are generally electron-deficient heteroaryl groups.
Furthermore, it can also be provided that the group Q represents a pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and/or benzimidazole group, preferably a pyrimidine, pyrazine, triazine, quinazoline, quinoxaline and/or benzimidazole group, particularly preferably a pyrimidine, triazine, quinazoline and/or quinoxaline group, particularly preferably a pyrimidine and/or triazine group, particularly preferably a triazine group which may be substituted by one or more residues R e.
In a particularly preferred embodiment, it can be provided that the group Q represents a pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, imidazole and/or benzimidazole group, preferably a pyrimidine, pyrazine, triazine, quinazoline, quinoxaline and/or benzimidazole group, which can be substituted by one or more residues R e, wherein the carbon atoms adjacent to at least two nitrogen atoms are attached to an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which ring systems can each be substituted by one or more residues R 1.
In a further embodiment, it can be provided that the group Q represents a pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, imidazole and/or benzimidazole radical, preferably a pyrimidine, pyrazine, triazine, quinazoline, quinoxaline and/or benzimidazole radical, which can be substituted by one or more residues R e, wherein the carbon atoms adjacent to at least two nitrogen atoms are linked to a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group adjacent to the carbon atom to which the corresponding N atom is linked does not have an azide hydrogen atom and can be substituted by one or more residues R 1, respectively. In this case, particular preference is given to embodiments in which the carbon atoms adjacent to at least two nitrogen atoms are preferably linked to an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which in each case may be substituted by one or more residues R 1.
In one embodiment, it can be provided that the group Ar does not comprise a triazine group, preferably does not comprise a pyrimidine and/or triazine group, particularly preferably does not comprise an electron-transporting group.
In one embodiment, it can be provided that the group L 1 contains no triazine groups, preferably no pyrimidine and/or triazine groups, particularly preferably no electron-transporting groups.
Compounds in which the groups L 1 and/or Ar do not contain electron-transporting groups are particularly suitable as hole-transporting, hole-injecting or electron-blocking materials for use in the corresponding layers, which layers are generally free of light-emitting compounds.
In another embodiment, it may be provided that the group L 1 comprises an electron-transporting group, preferably a pyrimidine and/or triazine group, particularly preferably a triazine group.
In another embodiment, it may be provided that the group Ar comprises an electron-transporting group, preferably a pyrimidine and/or triazine group, particularly preferably a triazine group.
Compounds in which the groups L 1 and/or Ar contain electron-transporting groups are particularly suitable as host materials for use in combination with luminescent compounds.
In a further preferred embodiment, it can be provided that the compounds according to the invention comprise the structures of the formulae (II-1) to (II-62), wherein the compounds according to the invention can particularly preferably be selected from the compounds of the formulae (II-2) to (II-62),
Wherein the symbols R, R a、Rb、Rc and R d have the meanings described above in particular for formula (I), and the following holds for the other symbols:
For the case where one group is bound to the structure, X, identically or differently at each occurrence, represents N, CR or C, preferably CR or C;
For the case where one group is bound to the structure, X 1, identically or differently at each occurrence, represents N, CR d or C, preferably CR d or C;
Y represents O, S, NR or C (R) 2, preferably O, NR or C (R) 2, and
Y 1 represents O, S, BR d、NRd、Si(Rd)2 or C (R d)2, preferably O, NR d or C (R d)2).
Here, the structures/compounds of the formulae (II-1) to (II-24) and (II-50) to (II-53) are preferred, and the structures/compounds of the formulae (II-3) to (II-6), (II-8), (II-15) to (II-18), (II-52) and (II-53) are particularly preferred.
Preferably, in particular in the structures/compounds of the formulae (II-1) to (II-62), it can be provided that up to three, preferably up to two, radicals X per ring represent N, preferably all X represent CR, preferably at least one, particularly preferably at least two, of the radicals X per ring are selected from C-H and C-D.
Furthermore, in particular in the structures/compounds of the formulae (II-1) to (II-62), it can be provided that no more than four, preferably no more than two, groups X represent N, particularly preferably all groups X represent CR, with groups CR represented by preferably up to 4, particularly preferably up to 3, particularly preferably up to 2X not being equal to the group CH.
In another embodiment, in particular in the structures/compounds of the formulae (II-1) to (II-62), it can be provided that up to three, preferably up to two, radicals X 1 per ring represent N, preferably all X 1 represent CR d, preferably at least one, particularly preferably at least two, radicals X 1 per ring are selected from C-H and C-D.
In a further preferred embodiment, in particular in the structures/compounds of the formulae (II-1) to (II-62), it can be provided that no more than four, preferably no more than two, groups X 1 represent N, particularly preferably all groups X 1 represent CR, with preferably up to 4, particularly preferably up to 3, particularly preferably up to 2 groups CR represented by X 1 not being equal to the group CH.
In a further preferred embodiment, it can be provided that the compounds according to the invention comprise structures of the formulae (III-1) to (III-62), wherein the compounds according to the invention can particularly preferably be selected from the compounds of the formulae (III-1) to (III-62),
Wherein the symbols R, R a、Rb、Rc and R d have the meanings described above in particular for formula (I), the following holds for the other symbols:
Y is O, S, NR or C (R) 2, preferably O, NR or C (R) 2;
Y 1 represents O, S, BR d、NRd or C (R d)2, preferably O, NR d or C (R d)2;
n is independently at each occurrence 0,1, 2 or 3, preferably 0,1 or 2;
m is independently at each occurrence 0, 1,2,3 or 4, preferably 0, 1 or 2;
l is independently at each occurrence 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2.
Here, the structures/compounds of the formulae (III-1) to (III-24) and (III-50) to (III-53) are preferred, and the structures/compounds of the formulae (III-3) to (III-6), (III-8), (III-15) to (III-18), (III-52) and (III-53) are particularly preferred.
In particular, in the structures/compounds of the formulae (III-1) to (III-62), the sum of the indices l, m and n can be defined as up to 10, preferably up to 8, particularly preferably up to 6, particularly preferably up to 4.
In a preferred embodiment, it may be provided that residue R, R a、Rc、Rd does not include an aromatic or heteroaromatic ring system having three linearly fused aromatic six-membered rings, wherein preferably none of residues R, R a、Rc、Rd includes an aromatic or heteroaromatic ring system having three linearly fused aromatic six-membered rings.
It is particularly preferred that residue R, R a、Rc、Rd not include an aromatic or heteroaromatic ring system having three aromatic six-membered rings fused to each other, wherein preferably none of residues R, R a、Rc、Rd includes an aromatic or heteroaromatic ring system having three aromatic six-membered rings fused to each other.
Furthermore, it may be provided that the radical L1 does not comprise an aromatic or heteroaromatic ring system having three aromatic six-membered rings fused to one another.
Furthermore, it may be provided that the group Ar does not comprise an aromatic or heteroaromatic ring system having three aromatic six-membered rings fused to one another.
It is particularly preferred that the compounds may be specified to exclude aromatic or heteroaromatic ring systems having three aromatic six-membered rings fused to one another.
In a preferred development of the invention, it can be provided that at least two preferably adjacent residues R, R d form a fused ring with the other groups to which the two residues R, R d are bound, wherein the two residues R, R d form at least one structure of the formulae (RA-1) to (RA-12),
Wherein R 1 has the meaning described above, the dashed bond represents the binding site on the atom of the group to which the two residues R, R d are bound, and the other symbols have the following meanings:
Y 3 is identically or differently at each occurrence C(R1)2、(R1)2C-C(R1)2、(R1)C＝C(R1)、NR1、NAr'、O or S, preferably C (R 1)2、(R1)2C-C(R1)2、(R1)C＝C(R1), O or S;
R f is in each case identical or different F, straight-chain alkyl, alkoxy or thioalkoxy having 1 to 40 carbon atoms, or alkenyl or alkynyl having 2 to 40 carbon atoms, or branched or cyclic alkyl, alkoxy or thioalkoxy having 3 to 20 carbon atoms, where alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl, respectively, can be substituted by one or more residues R 2, where one or more non-adjacent CH 2 groups can be replaced by R2C＝CR2、C≡C、Si(R2)2、C＝O、C＝S、C＝Se、C＝NR2、C(＝O)O、C(＝O)NR2-、NR2、P(＝O)(R2)、-O-、S、SO or SO 2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, respectively, which can be substituted by one or more residues R 2, or aryloxy or heteroaryloxy having 5 to 60 aromatic ring atoms, which can be substituted by one or more residues R 2, where two residues R f can also form a ring system with each other, or one residue R f can form a ring system with one residue R 1 or with another, where R 2 has the meaning as set forth in claim 1;
r is 0,1, 2,3 or 4, preferably 0,1 or 2, particularly preferably 0 or 1;
s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2;
t is 0, 1, 2,3, 4, 5, 6, 7 or 8, preferably 0, 1, 2,3 or 4, particularly preferably 0, 1 or 2;
v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2.
Here, the structures of the formulae RA-1, RA-3, RA-4 and RA-5 are preferred, and the structures of the formulae RA-4 and RA-5 are particularly preferred.
In a preferred embodiment of the invention, preferably at least two preferably adjacent residues R, R d form a fused ring with the other groups to which the two residues R, R d are bound, wherein the two residues R, R d form the structures of formulae (RA-1 a) to (RA-4 f),
Wherein the dashed bond represents the binding position on the atom of the group to which the two residues R, R d are bound, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the symbols R 1、R2、Rf and the indices s and t have the meanings described previously in particular for the formulae (I) and/or (RA-1) to (RA-12).
Preferred herein are structures of formula RA-4 f.
It can furthermore be provided that at least two residues R, R d forming the structures of the formulae (RA-1) to (RA-12) and/or (RA-1 a) to (RA-4 f) and forming a fused ring represent residues R and R d from the adjacent group X, X 1 or represent residues R, R d, respectively, bound to adjacent carbon atoms, wherein these carbon atoms are preferably linked by a bond.
In another preferred embodiment, at least two preferably adjacent residues R, R d form a fused ring with the other groups to which the two residues R, R d are attached, wherein the two residues R, R d form the structure of formula (RB),
Wherein R 1 has the meaning described above, in particular for formula (I), the dashed bond represents the binding site at which two residues R, R d are bound, the index m is 0, 1,2, 3 or 4, preferably 0, 1 or 2, Y 4 is C (R 1)2、NR1、NAr'、BR1, BAr ', O or S, preferably C (R 1)2, NAr ' or O, particularly preferably C (R 1)2 or O, wherein Ar ' has the meaning described above, in particular for formula (I)).
It can furthermore be provided that at least two residues R, R d forming the structure of formula (RB) and forming a fused ring represent residues R, R d from adjacent groups X, X 1 or represent residues R, R d each bound to an adjacent carbon atom, wherein these carbon atoms are preferably linked by a bond.
In particular, it can be provided that in the preferred structures/compounds the sum of indices r, s, t, v, m and n is preferably 0, 1,2 or 3, particularly preferably 1 or 2.
It is particularly preferred that the compound comprises at least one structure of the formulae (IV-1) to (IV-10), it is particularly preferred that the compound is selected from the group consisting of compounds of the formulae (IV-1) to (IV-10), wherein the compound has at least one fused ring,
Wherein the symbols R, R a、Rb、Rc and R d have the meanings described above in particular for formula (I), the symbol o represents the fused position of at least one fused ring, and the following holds for the other indices used:
i is independently at each occurrence 0, 1 or 2, preferably 0 or 1;
n is independently at each occurrence 0,1, 2 or 3, preferably 0,1 or 2;
m is independently at each occurrence 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and
L is independently at each occurrence 0,1, 2,3, 4 or 5, preferably 0,1 or 2.
In particular, in the structures/compounds of the formulae (IV-1) to (IV-10), it can be provided that the sum of the indices i, n, m and l is up to 10, preferably up to 8, particularly preferably up to 6, particularly preferably up to 4.
In addition, particularly for the structures/compounds of the formulae (IV-1) to (IV-10), it may be specified that the condensed rings are formed by the structures of the formulae (RA-1) to (RA-12), (RA-1 a) to (RA-4 f) and/or (RB) shown above, preferably by the structures of the formulae (RA-1) to (RA-12) and/or (RA-1 a) to (RA-4 f).
Preferably, it may be provided that the compound has at least two condensed rings, wherein at least one condensed ring is formed by the structures of formulae (RA-1) to (RA-12) and/or (RA-1 a) to (RA-4 f), and the other ring is formed by the structures of formulae (RA-1) to (RA-12), (RA-1 a) to (RA-4 f), or (RB).
It may furthermore be provided that the substituents R, R c、Rd、Re and R 1 according to the above formula do not form a fused aromatic or heteroaromatic ring system with the ring atoms of the ring system to which the substituents R, R c、Rd、Re and R 1 are bonded. This includes the formation of fused aromatic or heteroaromatic ring systems with possible substituents R 1 and R 2, which may be combined with substituents R, R c、Rd、Re and R 1.
Residue R a、Rb、Rc preferably forms no ring system with other groups. If the substituents R a form a ring system with one another, the ring is preferably formed from exactly two residues R a bound to a carbon atom.
If the compounds according to the invention are substituted by aromatic or heteroaromatic groups R, R c、Rd、Re、R1 or R 2, it is preferred that they do not have aryl or heteroaryl groups with more than two aromatic six-membered rings directly fused to one another. It is particularly preferred that the substituents do not have aryl or heteroaryl groups at all with six-membered rings directly fused to each other. This preference is due to the low triplet energy of this structure. Also suitable according to the invention are fused aryl groups having more than two aromatic six-membered rings directly fused to each other are phenanthrene and benzophenanthrene, since they also have a high triplet energy level.
It may furthermore be provided that residues R, R c、Rd、Re、R1 or R 2 do not comprise an aromatic or heteroaromatic ring system with three linearly fused aromatic six-membered rings, wherein preferably none of residues R comprises an aromatic or heteroaromatic ring system with 3 linearly fused aromatic six-membered rings.
Preferably, the group Z a、L1-N(Ar)2、L1 Q may form a continuous conjugate with the group Z a、L1-N(Ar)2、L1 Q according to formula (I) or the group to which the preferred embodiment of this formula is attached. Once a direct bond is formed between adjacent aromatic or heteroaromatic rings, continuous conjugation of the aromatic or heteroaromatic system is formed. Further linking between the conjugated groups mentioned above, for example by S-, N-or O-atoms or carbonyl groups, does not impair conjugation.
It may furthermore be provided that the substituents R, R c、Rd、Re and R 1 according to the above formula do not form a fused aromatic or heteroaromatic ring system, preferably do not form a fused ring system, with the ring atoms of the ring system. This includes the formation of a fused ring system with possible substituents R 1 and R 2, which may be combined with residue R, R c、Rd、Re、R1.
If in particular the two residues which can be selected from R, R c、Rd、Re、R1 and/or R 2 form a ring system with one another, it can be a monocyclic or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic ring. Here, the residues forming a ring system with each other may be adjacent, i.e. they are bound to the same carbon atom or to carbon atoms directly bound to each other, or they may be further apart from each other. Furthermore, the ring systems having substituents R, R d、Re、R1 and/or R 2 can also be linked to one another via bonds, so that ring formation can thereby be achieved.
It may furthermore be provided that at least one residue R, R d、Re is selected identically or differently on each occurrence from the group consisting of branched or cyclic alkyl, alkoxy or thioalkoxy groups having 3 to 20 carbon atoms or aromatic or heteroaromatic ring systems selected from the formulae Ar-1 to Ar-76, preferably that the substituents R, R d、Re either form fused rings, preferably fused rings according to the structure of the formulae (RA-1) to (RA-12) or (RB), or that the substituents R, R d、Re are identically or differently on each occurrence from the group consisting of aromatic or heteroaromatic ring systems selected from the formulae Ar-1 to Ar-76 and/or the groups Ar' are identically or differently selected on each occurrence from the groups of the formulae Ar-1 to Ar-76,
Wherein R 1 has the above-mentioned meaning, the dotted bond represents the connection on the corresponding group, and the following holds true:
Ar 1 is, identically or differently on each occurrence, a divalent aromatic or heteroaromatic ring system having from 6 to 18 aromatic ring atoms, each of which may be substituted by one or more residues R 1;
a is, identically or differently, C (R 1)2、NR1, O, or S;
p is 0 or 1, wherein p=0 means that the group Ar 1 is absent and the corresponding aromatic or heteroaromatic group is directly bound to the corresponding residue;
q is 0 or 1, where q=0 means that no group a is bound at this position, but instead the residue R 1 is bound to the corresponding carbon atom.
The previously described structures of the formulae (Ar-1) to (Ar-76) represent preferred designs of the residue Ar, for example the residue Ar defined in the structure of the formula (I), wherein in this case the substituents R 1 of the formulae (Ar-1) to (Ar-76) are to be replaced by R d, wherein R d has the meaning described above in particular for the formula (I).
The above-described structures of the formulae (Ar-1) to (Ar-76) represent a preferred design of the residue L 1, as defined for the structure of the formula (I) L 1, wherein in this case the substituents R 1 of the formulae (Ar-1) to (Ar-76) are to be replaced by R, wherein R has the meanings described above in particular for the formula (I). In addition, residue L 1 includes another binding position.
Here, the structure of formula (Ar-1)、(Ar-2)、(Ar-3)、(Ar-12)、(Ar-13)、(Ar-14)、(Ar-15)、(Ar-16)、(Ar-40)、(Ar-41)、(Ar-42)、(Ar-43)、(Ar-44)、(Ar-45)、(Ar-46)、(Ar-69)、(Ar-70)、(Ar-76) is preferable, and the structures of formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16) are particularly preferable.
If the abovementioned radicals of the structures of the formulae (Ar-1) to (Ar-76) have a plurality of radicals A, all combinations of the definitions of A are considered for this purpose. A preferred embodiment is one in which one group A represents NR 1 and the other group A represents C (R 1)2, or in which both groups A represent NR 1 or in which both groups A represent O.
If A represents NR 1, the substituent R 1 bound to the nitrogen atom preferably represents an aromatic or heteroaromatic ring system having from 5 to 24 aromatic ring atoms, which may also be substituted by one or more residues R 2. In a particularly preferred embodiment, the substituents R 1, identically or differently on each occurrence, represent an aromatic or heteroaromatic ring system having from 6 to 24, in particular from 6 to 18, aromatic ring atoms, which does not have a fused aryl and fused heteroaryl group in which two or more aromatic or heteroaromatic six-membered ring groups are directly fused to one another, and which in each case can also be substituted by one or more residues R 2. Preferred are phenyl, biphenyl, terphenyl and tetrabiphenyl. Also preferred are triazines, pyrimidines and quinazolines, as set forth above for Ar-47 to Ar-50, ar-57 and Ar-58, wherein these structures may be substituted with one or more residues R 2 instead of residue R 1.
If A represents C (R 1)2, the substituents R 1 bound to this carbon atom preferably represent, identically or differently on each occurrence, a linear alkyl radical having from 1 to 10 carbon atoms, or a branched or cyclic alkyl radical having from 3 to 10 carbon atoms, or an aromatic or heteroaromatic ring system having from 5 to 24 aromatic ring atoms, which may also be substituted by one or more residues R 2, it is particularly preferred that R 1 represents methyl or phenyl, where residues R 1 may also form a ring system with one another, which gives a spiro ring system.
Preferred substituents R, R a、Rb、Rc、Rd、Re and R f are described below.
It may be preferably provided that, for the symbols used in particular in the formulae (I), (I-1) to (I-4) and the like, the following holds:
R, R c、Rd is identical or different on each occurrence H、D、N(Ar')2、N(R1)2、C(Ar')3、C(R1)3、Si(Ar')3、Si(R1)3、B(Ar')2、B(R1)2、 is a straight-chain alkyl radical having from 1 to 40 carbon atoms or a branched or cyclic alkyl radical having from 3 to 20 carbon atoms, where the alkyl radical may each be substituted by one or more residues R 1, where one or more non-adjacent CH 2 groups may be replaced by R1C＝CR1、C≡C、Si(R1)2、C＝O、C＝S、C＝Se、C＝NR1、C(＝O)O、C(＝O)NR1-、NR1、P(＝O)(R1)、SO or SO 2, or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, which may each be substituted by one or more residues R 1, where two residues R, R d may also form a ring system with one another or one residue R, R d may form a ring system with another group, in particular with residue R c.
In a preferred embodiment of the invention R, R d、Re is selected identically or differently on each occurrence from H, D, F, CN, NO 2、Si(R1)3、B(OR1)2, straight-chain alkyl having 1 to 20 carbon atoms or branched or cyclic alkyl having 3 to 20 carbon atoms, where the alkyl radical may each be substituted by one or more residues R 1, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may each be substituted by one or more residues R 1.
In a further preferred embodiment of the invention, the substituents R, R d、Re are selected identically or differently on each occurrence from H, D, F, straight-chain alkyl having 1 to 20 carbon atoms or branched or cyclic alkyl having 3 to 20 carbon atoms, where the alkyl radical may each be substituted by one or more residues R 1, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may each be substituted by one or more residues R 1.
It may furthermore be provided that at least one residue R, R d、Re, preferably the substituent R, R d、Re, is selected identically or differently on each occurrence from H, D, an aromatic or heteroaromatic ring system having from 6 to 30 aromatic ring atoms, which may be substituted by one or more residues R 1, or a group N (Ar') 2, particularly preferably at least one substituent R, R d、Re is selected identically or differently on each occurrence from aromatic or heteroaromatic ring systems having from 6 to 30 aromatic ring atoms, which may be substituted by one or more residues R 1, or the group N (Ar') 2. It is particularly preferred that at least one substituent R, R d、Re is selected identically or differently on each occurrence from an aromatic or heteroaromatic ring system having from 6 to 30 aromatic ring atoms, which may be substituted by one or more residues R 1. In a further preferred embodiment of the invention, either the substituents R, R d、Re form a ring according to the structure of formulae (RA-1) to (RA-12), (RA-1 a) to (RA-4 f) or (RB), or the substituents R, R d、Re are selected identically or differently on each occurrence from H, D, aromatic or heteroaromatic ring systems having from 6 to 30 aromatic ring atoms, which may be substituted by one or more residues R 1, or the group N (Ar') 2. Particularly preferred is that residue R, R d、Re, preferably substituent R, R d、Re, is selected identically or differently on each occurrence from H or an aromatic or heteroaromatic ring system having from 6 to 24 aromatic ring atoms, preferably from 6 to 18 aromatic ring atoms, particularly preferably from 6 to 13 aromatic ring atoms, which in each case may be substituted by one or more residues R 1.
It may furthermore be provided that at least one residue R, R d、Re represents an aromatic or heteroaromatic ring system having 5 to 13 aromatic ring atoms, which may be substituted by one or more residues R 1.
Preferably, it may be provided that at least one residue, preferably the substituent R, R d、Re, is selected from phenyl, biphenyl, terphenyl, tetrabiphenyl, fluorenyl, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which may be substituted with one or more residues R 1. The term "substituent" as used herein means that R is not H. In addition, if two or more groups selected from the above aromatic or heteroaromatic groups are present, the substituents R may be the same or different.
It may furthermore be provided that the radicals R a bound to one carbon atom are identical.
It may furthermore be provided that the radicals R a bound to different carbon atoms are identical.
It is furthermore possible to provide that the radicals R a bound to different carbon atoms are different.
It may be provided that the radical R a bound to a carbon atom may be selected from linear alkyl radicals having 1 to 10 carbon atoms or branched or cyclic alkyl radicals having 3 to 10 carbon atoms, which may each be substituted, preferably deuterated, by one or more residues R 2, wherein two or more preferably adjacent substituents R a may form a ring system with each other. If adjacent substituents R a form a ring system with one another, the ring is preferably formed from two residues R a.
It may furthermore preferably be provided that the radical R a bound to a carbon atom is selected from aromatic or heteroaromatic ring systems having from 5 to 20 aromatic ring atoms, which in each case may be substituted by one or more residues R 2, preferably represents phenyl, which in each case may be substituted by one or more residues R 2, preferably deuterated, wherein two or more preferably adjacent substituents R a may form a ring system with one another. If adjacent substituents R a form a ring system with one another, this ring is preferably formed by exactly two residues R a.
Preferably, it can be provided that the radical R a represents methyl, ethyl, propyl, phenyl, or two radicals R a bound to the same carbon atom form a cycloalkyl residue having 5 or 6, preferably 5 carbon atoms, where the radical R a preferably represents methyl, where these radicals can be deuterated.
Preferably, it can be provided that the radical R b represents methyl, ethyl, propyl or two radicals R b bound to the same carbon atom form a cycloalkyl radical having 5 or 6, preferably 5, carbon atoms, where the radical R b preferably represents H, D, methyl, ethyl, propyl, where these radicals can be deuterated, where the radical R b particularly preferably represents H or D.
Preferably, it may be provided that the group R c represents H, D, methyl, ethyl, propyl, wherein these groups may be deuterated, wherein the group R c preferably represents H or D.
In a preferred embodiment of the invention, R f is selected identically or differently on each occurrence from a linear alkyl radical having from 1 to 20 carbon atoms or a branched or cyclic alkyl radical having from 3 to 20 carbon atoms, where the alkyl radical may each be substituted by one or more residues R 1, or an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, preferably from 5 to 40 aromatic ring atoms, which may each be substituted by one or more residues R 2.
In another preferred embodiment of the invention, R f is selected identically or differently on each occurrence from a straight-chain alkyl radical having from 1 to 10 carbon atoms or a branched or cyclic alkyl radical having from 3 to 10 carbon atoms, where the alkyl radical may each be substituted by one or more residues R 2, an aromatic or heteroaromatic ring system having from 6 to 30 aromatic ring atoms, which may be substituted by one or more residues R 2. It is particularly preferred that R f is selected identically or differently on each occurrence from a linear alkyl radical having from 1 to 5 carbon atoms or a branched or cyclic alkyl radical having from 3 to 5 carbon atoms, where the alkyl radical may each be substituted by one or more residues R 2, or an aromatic or heteroaromatic ring system having from 6 to 24 aromatic ring atoms, preferably having from 6 to 18 aromatic ring atoms, particularly preferably having from 6 to 13 aromatic ring atoms, which may each be substituted by one or more residues R 2.
In a preferred embodiment of the invention, R f is selected identically or differently on each occurrence from a linear alkyl radical having from 1 to 6 carbon atoms or a cyclic alkyl radical having from 3 to 6 carbon atoms, where the alkyl radical may each be substituted by one or more residues R 2, or an aromatic or heteroaromatic ring system having from 6 to 24 aromatic ring atoms, which may each be substituted by one or more residues R 2, where the two residues R f may also form a ring system with one another. It is particularly preferred that R f is selected identically or differently on each occurrence from a linear alkyl radical having 1,2,3 or 4 carbon atoms or a branched or cyclic alkyl radical having 3 to 6 carbon atoms, where the alkyl radical may each be substituted by one or more residues R 2, but preferably is unsubstituted, or an aromatic ring system having 6 to 12 aromatic ring atoms, in particular having 6 aromatic ring atoms, which may each be substituted by one or more preferably non-aromatic residues R 2, but preferably is unsubstituted, where two residues R f may each form a ring system with one another. It is particularly preferred that R f is, identically or differently, selected at each occurrence from straight-chain alkyl having 1,2,3 or 4 carbon atoms or branched alkyl having 3 to 6 carbon atoms. It is particularly preferred that R f represents methyl or represents phenyl, wherein two phenyl groups may together form a ring system, wherein methyl is more preferred than phenyl.
Preferred aromatic or heteroaromatic ring systems represented by substituents R, R c、Rd、Re、Rf or Ar' are selected from phenyl, biphenyl (in particular ortho-, meta-or para-biphenyl), terphenyl (in particular ortho-, meta-, para-or branched terphenyl), tetrabiphenyl, fluorene (which may be linked via the 1-, 2-, 3-or 4-position), spirobifluorene (which may be linked via the 1-, 2-, 3-or 4-position), naphthalene (in particular 1-or 2-linked naphthalene), indole, benzofuran, benzothiophene, carbazole (which may be linked via the 1-, 2-, 3-or 4-position), dibenzofuran (which may be linked via the 1-, 2-, 3-or 4-position), dibenzothiophene (which may be linked via the 1-, 2-, 3-or 4-position), indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, anthracene, pyrene, perylene,Phenanthrene or triphenylene, which may be substituted with one or more residues R, R 1 or R 2, respectively. Particularly preferred are structures Ar-1 through Ar-76 listed above, with structures of formula (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), (Ar-76), and structures of formula (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) being particularly preferred. It should be noted with respect to the structures Ar-1 to Ar-76 that they are represented by the substituent R 1. These substituents R 1 are substituted by R in the case of the ring system Ar and R 1 by R 2 in the case of R f.
Other suitable groups R, R d、Re are groups of the formula Ar 4-N(Ar2)(Ar3) in which Ar 2、Ar3 and Ar 4, identically or differently at each occurrence, represent an aromatic or heteroaromatic ring system having from 5 to 24 aromatic ring atoms, each of which may be substituted by one or more residues R 1. Here, the total number of aromatic ring atoms of Ar 2、Ar3 and Ar 4 is at most 60, preferably at most 40.
Here, ar 4 and Ar 2 may be connected to each other and/or Ar 2 and Ar 3 may be connected to each other through a group selected from C (R 1)2、NR1, O or S), preferably, the connection of Ar 4 and Ar 2 to each other or Ar 2 and Ar 3 to each other, respectively, is carried out ortho to the connection position of the nitrogen atom, neither group Ar 2、Ar3 nor Ar 4 is attached to each other.
Ar 4 is preferably an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, which may each be substituted by one or more residues R 1. It is particularly preferred that Ar 4 is selected from ortho, meta or para phenylene or ortho, para or meta biphenyl, which may each be substituted by one or more residues R 1, but is preferably unsubstituted. It is particularly preferred that Ar 4 is unsubstituted phenylene.
Preferably, ar 2 and Ar 3 are, identically or differently, in each case, an aromatic or heteroaromatic ring system having from 6 to 24 aromatic ring atoms, which in each case may be substituted by one or more residues R 1. Particularly preferred groups Ar 2 or Ar 3 are selected identically or differently on each occurrence from benzene, ortho-, meta-, para-, or branched terphenyl, ortho-, meta-, para-, or branched tetrabiphenyl, 1-, 2-, 3-, or 4-fluorenyl, 1-, 2-, 3-, or 4-spirobifluorenyl, 1-or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-, 3-, or 4-carbazole, 1-, 2-, 3-, or 4-dibenzofuran, 1-, 2-, 3-, or 4-dibenzothiophene, indenocarbazole, indolocarbazole, 2-, 3-, or 4-pyridine, 2-, 4-, or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene, or triphenylene, respectively, which may be substituted by one or more residues R 1. It is particularly preferred that Ar 2 and Ar 3 are selected identically or differently on each occurrence from benzene, biphenyl (especially ortho-, meta-or para-biphenyl), terphenyl (especially ortho-, meta-, para-or branched terphenyl), tetrabiphenyl (especially ortho-, meta-, para-or branched tetrabiphenyl), fluorene (especially 1-, 2-, 3-or 4-fluorene) or spirobifluorene (especially 1-, 2-, 3-or 4-spirobifluorene).
In another preferred embodiment of the invention, R 1 is selected identically or differently on each occurrence from H, D, F, CN, straight-chain alkyl having 1 to 10 carbon atoms or branched or cyclic alkyl having 3 to 10 carbon atoms, where the alkyl radical may each be substituted by one or more residues R 2, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may each be substituted by one or more residues R 2. In a particularly preferred embodiment of the invention, R 1 is selected identically or differently on each occurrence from H, straight-chain alkyl having 1 to 6 carbon atoms, in particular straight-chain alkyl having 1, 2, 3 or 4 carbon atoms, or branched or cyclic alkyl having 3 to 6 carbon atoms, where the alkyl may be substituted by one or more residues R 2, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, which may each be substituted by one or more residues R 5, but is preferably unsubstituted.
In another preferred embodiment of the invention, R 2 is, identically or differently on each occurrence, H, alkyl of 1 to 4 carbon atoms or aryl of 6 to 10 carbon atoms, which may be substituted by alkyl having 1 to 4 carbon atoms, but is preferably unsubstituted.
In the compounds according to the invention which are processed by vacuum evaporation, the alkyl groups preferably have not more than 5 carbon atoms, particularly preferably not more than 4 carbon atoms, particularly preferably not more than 1 carbon atom. Also suitable for compounds processed from solution are compounds substituted with alkyl groups of up to 10 carbon atoms, in particular branched alkyl groups, or with oligoarylene groups, for example ortho, meta, para or branched terphenyl or tetrabiphenyl groups.
If a compound of formula (I) or a preferred embodiment is used as host material for phosphorescent emitters or in a layer directly adjacent to a phosphorescent layer, it is further preferred that the compound does not contain a fused aryl or heteroaryl group in which more than two six-membered rings are directly fused to each other. One exception is phenanthrene and triphenylene, which, despite the presence of fused aromatic six-membered rings, may be preferred due to their high triplet energy.
It can furthermore be provided that the compound comprises exactly two or exactly three structures according to formula (I).
In a preferred embodiment, the compound is selected from the group consisting of compounds of formula (D-1),
Wherein the radical L 2 represents a linking group, preferably a bond, or an aromatic or heteroaromatic ring system having from 5 to 40, preferably from 5 to 30, aromatic ring atoms, which may be substituted by one or more residues R, and the other symbols and indices used have the meanings indicated in claim 1, wherein the radical L 2, instead of a hydrogen atom or a substituent, forms a bond to the basic structure, preferably the radical L 2 is bonded to the residue L 1、Ar、Za.
In a further preferred embodiment of the invention L 2 represents a bond or an aromatic or heteroaromatic ring system having from 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having from 6 to 12 carbon atoms, which may be substituted by one or more residues R, but is preferably unsubstituted, wherein R may have the meaning described above in particular for formula (I), particularly preferably L 2 represents an aromatic ring system having from 6 to 10 aromatic ring atoms or a heteroaromatic ring system having from 6 to 13 heteroaromatic ring atoms, which may each be substituted by one or more residues R 1, but is preferably unsubstituted, wherein R 1 may have the meaning described above in particular for formula (I).
It is further preferred that the symbol L 2 shown in formula (D1), in particular, represents identically or differently on each occurrence a bond or an aryl or heteroaryl residue having from 5 to 24 ring atoms, preferably from 6 to 13 ring atoms, particularly preferably from 6 to 10 ring atoms, so that the aromatic or heteroaromatic group in the aromatic or heteroaromatic ring system is bonded directly to the corresponding atom of the other group, i.e. via an atom of the aromatic or heteroaromatic group.
It may furthermore be provided that the radical L 2 represented by the formula (D1) comprises an aromatic ring system having up to four, preferably up to three, particularly preferably up to two fused aromatic and/or heteroaromatic six-membered rings, preferably no fused aromatic or heteroaromatic ring system. Therefore, a naphthyl structure is preferable to an anthracene structure. Furthermore, fluorenyl, spirobifluorenyl, dibenzofuranyl and/or dibenzothiophenyl structures are preferred over naphthyl structures.
Particularly preferably not having a condensed structure, such as phenyl, biphenyl, terphenyl and/or tetrabiphenyl structures.
Examples of suitable aromatic or heteroaromatic ring systems L 2 are selected from the group consisting of ortho-, meta-or para-phenylene, ortho-, meta-or para-biphenylene, terphenylene, in particular branched terphenylene, tetraphenylene, in particular branched tetraphenylene, fluorenylene, spirobifluorenylene, dibenzofuranylene, dibenzothiophenylene and carbazolylene, which may each be substituted by one or more residues R 1, but are preferably unsubstituted.
According to a preferred embodiment, the compounds according to the invention can be represented by at least one of the structures according to formulae (I), (I-1) to (I-4), (II-1) to (II-62), (III-1) to (III-62) and/or (IV-1) to (IV-10). Preferably, the compounds according to the invention, preferably comprising structures according to formulae (I), (I-1) to (I-4), (II-1) to (II-62), (III-1) to (III-62) and/or (IV-1) to (IV-10), have a molecular weight of less than or equal to 5000g/mol, preferably less than or equal to 4000g/mol, particularly preferably less than or equal to 3000g/mol, particularly preferably less than or equal to 2000g/mol, more preferably less than or equal to 1200g/mol, particularly preferably less than or equal to 900 g/mol.
Furthermore, preferred compounds according to the invention are characterized in that they are sublimable. These compounds generally have a molar mass of less than about 1200 g/mol.
Preferably, it may be provided that the compound does not include an alkoxy, thioalkoxy or hydroxy group.
In another preferred embodiment, it may be provided that the compound does not comprise a cyclobutyl residue having two oxygen atoms bonded thereto.
Preferably, it may also be provided that the compound does not contain thiadiazine groups.
Compounds may also be specified:
Is not protected.
It may furthermore be provided that the ratio of hole-transporting groups, preferably N (Ar) 2 groups, to phenyl groups fused to two cyclopentyl residues is at least 0.6, preferably at least 0.8, particularly preferably at least 0.9.
It may furthermore be provided that the ratio of hole-transporting groups, preferably N (Ar) 2 groups, to phenyl groups condensed on the two cyclopentyl residues is up to 10, preferably up to 4, particularly preferably up to 1.5.
Hole transport groups are well known in the art. It includes especially diarylamine and triarylamine groups, carbazole groups and groups having similar properties.
It can also be provided that the compound comprising the structure according to formula (I), preferably the compound according to formula (I) or a preferred embodiment of the structure/compound is not in direct contact with a metal atom, preferably does not constitute a ligand of a metal complex.
The above preferred embodiments may be combined with each other in any desired manner within the limits defined in claim 1. In a particularly preferred embodiment of the invention, the above-described preferences occur simultaneously.
Examples of preferred compounds according to the above embodiments are the compounds listed in the following table.
The basic structure of the compounds according to the invention can be represented in the manner outlined in the schemes below. The individual synthesis steps, for example coupling reactions to give C-C linkages and/or C-N linkages, are known in principle to the person skilled in the art. It includes, inter alia, BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA and HIYAMA reactions.
Further information about the synthesis of the compounds according to the invention can be obtained from the synthesis examples.
The following schemes describe the representation of compounds according to the invention by using an explicit phenyl compound to which one cyclopentyl, preferably two cyclopentyl, are fused. The use is to be understood as exemplary, and thus other compounds according to the invention can be obtained by analogous synthetic routes, starting from other basic structures.
The synthesis of phenyl compounds on which cyclopentyl, preferably both cyclopentyl, are condensed is well known in the art. Many of these compounds are commercially available. For example, it includes the compounds mentioned in the synthesis examples.
The compounds according to the invention having an amine group, in particular compounds comprising a structure according to formula (I), can be obtained starting from the phenyl compound (1) on which cyclopentyl, preferably two cyclopentyl, are condensed, by the following synthetic route:
1) organocupric chloride (3) was obtained by lithiation (2) with transition metallization of cupric chloride (I) according to M.Oi et al, chem. Sci.,2019,10,6107, followed by oxygen-mediated C-N coupling with lithium diarylamino LiNAr according to H.Yamamoto et al, J.org. chem.,1980,45,2739:
2) Organo-cupric chloride (3) is obtained by lithiation (2), transition metallization with cupric chloride (I) according to m.oi et al, chem. Sci.,2019,10,6107, followed by palladium-phosphine mediated C-C coupling with bromo or iodo-arylamine or carbazole X-Ar-NAr 2:
If the radical X on the phenyl compound (1) on which cyclopentyl, preferably both cyclopentyl, are condensed is a bromine atom of (1), the reaction sequence 1) or 2) can be repeated successively in order to obtain compounds according to the invention which are symmetrically or asymmetrically disubstituted with NAr 2 or-Ar-NAr 2 groups.
Schemes (1) and (2) should be understood as exemplary, and thus other groups X are also suitable, as shown in the examples.
The meaning of the symbols used in the above schemes essentially corresponds to that defined for formula (I), wherein the numbers and complete representations of all symbols are omitted for clarity.
Thus, a further object of the present invention is a process for the preparation of a compound according to the invention, wherein a phenyl compound to which cyclopentyl groups, preferably two cyclopentyl groups, are fused is synthesized and at least one aromatic or heteroaromatic residue is introduced, preferably by nucleophilic aromatic substitution or coupling reactions.
By this method, optionally followed by purification, such as recrystallisation or sublimation, the compounds according to the invention can be obtained in high purity, preferably greater than 99% (determined by 1 H-NMR and/or HPLC).
The compounds according to the invention may also be mixed with polymers. These compounds can also be covalently incorporated into polymers. This is especially possible for compounds substituted with reactive leaving groups such as bromine, iodine, chlorine, boric acid or borates or compounds substituted with reactive polymerizable groups such as olefins or oxetanes. They can be used as monomers for the production of the corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably carried out here by halogen functions or boric acid functions or by polymerizable groups. The polymers can also be crosslinked by such groups. The compounds and polymers according to the invention can be used as crosslinked or uncrosslinked layers.
Thus, a further subject of the invention is an oligomer, polymer or dendrimer comprising one or more of the above-described structures of formula (I) and preferred embodiments of the formula or a compound according to the invention, wherein one or more bonds are present between the compound according to the invention or the preferred embodiments of the structures of formula (I) and the polymer, oligomer or dendrimer. Thus, according to the linkage of the structure of formula (I) and the preferred embodiment of the formula or compound, they form side chains of the oligomer or polymer, or are linked to the main chain. The polymer, oligomer or dendrimer may be conjugated, partially conjugated or non-conjugated. The oligomer or polymer may be linear, branched or dendritic. The same preferences as described above apply for the repeating units of the compounds according to the invention in oligomers, dendrimers and polymers.
For the preparation of oligomers or polymers, the monomers according to the invention are homo-or copolymerized with other monomers. Preference is given to copolymers in which the units according to formula (I) or the preferred embodiments described above and below are present in an amount of from 0.01 to 99.9 mol%, preferably from 5 to 90 mol%, particularly preferably from 20 to 80 mol%. Suitable and preferred comonomers forming the polymer backbone are selected from fluorene (e.g. according to EP 842208 or WO 2000/022026), spirobifluorene (e.g. according to EP 707020, EP 894107 or WO 2006/061181), p-phenylene (e.g. according to WO 92/18552), carbazole (e.g. according to WO 2004/070772 or WO 2004/113468), thiophene (e.g. according to EP 1028136), dihydrophenanthrene (e.g. according to WO 2005/014689), cis-and trans-indenofluorene (e.g. according to WO 2004/04901 or WO 2004/113412), ketone (e.g. according to WO 2005/040302), phenanthrene (e.g. according to WO 2005/104264 or WO 2007/017066) or a plurality of these units. The polymers, oligomers and dendrimers may also contain other units, such as hole transporting units, in particular hole transporting units based on triarylamines, and/or electron transporting units.
Of particular interest are also the compounds according to the invention which are characterized by a high glass transition temperature. In this connection, particular preference is given to compounds according to the invention comprising structures according to the formula (I) or the preferred embodiments described above and below, which have a glass transition temperature, measured according to DIN 51005 standard (2005-08 edition), of at least 70 ℃, particularly preferably at least 110 ℃, very particularly preferably at least 125 ℃, particularly preferably at least 150 ℃.
For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, formulations of the compounds according to the invention are required. For example, these formulations may be solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents may be preferably used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-, or p-xylene, methylbenzoate, mesitylene, tetrahydronaphthalene, veratrole, tetrahydrofuran, methyltetrahydrofuran, THP, chlorobenzene, dioxane, phenoxytoluene (especially 3-phenoxytoluene), (-) -fenchyl ketone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylbenzene, 3, 5-dimethylbenzene, acetophenone, -terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene ethyl benzoate, indane, NMP, p-isopropylphenyl methane, 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-bis (3, 4-dimethylphenyl) ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptyl benzene, menthyl isovalerate, cyclohexyl hexanoate, or a mixture of these solvents.
Thus, another subject of the invention is a formulation or composition containing at least one compound according to the invention and at least one other compound. The further compound may be, for example, a solvent, in particular one of the solvents mentioned above or a mixture of these solvents. If the additional compound includes a solvent, the mixture is referred to herein as a formulation. However, the further compound may also be at least one further organic or inorganic compound, such as a luminescent compound and/or another host material, which is also used in an electronic device. Preferably, it may be provided that the at least one further compound is selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF, host materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, electron blocking materials and hole blocking materials, preferably host materials.
Another subject of the invention is the use of the compounds according to the invention in electronic devices, in particular in organic electroluminescent devices. Preferably, the compound according to the present invention can be prescribed for use as a host material, a hole transporting material, a hole injecting material, or an electron blocking material in an electronic device.
A further subject of the invention is an electronic device comprising at least one compound according to the invention. An electronic device in the sense of the present invention is a device comprising at least one layer comprising at least one organic compound. The component may also comprise an inorganic material or a layer consisting entirely of an inorganic material.
Particularly preferred are electronic devices selected from the group consisting of organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), preferably Organic Light Emitting Diodes (OLEDs), small molecule based organic light emitting diodes (sOLED), polymer based organic light emitting diodes (PLEDs), light emitting electrochemical cells (LECs), organic Laser diodes (O lasers), "organic plasma emitting devices" (d.m. koller et al, nature Photonics 2008, 1-4), organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O TFTs), organic light emitting transistors (O LETs), organic solar cells (O SCs), organic optical detectors, organic photoreceptors, organic field quench devices (O FQDs) and organic electric sensors, preferably organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), particularly preferred Organic Light Emitting Diodes (OLED), small molecule based organic light emitting diodes (sOLED), polymer based organic light emitting diodes (ed), especially phosphorescent OLEDs.
The organic electroluminescent device comprises a cathode, an anode and at least one light emitting layer. In addition to these layers, it may also comprise further layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, charge blocking layers and/or Charge generation layers (Charge-Generation Layers), respectively. An intermediate layer, for example, having an exciton blocking function, may also be introduced between the two light-emitting layers. It should be noted, however, that not every one of these layers must be present. Here, the organic electroluminescent device may include one light emitting layer, or may include a plurality of light emitting layers. If a plurality of luminescent layers are present, they preferably have a total of a plurality of luminescence maxima between 380nm and 750nm, so that an overall white luminescence is produced, i.e. different luminescent compounds which can fluoresce or phosphoresce are used in the luminescent layers. Particularly preferred are systems with three light-emitting layers, wherein the three layers display blue, green and orange or red light emission. The organic electroluminescent device according to the invention may also be a tandem electroluminescent device, in particular for white-emitting OLEDs.
Depending on the exact structure, the compounds according to the invention can be used in different layers. Preferred are organic electroluminescent devices comprising in the light-emitting layer a compound according to formula (I) or the preferred embodiments described above as phosphorescent light-emitters or as host materials for light-emitters exhibiting TADF (thermally activated delayed fluorescence), in particular phosphorescent light-emitters. Furthermore, the compounds according to the invention can also be used in hole transport layers and/or exciton blocking layers. It is particularly preferred that the compounds according to the invention are used in the light-emitting layer as host material for phosphorescent emitters, in particular for red, orange, blue, green or yellow phosphorescent emitters, preferably for blue or green phosphorescent emitters, as host material, hole-transporting material, hole-injecting material or electron-blocking material.
Preferably, carbazole may be provided in particular as host material. For example, arylamines which do not constitute carbazole represented by the formulas (II-1), (II-3), (II-4) and the like can be preferably used as a hole transporting material, a hole injecting material or an electron blocking material.
Preferably, it may be provided that the organic electroluminescent device comprises at least one light-emitting layer and at least one hole-transporting layer, and that the hole-transporting layer comprises a compound according to the invention.
When the compound according to the application is used as a host material for phosphorescent compounds in the light-emitting layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). Phosphorescence in the sense of the present application refers to luminescence from an excited state having higher spin multiplicity, i.e. spin state >1, especially luminescence from an excited triplet state. For the purposes of the present application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.
The mixture of compounds according to the invention and luminescent compounds contains 99 to 1% by volume, preferably 98 to 10% by volume, particularly preferably 97 to 60% by volume, in particular 95 to 80% by volume, of the compounds according to the invention, relative to the total mixture of the luminophore and matrix material. Thus, the mixture contains from 1 to 99% by volume, preferably from 2 to 90% by volume, particularly preferably from 3 to 40% by volume, in particular from 5 to 20% by volume, of the luminophore relative to the total mixture of luminophore and matrix material.
In one embodiment of the invention, the compounds according to the invention are used here as single matrix materials ("single bodies") for phosphorescent emitters.
Another embodiment of the invention is the use of a compound according to the invention in combination with another host material as a host material for a phosphorescent emitter. Suitable matrix materials which can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004/0130880, WO 2004/093207, WO 2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives, for example CBP (N, N-biscarbazolylbiphenyl), or in WO 2005/039246, US2005/0069729, JP 2004/288381, EP 1205527, WO 2008/086851 or WO 2013/04176, indolocarbazole derivatives, for example according to WO 2007/063254 or WO 2008/056756, indenocarbazole derivatives, for example according to WO 2010/136109, WO 2011/000455, WO 2013/04176 or WO 2013/056776, azocarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005/7160, bipolar matrix materials, for example according to WO 2007/137725, silanes, for example according to WO 2005/111172, azaboroles or boron esters, for example according to WO 2006/1170552, triazine derivatives, for example according to WO 2007/063254, WO 2008/056746, WO 2010/015306, WO 2011/057706, WO 2011/060859 or WO 2011/060877, zinc complexes, for example according to EP 652273 or WO 2009/062578, diazasiloles or tetraazasiloles derivatives, for example according to WO 2010/054729, diazaphosphole derivatives, for example according to WO 2010/054730, bridged carbazole derivatives, for example according to WO 2011/042107, WO 2011/060867, WO 2011/088877 and WO 2012/143080, triphenylene derivatives, for example according to WO 2012/048781, dibenzofuran derivatives, for example according to WO 2015/169412, WO 2016/015810, WO 2016/023608, WO 2017/148564 or WO 2017/148565, or dicarbazole, for example according to JP 3139321B2.
Likewise, another phosphorescent emitter having an emission wavelength shorter than that of the real emitter may be present as a co-host in the mixture. Particularly good results are obtained when a red phosphorescent emitter is used as emitter and a yellow phosphorescent emitter is used as co-host in combination with the compound according to the invention.
Furthermore, compounds that do not participate or do not significantly participate in charge transport (as described, for example, in WO 2010/108579) may be used as co-hosts. In particular, compounds which have a large band gap and do not themselves participate, or at least do not significantly participate, in the charge transport of the light-emitting layer are suitable for incorporation with the compounds according to the invention as co-matrix materials. Such materials are preferably pure hydrocarbons. Examples of such materials are found, for example, in WO 2009/124627 or WO 2010/006680. It should be noted in this connection that the compounds according to the invention without specific functional groups, such as hole-transporting groups and/or electron-transporting groups, have advantageous properties.
Particularly suitable as phosphorescent compounds (=triplet emitters) are compounds which emit light under suitable excitation, preferably in the visible range, and which also contain at least one atom having an atomic number of more than 20, preferably more than 38 and less than 84, particularly preferably more than 56 and less than 80, in particular a metal having such an atomic number. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium are used as phosphorescent emitters, in particular compounds containing iridium or platinum.
Examples of such luminophores can be found in application WO 00/70655、WO 2001/41512、WO 2002/02714、WO 2002/15645、EP 1191613、EP 1191612、EP 1191614、WO 05/033244、WO 05/019373、US2005/0258742、WO 2009/146770、WO 2010/015307、WO 2010/031485、WO 2010/054731、WO 2010/054728、WO 2010/086089、WO 2010/099852、WO 2010/102709、WO 2011/032626、WO 2011/066898、WO 2011/157339、WO 2012/007086、WO 2014/008982、WO 2014/023377、WO 2014/094961、WO 2014/094960、WO 2015/036074、WO 2015/104045、WO 2015/117718、WO 2016/015815、WO 2016/124304、WO 2017/032439 and WO 2018/01186. In general, all phosphorescent complexes known to those skilled in the art for phosphorescent electroluminescent devices and also to those skilled in the art of organic electroluminescence are suitable, and other phosphorescent complexes can be used by those skilled in the art without any inventive effort.
Examples of phosphorescent dopants are listed in the following table.
The compounds according to the invention are also particularly suitable as matrix materials for phosphorescent emitters in organic electroluminescent devices, as described in WO 98/24271, US 2011/024847 and US 2012/0223633. In these multicolor display assemblies, an additional blue light emitting layer is evaporated over the entire surface of all pixels, including those other than blue.
In another embodiment of the invention the organic electroluminescent device according to the invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light emitting layer is directly adjacent to the hole injection layer or anode and/or the light emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode, as described for example in WO 2005/053051. Furthermore, the same or similar metal complex as in the light emitting layer may be used directly adjacent to the light emitting layer as a hole transporting or hole injecting material, as described in WO 2009/030981.
In the other layers of the organic electroluminescent device according to the invention, all materials which are generally used according to the prior art can be used. Thus, the person skilled in the art can, without inventive effort, use all materials known for organic electroluminescent devices in combination with the compounds according to the invention according to formula (I) or the preferred embodiments described above.
It is furthermore preferred that the organic electroluminescent device is characterized in that one or more layers are coated with a sublimation process. In this case, the material is evaporated in the vacuum sublimation system at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 mbar. However, it is also possible for the initial pressure to be lower, for example less than 10 -7 mbar.
It is also preferred that the organic electroluminescent device is characterized in that one or more layers are applied by an OVPD (organic vapour deposition) process or by sublimation with the aid of a carrier gas. The material is applied here at a pressure of 10 -5 mbar to 1 bar. One special case of such a process is the OVJP (organic vapor jet printing) process, in which the material is applied directly through a nozzle and is thus structured.
It is also preferred that the organic electroluminescent device is characterized in that one or more layers are manufactured from a solution, for example by spin coating or using any printing method, such as screen printing, flexography, offset printing, LITI (photo induced thermal imaging, thermal transfer printing), inkjet printing (inkjet printing) or nozzle printing. For this purpose, there is a need for soluble compounds, which are obtained, for example, by suitable substitution.
The formulation for applying the compound according to formula (I) or the preferred embodiments thereof described above is novel, and therefore a further subject of the present invention is a formulation comprising at least one solvent and the compound according to formula (I) or the preferred embodiments thereof described above.
Furthermore, a mixing method is possible, in which, for example, one or more layers are applied from solution and one or more additional layers are evaporated.
These methods are generally known to the person skilled in the art and can be applied, without inventive effort, to organic electroluminescent devices containing the compounds according to the invention.
The compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished by a low refractive index (refractive index RI) compared with the prior art. In addition, these compounds and the organic electroluminescent devices obtained therefrom have improved service lives. At the same time, other electronic properties of the electroluminescent device, such as efficiency or operating voltage, are at least as good. In a further variant, the compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished by improved efficiency and/or operating voltage and a higher service life than in the prior art.
The electronic device, in particular the organic electroluminescent device, according to the invention has one or more of the following surprising advantages over the prior art:
1. Electronic devices, in particular organic electroluminescent devices, comprising the compounds according to formula (I) or the preferred embodiments described above and below, in particular as matrix materials or hole-conducting materials, have outstanding efficiency. The compounds according to the invention according to formula (I) or the preferred embodiments described above and below here give rise to low operating voltages when used in electronic devices.
2. Electronic devices, in particular organic electroluminescent devices, comprising the compounds according to formula (I) or the preferred embodiments described above and below, in particular as matrix materials or hole-conducting materials, have very good service lives. Here, these compounds produce low roll-off, i.e., the energy efficiency of the device is reduced at high brightness.
3. The compounds according to the invention according to formula (I) or the preferred embodiments described above and below exhibit very high stability and service life.
4. Electronic devices, in particular organic electroluminescent devices, comprising the compounds according to formula (I) or the preferred embodiments described above and below, in particular as matrix materials or hole-conducting materials, have a very low refractive index.
5. With the compounds according to formula (I) or the preferred embodiments described above and below, the formation of optically lossy channels in electronic devices, in particular organic electroluminescent devices, can be avoided. Thus, these devices are characterized by high PL efficiency of the emitter, and thus high EL efficiency, and excellent energy transfer from the host to the dopant.
6. The compounds according to formula (I) or the preferred embodiments described above and below have excellent glass film forming ability.
7. The compounds according to formula (I) or the preferred embodiments described above and below form very good films from solutions.
The above advantage is not accompanied by excessive deterioration of other electronic characteristics.
It should be noted that variations of the embodiments described in the present invention are within the scope of the present invention. Any feature disclosed in this application may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly excluded. Thus, unless otherwise indicated, each feature disclosed in this specification may be considered an example of a generic sequence, or an equivalent or similar feature.
All features of the invention may be combined in any way unless certain features and/or steps are mutually exclusive. This applies in particular to the preferred features of the invention. Also, features that are not necessarily combined may be used alone (rather than in combination).
It should also be noted that many features, particularly those of the preferred embodiments of the invention, should be considered as being inventive in itself and not merely part of an embodiment of the invention. In addition to or instead of these features, independent protection may be sought for the presently claimed invention.
The teachings of the technical operations of the present disclosure may be abstracted and combined with other examples.
Detailed Description
The invention will be explained in more detail by the following examples, without wishing to be limited thereby. Those skilled in the art can practice the invention within the full scope of the disclosure from the description and produce and use other compounds according to the invention for electronic devices or apply methods according to the invention without creative effort.
Examples:
Unless otherwise specified, the following syntheses were carried out in a dry solvent under a protective gas atmosphere. The metal complexes are additionally operated under light-protected conditions or under yellow light. Solvents and reagents may for example be Sigma-ALDRICH or ABCR. The information given in brackets or the numbers given for the individual compounds refer to the CAS numbers for the compounds known from the literature. Among compounds that may have multiple enantiomers, diastereomers, or tautomers, one form is representatively represented.
Synthetic LS known in literature:
synthesis of compounds according to the invention:
Example A, B and synthesis S:
Example A1:
Organic copper chloride was produced according to m.oi et al chem.sci.,2019,10,6107 and oxygen-mediated C-N coupling was performed according to h.yamamoto et al, j.org.chem.,1980,45,2739.
Rind-CuCl was prepared from 3.49g (10 mmol) LS1 as described in M.Oi et al, chem.Sci.,2019,10,6107, example 36. After heating to 0 ℃ and stirring for 1 hour, the Rind-CuCl solution was cooled to-20 ℃ and then, with good stirring, a solution of lithium diphenylamide freshly prepared from 1.86g (11 mmol) of diphenylamine [122-39-4] in 1.6M n-butyllithium in 30ml THF and 6.9ml n-hexane was added and stirred for 2 hours. An oxygen stream was then directed through the solution via a glass dropper for 5 minutes, stirred for 20 minutes, quenched by the addition of 50ml of saturated ammonium chloride solution, 200ml of ethyl acetate was added, the organic phase was separated and the solvent was removed under vacuum. The crude product is further purified by chromatography and repeated thermal extraction crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-Dichloromethane (DCM), 1:3 to 3:1 vv) and fractional sublimation or annealing in high vacuum, respectively. Yield 3.1g (6.9 mmol) 69% purity about 99.9%. HPLC.
Similarly, the following compounds may be prepared. The yields depend on the one hand on the steric demands of LS1 to LS8, wherein the following decreasing sequences LS1 to LS2 to LS3> LS4> LS5 to LS6 to LS7 to LS8 are generally observed, and on the other hand on the steric demands of secondary amines, which are generally in the range of 50 to 80%.
Examples C, D and E:
example C1:
Example 36 was performed according to m.oi et al, chem.sci.,2019,10,6107.
Method 34.9g (100 mmol) LS1, 40.8g (110 mmol) [38257-52-2] 4-iodotriphenylamine instead of methyl 4-iodobenzoate were placed in a stirred autoclave at 120℃for 24 hours. The crude product is purified by chromatography and/or repeated thermal extraction crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) and fractional sublimation or annealing in high vacuum, respectively. The yield was 33.4g (65 mmol) of 65%, and the purity was about 99.9%. HPLC.
Similarly, compounds may be prepared in which the stoichiometry is adjusted according to the C-C bond to be bound when using dibromides and tribromides. The yield depends on the one hand on the steric requirements of LS1 to LS8, wherein the following decreasing sequences LS1 to LS2 to LS3> LS4> LS5 to LS6 to LS7 to LS8 are generally observed. On the other hand, for aryl amino halogen coupling agents for bromides, they are generally in the range of 40-60% and for iodides they are in the range of 50-70%.
Example production of OLED
1) Vacuum processing equipment:
The OLED according to the invention, as well as the OLED to be referred to, is produced according to the general process described in WO 2004/058911, which process is adapted to the conditions described herein (layer thickness variation, materials used).
The results for different OLEDs are given in the examples below. The purified glass sheet (washed in a Miele laboratory washer, merck Extran washer) was coated with structured ITO (indium tin oxide) with a thickness of 50nm and the glass sheet was pre-treated with UV ozone for 25 minutes (UV ozone generator PR-100, UVP company). These coated glass sheets form a substrate onto which the OLED is applied.
1A) Blue fluorescent OLED assembly-BF:
The compounds according to the present invention may be used in Hole Injection Layers (HILs), hole Transport Layers (HTLs) and Electron Blocking Layers (EBLs). All materials were thermally evaporated in a vacuum chamber. The light-emitting layer (EML) is always composed of at least one matrix material (host material ) SMB (see table 1) and one light-emitting dopant (dopant, emitter) D, which is incorporated into one or more matrix materials in a certain volume ratio by co-evaporation. Here, for example, the data for SMB: D (97:3%) indicates that the SMB material is present in the layer in a proportion of 97% by volume and the dopant D is present in the layer in a proportion of 3% by volume. Similarly, the electron transport layer may also consist of a mixture of two materials, see table 1. The materials used to make the OLEDs are shown in table 5, or referred to the synthetic examples above.
The OLED was characterized according to the standard. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd/a), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) (depending on the brightness) and the service life are determined, the external quantum efficiency being calculated from the current-voltage-brightness characteristic curve (IUL characteristic curve) assuming lambertian radiation characteristics. The EQE in% and the voltage in V are given at a luminance of 1000cd/m 2. The service life was determined at a start-up luminance of 10000cd/m 2. The measurement time for the reference illuminance to drop to 80% of the initial illuminance was set to 100%. The useful life of an OLED assembly containing a compound according to the invention is given in percent relative to a reference.
The OLED has the following layer structure:
Substrate
Hole Injection Layer (HIL) made of HTM1 doped with 5% NDP-9 (Novaled, available from company) 20nm
Hole Transport Layers (HTL) are shown in Table 1
Electron Blocking Layers (EBL), see Table 1
Luminescent layer (EML), see Table 1
Electron Transport Layer (ETL), see Table 1
Electron Injection Layer (EIL) made of ETM2, 1nm
Aluminum cathode, 100nm
TABLE 1 Structure of blue fluorescent OLED Assembly
TABLE 2 results for blue fluorescent OLED assemblies
1B) Phosphorescent OLED assembly:
The compound a according to the present invention may be used as a matrix material (host material ) M (see table 5) or a (see material according to the present invention) in a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), and an emission layer (EML). For this purpose, all materials are thermally evaporated in a vacuum chamber. The light-emitting layer is composed of at least one or more matrix materials M and a phosphorescent dopant Ir, which is incorporated into the one or more matrix materials in a certain volume proportion by co-evaporation. For example, the data for M1:M2:Ir (55%: 35%: 10%) indicate that the material M1 is present in the layer in a proportion of 55% by volume, M2 in a proportion of 35% by volume, ir in a proportion of 10% by volume. Similarly, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLED can be seen in table 3. The materials used to make the OLEDs are shown in table 5, or referred to the synthetic examples above.
The OLED was characterized according to the standard. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd/a), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) (depending on the brightness) and the service life are determined, the external quantum efficiency being calculated from the current-voltage-brightness characteristic curve (IUL characteristic curve) assuming lambertian radiation characteristics. The EQE in% and the voltage in V are given at a luminance of 1000cd/m 2. The service life was determined at a start luminance of 1000cd/m 2 for blue and red, 10000cd/m 2 for green and yellow. The measurement time for the reference illuminance to drop to 80% of the initial illuminance was set to 100%. The useful life of an OLED assembly containing a compound according to the invention is given in percent relative to the corresponding reference.
The OLED has the following layer structure:
Substrate
Hole Injection Layer (HIL) made of HTM1 doped with 5% NDP-9 (Novaled, available from company) 20nm
Hole Transport Layer (HTL), see Table 3
Electron Blocking Layer (EBL), see Table 3
Luminescent layer (EML), see Table 3
Hole Blocking Layer (HBL), see Table 3
An Electron Transport Layer (ETL) made of ETM 1/ETM 2 (50%: 50%), a 30nm Electron Injection Layer (EIL) made of ETM2, 1nm
Aluminum cathode, 100nm
TABLE 3 Structure of phosphorescent OLED Assembly
TABLE 4 results for phosphorescent OLED assemblies
TABLE 5 structural formula of the materials used

Claims (19)

1.一种包含至少一种式(I)结构的化合物，1. A compound comprising at least one structure of formula (I), 其中符号代表：The symbols represent: Za在每次出现时相同或不同地代表Ar、Rc、L1-N(Ar)2或L1-Q；Za , on each occurrence, identically or differently, represents Ar, Rc , L1 -N(Ar) 2 or L1 -Q; Ar在每次出现时相同或不同地为具有5至60个芳族环原子的芳族或杂芳族环系，其能被一个或多个残基Rd取代，其中与相同N原子结合的两个残基Ar也能通过单键或选自B(Rd)、C(Rd)2、Si(Rd)2、C＝O、C＝N Rd、C＝C(Rd)2、RdC＝CRd、O、S、S＝O、SO2、N(Rd)、P(Rd)、P(＝O)Rd以及能被一个或多个残基Rd取代的邻位连接亚苯基的桥彼此桥接；Ar is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R d , whereby two radicals Ar bound to the same N atom can also be bridged to one another by a single bond or by a bridge selected from B(R d ), C(R d ) 2 , Si(R d ) 2 , C═O, C═NR d , C═C(R d ) 2 , R d C═CR d , O, S, S═O, SO 2 , N(R d ), P(R d ), P(═O)R d and ortho-bound phenylene which can be substituted by one or more radicals R d ; L1在每次出现时相同或不同地代表键或具有5至60个芳族环原子的芳族或杂芳族环系，所述环系能被一个或多个残基R取代；L 1 represents, identically or differently on each occurrence, a bond or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R; Ra在每次出现时相同或不同地为具有1至10个碳原子的直链烷基、烷氧基或硫代烷氧基，或具有3至10个碳原子的支链或环状烷基、烷氧基或硫代烷氧基，其分别能被一个或多个残基R2取代，或者是具有5至20个芳族环原子的芳族或杂芳族环系，其分别能被一个或多个残基R2取代，其中两个或更多个取代基Ra能彼此形成环系；Ra , identically or differently on each occurrence, is a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 10 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 10 carbon atoms, each of which can be substituted by one or more radicals R2 , or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, each of which can be substituted by one or more radicals R2 , wherein two or more substituents Ra can form a ring system with one another; Rb在每次出现时相同或不同地为H、D、具有1至10个碳原子的直链烷基、烷氧基或硫代烷氧基，或具有3至10个碳原子的支链或环状烷基、烷氧基或硫代烷氧基，其分别能被一个或多个残基R2取代，或具有5至20个芳族环原子的芳族或杂芳族环系，其分别能被一个或多个残基R2取代，其中两个取代基Rb能够彼此形成环系；R b is, identically or differently on each occurrence, H, D, straight-chain alkyl, alkoxy or thioalkoxy having 1 to 10 carbon atoms, or branched or cyclic alkyl, alkoxy or thioalkoxy having 3 to 10 carbon atoms, each of which can be substituted by one or more radicals R 2 , or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, each of which can be substituted by one or more radicals R 2 , where two substituents R b can form a ring system with one another; Q在每次出现时相同或不同地代表电子传输基团，优选具有5至12个环原子的含氮杂芳基，其能被一个或多个残基Re取代；Q, identically or differently on each occurrence, represents an electron-transporting group, preferably a nitrogen-containing heteroaryl group having 5 to 12 ring atoms, which can be substituted by one or more residues Re ; R、Rc、Rd、Re在每次出现时相同或不同地为H、D、OH、F、Cl、Br、I、CN、NO2、N(Ar’)2、N(R1)2、C(＝O)N(Ar’)2、C(＝O)N(R1)2、C(Ar’)3、C(R1)3、Si(Ar’)3、Si(R1)3、B(Ar’)2、B(R1)2、C(＝O)Ar'、C(＝O)R1、P(＝O)(Ar’)2、P(＝O)(R1)2、P(Ar’)2、P(R1)2、S(＝O)Ar'、S(＝O)R1、S(＝O)2Ar'、S(＝O)2R1、OSO2Ar'、OSO2R1、具有1至40个碳原子的直链烷基、烷氧基或硫代烷氧基，或具有2至40个碳原子的烯基或炔基，或具有3至20个碳原子的支链或环状烷基、烷氧基或硫代烷氧基，其中烷基、烷氧基、硫代烷氧基、烯基或炔基分别能被一个或多个残基R1取代，其中一个或多个不相邻的CH2基团能被R1C＝CR1、C≡C、Si(R1)2、C＝O、C＝S、C＝Se、C＝NR1、C(＝O)O、C(＝O)NR1-、NR1、P(＝O)(R1)、-O-、S、SO或SO2替代，或具有5至60个芳族环原子的芳族或杂芳族环系，其分别能被一个或多个残基R1取代，或具有5至60个芳族环原子的芳氧基或杂芳氧基，其能被一个或多个残基R1取代，其中两个残基R、Rd、Re也能彼此形成环系，或残基R、Rd、Re与另外的基团、特别是残基Rc能形成环系；R, R c , R d , and Re are , at each occurrence, identically or differently, H, D, OH, F, Cl, Br, I, CN, NO 2 , N(Ar′) 2 , N(R 1 ) 2 , C(═O)N(Ar′) 2 , C(═O)N(R 1 ) 2 , C(Ar′) 3 , C(R 1 ) 3 , Si(Ar ′ ) 3 , Si(R 1 ) 3 , B(Ar′) 2 , B(R 1 ) 2 , C(═O)Ar′, C(═O)R 1 , P(═O)(Ar′) 2 , P(═O)(R 1 ) 2 , P(Ar′) 2 , P(R 1 ) 2 , S(═O)Ar′, S(═O)R 1 , S(═O ) Ar', S(=O) 2 R 1 , OSO 2 Ar', OSO 2 R 1 , straight-chain alkyl, alkoxy or thioalkoxy having 1 to 40 carbon atoms, or alkenyl or alkynyl having 2 to 40 carbon atoms, or branched or cyclic alkyl, alkoxy or thioalkoxy having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl can be substituted by one or more residues R 1 , wherein one or more non-adjacent CH 2 groups can be replaced by R 1 C=CR 1 , C≡C, Si(R 1 ) 2 , C=O, C=S, C=Se, C=NR 1 , C(=O)O, C(=O)NR 1 -, NR 1 , P(=O)(R 1 ), -O-, S, SO or SO 2 , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R 1 , or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R 1 , wherein two radicals R, R d , Re can also form a ring system with each other, or radicals R, R d , Re with another group, in particular radical R c, can form a ring system; Ar'在每次出现时相同或不同地为具有5至60个芳族环原子的芳族或杂芳族环系，其能被一个或多个残基R1取代，其中与相同的C原子、Si原子、N原子、P原子或B原子结合的两个残基Ar'也能够通过单键或选自B(R1)、C(R1)2、Si(R1)2、C＝O、C＝NR1、C＝C(R1)2、O、S、S＝O、SO2、N(R1)、P(R1)和P(＝O)R1的桥彼此桥接；Ar′ is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R 1 , wherein two radicals Ar′ which are bonded to the same C atom, Si atom, N atom, P atom or B atom can also be bridged to one another via a single bond or a bridge selected from the group consisting of B(R 1 ), C(R 1 ) 2 , Si(R 1 ) 2 , C═O, C═NR 1 , C═C(R 1 ) 2 , O, S, S═O, SO 2 , N(R 1 ), P(R 1 ) and P(═O)R 1 ; R1在每次出现时相同或不同地为H、D、F、Cl、Br、I、CN、NO2、N(Ar”)2、N(R2)2、C(＝O)Ar”、C(＝O)R2、P(＝O)(Ar”)2、P(Ar”)2、B(Ar”)2、B(R2)2、C(Ar”)3、C(R2)3、Si(Ar”)3、Si(R2)3、具有1至40个碳原子的直链烷基、烷氧基或硫代烷氧基，或具有3至40个碳原子的支链或环状烷基、烷氧基或硫代烷氧基，或具有2至40个碳原子的烯基，其分别能被一个或多个残基R2取代，其中一个或多个不相邻的CH2基团能被-R2C＝CR2-、C≡C-、Si(R2)2、C＝O、C＝S、C＝Se、C＝NR2、C(＝O)O-、C(＝O)NR2-、NR2、P(＝O)(R2)、-O-、S、SO或SO2替代，并且其中一个或多个H原子能被D、F、Cl、Br、I、CN或NO2替代，或具有5至60个芳族环原子的芳族或杂芳族环系，其分别能被一个或多个残基R2取代，或具有5至60个芳族环原子的芳氧基或杂芳氧基，其能被一个或多个残基R2取代，或具有5至60个芳族环原子的芳烷基或杂芳烷基，其能被一个或多个残基R2取代，或这些体系的组合；其中两个或更多个残基R1能够彼此形成环系，其中一个或多个残基R1能够与化合物的另一部分形成环系；R 1 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, CN, NO 2 , N(Ar”) 2 , N(R 2 ) 2 , C(═O)Ar”, C(═O)R 2 , P(═O)(Ar”) 2 , P(Ar”) 2 , B(Ar”) 2 , B(R 2 ) 2 , C(Ar”) 3 , C(R 2 ) 3 , Si(Ar”) 3 , Si(R 2 ) 3 , straight-chain alkyl, alkoxy or thioalkoxy having 1 to 40 carbon atoms, or branched or cyclic alkyl, alkoxy or thioalkoxy having 3 to 40 carbon atoms, or alkenyl having 2 to 40 carbon atoms, which can each be substituted by one or more radicals R 2 , wherein one or more non-adjacent CH 2 groups can be replaced by —R 2 C＝CR2-, C≡C-, Si(R 2 ) 2 , C＝O, C＝S, C＝Se, C＝NR 2 , C(＝O)O-, C(＝O)NR 2 -, NR 2 , P(＝O)(R 2 ), -O-, S, SO or SO 2 , and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can be substituted by one or more residues R 2 , respectively, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which can be substituted by one or more residues R 2 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which can be substituted by one or more residues R 2 , or a combination of these systems; wherein two or more residues R 1 can form a ring system with each other, wherein one or more residues R 1 can form a ring system with another part of the compound; Ar”在每次出现时相同或不同地为具有5至30个芳族环原子的芳族或杂芳族环系，其能被一个或多个残基R2取代，其中与相同的C原子、Si原子、N原子、P原子或B原子结合的两个残基Ar”也能够通过单键或选自B(R2)、C(R2)2、Si(R2)2、C＝O、C＝NR2、C＝C(R2)2、O、S、S＝O、SO2、N(R2)、P(R2)和P(＝O)R2的桥彼此桥接；Ar" is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which can be substituted by one or more radicals R 2 , wherein two radicals Ar" which are bonded to the same C atom, Si atom, N atom, P atom or B atom can also be bridged to one another via a single bond or a bridge selected from the group consisting of B(R 2 ), C(R 2 ) 2 , Si(R 2 ) 2 , C═O, C═NR 2 , C═C(R 2 ) 2 , O, S, S═O, SO 2 , N(R 2 ), P(R 2 ) and P(═O)R 2 ; R2在每次出现时相同或不同地选自H、D、F、CN、具有1至20个碳原子的脂族烃残基或具有5至30个芳族环原子的芳族或杂芳族环系，其中一个或多个H原子能被D、F、Cl、Br、I或CN替代，并能被分别具有1至4个碳原子的一个或多个烷基取代，其中两个或更多个取代基R2能够彼此形成环系。 R2 is selected, identically or differently on each occurrence, from H, D, F, CN, an aliphatic hydrocarbon residue having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein one or more H atoms can be replaced by D, F, Cl, Br, I or CN and by one or more alkyl radicals each having 1 to 4 carbon atoms, wherein two or more substituents R2 can form a ring system with one another. 2.根据权利要求1所述的化合物，其包含至少一种式(I-1)至(I-4)的结构，2. The compound according to claim 1, comprising at least one structure of formula (I-1) to (I-4), 其中符号Ar、Lr1、Q、Ra、Rb和Rc具有权利要求1中所述的含义。The symbols Ar, Lr 1 , Q, Ra , Rb and Rc have the meanings given in claim 1. 3.根据权利要求1或2所述的化合物，其特征在于，基团Ar在每次出现时相同或不同地选自式(Ara-1)至(Ara-28)的结构，3. The compound according to claim 1 or 2, characterized in that the group Ar is selected from the structures of formula (Ar a -1) to (Ar a -28) at each occurrence, identically or differently, 其中对于使用的符号以下成立：where the following holds for the symbols used: Y2是O、S、NRd或C(Rd)2； Y2 is O, S, NRd or C( Rd ) 2 ; k在每次出现时独立地为0或1；k is independently 0 or 1 at each occurrence; i在每次出现时独立地为0、1或2；i is independently 0, 1, or 2 at each occurrence; j在每次出现时独立地为0、1、2或3；j is independently 0, 1, 2, or 3 at each occurrence; h在每次出现时独立地为0、1、2、3或4；h is independently 0, 1, 2, 3, or 4 at each occurrence; g在每次出现时独立地为0、1、2、3、4或5；g is independently 0, 1, 2, 3, 4, or 5 at each occurrence; Rd具有以上特别是对于权利要求1所述的含义，并且虚线键标记了结合位置。R d has the meaning given above, in particular for claim 1 , and the dashed bond marks the binding site. 4.根据权利要求1至3中的一项或多项所述的化合物，其特征在于，所述化合物不包含具有三个彼此稠合的芳族六元环的芳族或杂芳族环系。4 . The compound according to claim 1 , wherein the compound does not contain any aromatic or heteroaromatic ring system having three aromatic six-membered rings fused to one another. 5.根据前述权利要求1至4中至少一项所述的化合物，其特征在于，所述化合物不包含其上结合有两个氧原子的环丁基残基，并且所述化合物也不包含噻二嗪基团。5 . The compound according to claim 1 , wherein the compound contains no cyclobutyl residues to which two oxygen atoms are bonded and also contains no thiadiazine groups. 6.根据前述权利要求1至5中至少一项所述的化合物，其特征在于，所述化合物不包含烷氧基、硫代烷氧基或羟基。6 . The compound according to claim 1 , wherein the compound contains no alkoxy, thioalkoxy or hydroxyl groups. 7.根据权利要求1至6中的一项或多项所述的化合物，其特征在于，基团L1相同或不同地代表键或选自式(L1-1)至(L1-22)的结构，7. Compounds according to one or more of claims 1 to 6, characterized in that the groups L1, identically or differently, represent a bond or a structure selected from the group consisting of the formulae ( L1-1 ) to ( L1-22 ), 其中对于使用的符号以下成立：where the following holds for the symbols used: Y是CR2、O、S或NR；Y is CR 2 , O, S or NR; j在每次出现时独立地为0、1、2或3；j is independently 0, 1, 2, or 3 at each occurrence; h在每次出现时独立地为0、1、2、3或4；h is independently 0, 1, 2, 3, or 4 at each occurrence; R具有以上特别是对于权利要求1所述的含义，并且虚线键标记了结合位置。R has the meaning given above, in particular for claim 1 , and the dashed bond marks the binding site. 8.根据权利要求1至7中的一项或多项所述的化合物，其包含至少一种式(II-1)至(II-62)的结构，8. A compound according to one or more of claims 1 to 7, comprising at least one structure of formula (II-1) to (II-62), 其中符号R、Ra、Rb、Rc和Rd具有权利要求1中所述的含义，并且对于其他符号以下成立：wherein the symbols R, Ra , Rb , Rc and Rd have the meanings given in claim 1, and the following holds true for the other symbols: 对于一个基团与所述结构结合的情况，X在每次出现时相同或不同地代表N、CR或C；In the case where a group is attached to the structure, X represents N, CR or C identically or differently at each occurrence; 对于一个基团与所述结构结合的情况，X1在每次出现时相同或不同地代表N、CRd或C；In the case where a group is attached to the structure, X 1 represents N, CR d or C the same or different at each occurrence; Y代表O、S、NR或C(R)2，优选O、NR或C(R)2；并且Y represents O, S, NR or C(R) 2 , preferably O, NR or C(R) 2 ; and Y1代表O、S、BRd、NRd、Si(Rd)2或C(Rd)2。 Y1 represents O, S, BRd , NRd , Si( Rd ) 2 or C( Rd ) 2 . 9.根据权利要求1至8中任一项所述的化合物，其包含式(III-1)至(III-62)的至少一种结构，9. A compound according to any one of claims 1 to 8, comprising at least one structure of formula (III-1) to (III-62), 其中符号R、Ra、Rb、Rc和Rd具有权利要求1中所述的含义，并对于所使用的符号以下成立：The symbols R, Ra , Rb , Rc and Rd have the meanings given in claim 1, and the following applies to the symbols used: Y是O、S、NR或C(R)2；Y is O, S, NR or C(R) 2 ; Y1代表O、S、BRd、NRd、Si(Rd)2或C(Rd)2； Y1 represents O, S, BRd , NRd , Si( Rd ) 2 or C( Rd ) 2 ; n在每次出现时独立地为0、1、2或3；n is independently 0, 1, 2, or 3 at each occurrence; m在每次出现时独立地为0、1、2、3或4；m is independently 0, 1, 2, 3, or 4 at each occurrence; l在每次出现时独立地为0、1、2、3、4或5。l is independently 0, 1, 2, 3, 4, or 5 at each occurrence. 10.根据前述权利要求1至9中至少一项所述的化合物，其特征在于，残基Rc代表H、D、甲基、乙基、丙基，其中这些基团能够被氘代。10 . The compound according to claim 1 , wherein the radical R c represents H, D, methyl, ethyl, propyl, wherein these radicals can be deuterated. 11.根据前述权利要求1至10中至少一项所述的化合物，其特征在于，对于所述符号以下成立：11. Compound according to at least one of the preceding claims 1 to 10, characterized in that the following holds for the symbols: R、Rc、Rd在每次出现时相同或不同地为H、D、N(Ar’)2、N(R1)2、C(Ar’)3、C(R1)3、Si(Ar’)3、Si(R1)3、B(Ar’)2、B(R1)2、具有1至40个碳原子的直链烷基或具有3至20个碳原子的支链或环状烷基，其中所述烷基分别能被一个或多个残基R1取代，其中一个或多个不相邻的CH2基团能被R1C＝CR1、C≡C、Si(R1)2、C＝O、C＝S、C＝Se、C＝NR1、C(＝O)O、C(＝O)NR1-、NR1、P(＝O)(R1)、SO或SO2替代，或具有5至30个芳族环原子的芳族或杂芳族环系，其分别能被一个或多个残基R1取代；在此，两个残基R、Rd也能够彼此形成环系或者一个残基R、Rd与另一个基团、特别是残基Rc能够形成环系。R, R c , R d are, at each occurrence, identically or differently, H, D, N(Ar′) 2 , N(R 1 ) 2 , C(Ar′) 3 , C(R 1 ) 3 , Si(Ar′) 3 , Si(R 1 ) 3 , B(Ar′) 2 , B(R 1 ) 2 , straight-chain alkyl having 1 to 40 carbon atoms or branched or cyclic alkyl having 3 to 20 carbon atoms, wherein the alkyl radicals can each be substituted by one or more radicals R 1 , wherein one or more non-adjacent CH 2 groups can be replaced by R 1 , C═CR 1 , C≡C, Si(R 1 ) 2 , C═O, C═S, C═Se, C═NR 1 , C(═O)O, C(═O)NR 1 -, NR 1 , P(═O)(R 1 ), SO or SO 2 , or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which can each be substituted by one or more radicals R 1 ; in this case, two radicals R, R d can also form a ring system with each other or a radical R, R d with another group, in particular a radical R c, can form a ring system. 12.根据前述权利要求1至11中至少一项所述的化合物，其特征在于，所述化合物具有小于或等于5000g/mol、优选小于或等于4000g/mol、特别优选小于或大于3000g/mol、特别优选小于或等于2000g/mol、更特别优选小于或等于1200g/mol、并且尤其优选小于或等于900g/mol的分子量。12. The compound according to at least one of the preceding claims 1 to 11, characterized in that the compound has a molecular weight of less than or equal to 5000 g/mol, preferably less than or equal to 4000 g/mol, particularly preferably less than or greater than 3000 g/mol, particularly preferably less than or equal to 2000 g/mol, more particularly preferably less than or equal to 1200 g/mol, and especially preferably less than or equal to 900 g/mol. 13.含有根据权利要求1至12中任一项所述的一种或多种化合物的低聚物、聚合物或树枝状大分子，其中代替氢原子或取代基，存在所述化合物与聚合物、低聚物或树枝状大分子的一个或多个键。13. Oligomer, polymer or dendrimer containing one or more compounds according to any one of claims 1 to 12, wherein instead of a hydrogen atom or a substituent there are one or more bonds of said compound to the polymer, oligomer or dendrimer. 14.含有至少一种根据权利要求1至12中的一项或多项所述的化合物或根据权利要求13所述的低聚物、聚合物或树枝状大分子和至少一种其他化合物的制剂，其中所述其他化合物优选选自一种或多种溶剂。14. Preparation containing at least one compound according to one or more of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13 and at least one further compound, wherein the further compound is preferably selected from one or more solvents. 15.一种组合物，其包含至少一种根据权利要求1至12中的一项或多项所述的化合物或根据权利要求13所述的低聚物、聚合物或树枝状大分子，以及至少一种选自荧光发光体、磷光发光体、表现出TADF的发光体、主体材料、电子传输材料、电子注入材料、空穴传输材料、空穴注入材料、电子阻挡材料和空穴阻挡材料的其他化合物，优选主体材料。15. A composition comprising at least one compound according to one or more of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF, host materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, electron blocking materials and hole blocking materials, preferably host materials. 16.用于制备根据权利要求1至12中的一项或多项所述的化合物的方法，其特征在于，合成其上稠合有环戊基的苯基化合物，并优选通过亲核芳族取代反应或偶联反应引入至少一个芳族或杂芳族残基。16. Process for preparing compounds according to one or more of claims 1 to 12, characterized in that a phenyl compound to which a cyclopentyl group is fused is synthesized and at least one aromatic or heteroaromatic residue is introduced, preferably by a nucleophilic aromatic substitution reaction or coupling reaction. 17.根据权利要求1至12中的一项或多项所述的化合物或根据权利要求13所述的低聚物、聚合物或树枝状大分子在电子器件中的用途，优选用作主体材料、空穴传输材料、空穴注入材料或电子阻挡材料。17. Use of a compound according to one or more of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13 in electronic devices, preferably as host material, hole transport material, hole injection material or electron blocking material. 18.一种电子器件，其包含至少一种根据权利要求1至12中的一项或多项所述的化合物或根据权利要求13所述的低聚物、聚合物或树枝状大分子。18. An electronic device comprising at least one compound according to one or more of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13. 19.根据权利要求18所述的电子器件，其中，所述电子器件是有机电致发光器件，其特征在于，所述有机电致发光器件包括至少一个发光层和至少一个空穴传输层，并且所述空穴传输层包含根据权利要求1至13中的一项或多项所述的化合物或根据权利要求14所述的低聚物、聚合物或树枝状大分子。19. The electronic device according to claim 18, wherein the electronic device is an organic electroluminescent device, characterized in that the organic electroluminescent device comprises at least one light-emitting layer and at least one hole transport layer, and the hole transport layer comprises a compound according to one or more of claims 1 to 13 or an oligomer, polymer or dendrimer according to claim 14.
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