Novel materials for organic electroluminescent devices

Abstract

The present application relates to a novel material for use in organic electroluminescent devices. In particular, the present application relates to novel compounds and to organic electroluminescent devices, such as OLEDs (organic light emitting diodes), containing these compounds, for example as electron transport material and / or matrix material, optionally in combination with other matrix materials. The present application also relates to mixtures and formulations containing these novel compounds.

Description

[0001] This application is a divisional application of Chinese invention patent application filed on December 19, 2023, with application number 202380087940.6 and invention title "Novel Material for Organic Electroluminescent Devices". Technical Field

[0002] This application relates to a novel material for organic electroluminescent devices. Specifically, the present invention relates to novel compounds and organic electroluminescent devices such as OLEDs (organic light-emitting diodes) containing these compounds, which are used, for example, as electron transport materials and / or matrix materials, optionally in combination with other matrix materials. The present invention also relates to mixtures and formulations containing these novel compounds. Background Technology

[0003] For example, structures of organic electroluminescent devices (such as organic light-emitting diodes (OLEDs) or organic light-emitting electrochemical cells (OLECs) that use organic semiconductors as organic functional materials are described in US 4539507, US 5151629, EP 0676461, and WO 98 / 27136. The luminescent materials and phosphors used here are increasingly organometallic complexes exhibiting phosphorescence (MA Baldo et al., Appl. Phys. Lett. 1999, Vol. 75, pp. 4-6). For quantum mechanical reasons, using organometallic compounds as phosphorescent emitters can improve energy efficiency and power efficiency by a factor of four. Generally, both singlet and triplet OLEDs still require improvement, particularly in terms of efficiency, operating voltage, and lifetime.

[0004] The performance of organic electroluminescent devices depends not only on the light-emitting element used. Other materials employed, such as host and matrix materials, hole-blocking materials, electron transport materials, and electron or exciton-blocking materials, are also crucial. Improvements in these materials can significantly enhance the performance of electroluminescent devices.

[0005] In the prior art, heteroaromatic compounds are particularly used as matrix materials for electron transport materials and phosphorescent compounds. The commonly used term "matrix material" refers to the host material of a phosphorescent emitter. This invention also uses the term "matrix material."

[0006] Triazine benzimidazole derivatives are compounds known to be used as electron transport materials and / or matrix materials in OLEDs (see KR 2018 / 007329, CN 106946853, CN 110922388, CN 112159361, CN202110215311, WO 2015 / 000549, WO 2016 / 012075, WO 2015 / 000549, WO 2019 / 017734 or WO 2020 / 9679).

[0007] However, improvements are still needed when these compounds are used, for example, as matrix materials, particularly in terms of lifetime, but also in terms of device efficiency and operating voltage. Summary of the Invention

[0008] Therefore, the object of this invention is to provide compounds suitable for use in organic electroluminescent devices and resulting in good device performance when used in such devices; and to provide corresponding organic electroluminescent devices. More specifically, the problem to be solved by this invention is to provide compounds that achieve long lifetime, high efficiency, and low operating voltage. In particular, the properties of the matrix material also have a significant impact on the lifetime and efficiency of organic light-emitting devices.

[0009] Another problem to be solved by the present invention is to provide compounds suitable for use in phosphorescence or fluorescence, especially in phosphorescent OLEDs, particularly as matrix materials.

[0010] Surprisingly, it has been discovered that these objectives can be achieved using a compound of formula (1):

[0011] Equation (1)

[0012] The symbols and markings used have the following meanings: L 1 Selected from single-bonded aromatic ring systems with 6-40 ring atoms or heteroaromatic ring systems with 5-40 ring atoms, wherein either ring system is optionally and independently partially or completely substituted by D. L 2 Aromatic ring systems consisting of single bonds or having 6-40 ring atoms, optionally partially or completely substituted by D; L 3 Selected from single-bonded aromatic ring systems with 6-40 ring atoms or heteroaromatic ring systems with 5-40 ring atoms, wherein either ring system is optionally and independently partially or completely substituted by D. Het is a group selected from the following groups: Het (1), Het (2), Het (3), Het (4) or Het (5); Indicates with L 2 The key to the connection; Het 1 Selected from aromatic ring systems having 6 to 40 ring atoms or heteroaromatic ring systems having 5 to 40 ring atoms, wherein either ring system is optionally and independently controlled by R. 3 To partially or completely replace; R may be the same or different in various cases and is selected from: H, D, F, CN; a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S, and wherein at least one hydrogen atom may be replaced by D, F or CN; or an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms, wherein at least one hydrogen atom may be replaced by D, F, Cl, Br, I or CN, and said aromatic ring system or heteroaromatic ring system may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more adjacent substituents R may together form an aliphatic, aromatic or heteroaromatic ring system; R 1 In various cases, the same or different, and selected from: H, D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S, and wherein at least one hydrogen atom may be replaced by D, F or CN, or an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms, wherein at least one hydrogen atom may be replaced by D, F, Cl, Br, I or CN, and said aromatic ring system or heteroaromatic ring system may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more adjacent substituents R may together form an aliphatic, aromatic or heteroaromatic ring system; R 2 In various cases, they may be the same or different, and are selected from aromatic ring systems having 6 to 40 ring atoms or heteroaromatic ring systems having 5 to 40 ring atoms, wherein the two ring systems are optionally and independently determined by R. 4 To partially or completely replace; R 3In various cases, the same or different, and selected from: H, D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S, and wherein at least one hydrogen atom may be replaced by D, F or CN, or an aromatic ring system having 6 to 40 carbon atoms or a heteroaromatic ring system having 5 to 40 ring atoms, wherein at least one hydrogen atom may be replaced by D, F, Cl, Br, I or CN, and said aromatic ring system or heteroaromatic ring system may be replaced by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more adjacent substituents R may together form an aliphatic, aromatic or heteroaromatic ring system; R 4 They may be the same or different in various cases, and are selected from H, D, F or CN; When m is 4, n is 3, or When n is 4, m is 3, and The following compounds are excluded from this invention: .

[0013] In this patent application, “D” or “D atom” represents deuterium.

[0014] In the context of this invention, an aryl group contains 6 to 40 ring atoms, preferably carbon atoms. In the context of this invention, a heteroaryl group contains 5 to 40 ring atoms, wherein the ring atoms comprise carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. The aryl group or heteroaryl group referred to herein means: a simple aromatic ring derived from benzene, i.e., phenyl; or, for example, a simple heteroaryl ring derived from pyridine, pyrimidine, or thiophene; or, for example, a fused aryl or heteroaryl group derived from naphthalene, anthracene, phenanthrene, quinoline, or isoquinoline. Therefore, an aryl group having 6 to 30 carbon atoms is preferably phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, biphenylidene, fluoranthyl, dibenzoanthryl, fulminyl, or perylene, and there is no limitation on the connection of the aryl group as a substituent.

[0015] In the context of this invention, an aromatic ring system contains 6 to 40 carbon atoms in the ring system, and said ring system further includes the aforementioned aryl group.

[0016] In the context of this invention, heteroaromatic ring systems contain 5 to 40 ring atoms and at least one heteroatom. Preferred heteroaromatic ring systems have 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system also includes heteroaryl groups as described above. The heteroatom in the heteroaromatic ring system is preferably selected from N, O, and / or S.

[0017] In the context of this invention, aromatic or heteroaromatic ring systems refer to systems that do not necessarily contain only aryl or heteroaromatic groups, but in which multiple aryl or heteroaromatic groups may be interrupted by non-aromatic units (preferably less than 10% of atoms other than H), such as carbon atoms, oxygen atoms, or carbonyl groups. For example, systems such as 9,9'-spirodifluorene, 9,9-diarylfluorene, 9,9-dialkylfluorene, diaryl ethers, stilbene, etc., should therefore also be considered aromatic or heteroaromatic ring systems in the context of this invention. Similarly, systems in which two or more aryl groups are interrupted by, for example, linear or cyclic alkyl groups or by silyl groups should also be considered aromatic or heteroaromatic ring systems. Furthermore, systems in which two or more aryl or heteroaromatic groups are directly bonded to each other, such as biphenyl, terphenyl, tetraphenyl, or bipyridyl, are also included in the definition of aromatic or heteroaromatic ring systems.

[0018] Aromatic or heteroaromatic ring systems having 5-40 ring atoms and being able to be linked to aromatic or heteroaromatic systems via any desired position refer to, for example, groups derived from the following: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, celestane, perylene, fluoranthene, benzo[a]fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, diphenylidene, terphenyl, diphenylidene, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans ind[a]fluorene, cis or trans monobenzo[a]ind[a]fluorene, cis or trans dibenzo[a]ind[a]fluorene, trimer indene, isotrimer indene. Spirotrimeric indene, spiroisotrimeric indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indole-carbazole, indole-carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenothiazine, pyrazole, indazole, imidazole, benzimidazole, naphthiamidazole, phenanthrenemidazole, pyridinium-imidazolium, quinoxaline-imidazolium, pyrazole Benzo[a]azole, naphtho[a]azole, anthraxazole, phenanthrene[a]azole, iso[a]azole, 1,2-thiazole, 1,3-thiazole, benzo[a]thiazole, pyridazine, benzo[a]pyridazine, pyrimidine, benzo[a]pyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenanthrene, phenothiazine, fluorescein ring, naphthidine, azacarbazole, benzo[a]carbline, phenanthrene, 1,2,3-triazine Azole, 1,2,4-triazole, benzotriazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 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, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indoleazine, and benzothiadiazole.

[0019] Furthermore, straight-chain alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms refer to, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methyl 1-Heptyl, n-Heptyl, 2-Heptyl, 3-Heptyl, 4-Heptyl, Cyclohepyl, 1-Methylcyclohexyl, n-Octyl, 2-Ethylhexyl, Cyclooctyl, 1-Bicyclo[2.2.2]Octyl, 2-Bicyclo[2.2.2]Octyl, 2-(2,6-Dimethyl)Octyl, 3-(3,7-Dimethyl)Octyl, Adamantyl, Trifluoromethyl, Pentafluoroethyl, 2,2,2-Trifluoroethyl, 1,1-Dimethyl-n-hex-1-yl, 1,1-Dimethyl- n-Hept-1-yl, 1,1-Dimethyl-n-oct-1-yl, 1,1-Dimethyl-n-dec-1-yl, 1,1-Dimethyl-n-dodecane-1-yl, 1,1-Dimethyl-n-tetradecane-1-yl, 1,1-Dimethyl-n-hexadecane-1-yl, 1,1-Dimethyl-n-octadecane-1-yl, 1,1-diethyl-n-hexane-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-octane-1-yl, 1,1-di Ethyl-n-decyl-1-yl, 1,1-diethyl-n-dodecyl-1-yl, 1,1-diethyl-n-tetradecyl-1-yl, 1,1-diethyl-n-hexadecyl-1-yl, 1,1-diethyl-n-octadecyl-1-yl, 1-(n-propyl)-cyclohexyl-1-yl, 1-(n-butyl)-cyclohexyl-1-yl, 1-(n-hexyl)-cyclohexyl-1-yl, 1-(n-octyl)-cyclohexyl-1-yl, and 1-(n-decyl)-cyclohexyl-1-yl groups. The term "cycloalkyl group" herein encompasses monocyclic, bicyclic, or polycyclic groups.

[0020] Alkenyl groups having 2 to 20 carbon atoms should be understood to refer to, for example, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, or cyclooctadienyl. Alkynyl groups having 2 to 20 carbon atoms should be understood to refer to, for example, ethynyl, propynyl, butynyl, penynyl, hexynyl, heptenyl, or octynyl.

[0021] A straight-chain alkyl group having 1 to 20 carbon atoms or a branched-chain alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S and at least one hydrogen atom may be replaced by D, F or CN, refers to, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methylbutoxy, thiomethyl, 1-thioethyl, 1-thioisopropyl, 1-thion-propyl, 1-thioisobutyl, 1-thion-butyl or 1-thiotert-butyl.

[0022] If an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, the alkyl group may be selected from the aforementioned alkyl groups.

[0023] In the context of this invention, adjacent carbon atoms refer to carbon atoms that are directly bonded to each other. Furthermore, in the definition of a group, "adjacent group" refers to groups that are bonded to the same or adjacent carbon atoms. In particular, these definitions also apply to the terms "adjacent group" and "adjacent substituent".

[0024] The phrase "two or more groups can form a ring system together" refers to the formation of an aliphatic, aromatic, or heteroaromatic ring system, and in the context of this specification, it should specifically refer to the two groups being chemically bonded together under conditions that formally eliminate two hydrogen atoms. This is illustrated by the following scheme: .

[0025] However, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group bonds to the position where the hydrogen atom is bonded, thereby forming a ring. This will be illustrated by the following scheme: .

[0026] The compounds of formula (1) and their preferred embodiments are described below.

[0027] The compounds of formula (1) of the present invention may be selected from compounds of formula (1a) or formula (1b), preferably selected from compounds of formula (1a): Equation (1a) or Equation (1b).

[0028] In a further preferred embodiment of the invention, Het 1 Selected from aromatic ring systems with 6-25 ring atoms or heteroaromatic ring systems with 5-24 ring atoms, wherein either ring system can be independently and arbitrarily controlled by R. 3Partial or complete replacement. More preferably, Het 1 Selected from aromatic ring systems with 6-18 ring atoms or heteroaromatic ring systems with 5-18 ring atoms, wherein either ring system can be independently and arbitrarily controlled by R. 3 To partially or completely replace.

[0029] Aromatic ring systems having 6 to 25 ring atoms are preferably selected from: ortho-, meta-, or para-phenyl; ortho-, meta-, or para-biphenyl; ortho-terphenyl, meta-terphenyl, para-terphenyl, or branched terphenyl; tetraphenyl, especially ortho-tetraphenyl, meta-tetraphenyl, para-tetraphenyl, or branched tetraphenyl; 1- or 2-naphthyl; anthracene, preferably 9-anthrayl; phenanthryl; biphenylenetriyl; 1-, 2-, 3-, or 4-fluorenyl; 1-, 2-, 3-, or 4-spirodifluorenyl; fluoranthyl; benzofluoranthyl; and dibenzoanthyl, and aromatic ring systems having 6 to 18 ring atoms are preferably selected from the above-mentioned phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, biphenylenetriyl, and fluoranthyl.

[0030] Furthermore, heteroaromatic ring systems having 5 to 24 ring atoms are preferably selected from the structures of the following formulas Het(1) to Het(5), if not a linking group: Het (1), Het (2), Het (3), Het (4), Het (5) in Indicates, for example, L 3 The connection, R 1 and R 2 It has the meaning given above; Or according to the structure of Het (6) to Het (17): , in Dashed lines represent lines such as L. 3 Or Het 1 The key to the connection, and R 5 The meaning is the same as R.

[0031] If Het 1The group is a heteroaromatic group having 5 to 24 ring atoms, and more preferably, the group is selected from the structures of formulas Het (1) to Het (4) and Het (6) to Het (17); more preferably, Het 1 It is a heteroaromatic group having 5 to 18 ring atoms and selected from the structure of formula Het (6) to Het (17), and the heteroaromatic group having 5 to 18 ring atoms is most preferably selected from the structure of formula Het (10) to Het (17).

[0032] In a further preferred embodiment of the invention, Het is selected from Het (1) to Het (3) or Het (5): Het (1), Het (2), Het (3) or Het (5), in Indicates with L 2 The key to the connection, and R 1 and R 2 It has the meaning given above.

[0033] Het is more preferably selected from Het (1), Het (2) and Het (3).

[0034] In another preferred embodiment of the invention, the linking group L 1 It is selected from aromatic ring systems with single bonds and 6 to 25 ring atoms, or heteroaromatic ring systems with 5 to 18 ring atoms. Particularly preferred is L... 1 It is an aromatic ring system with a single bond and 6 to 18 ring atoms, or a heteroaromatic ring system with 5 to 18 ring atoms. In the case of a heteroaromatic ring system, the ring system is preferably dibenzofuran or dibenzothiophene. These ring systems are optionally partially or completely substituted with D.

[0035] In yet another preferred embodiment of the invention, the linking group L 2 Selected from aromatic ring systems with single bonds or 6 to 25 ring atoms. Particularly preferred is L... 2 It is an aromatic ring system with single bonds or 6 to 18 ring atoms. The ring system is optionally partially or completely substituted by D.

[0036] Linking group L 3 Preferably, it is selected from aromatic ring systems with single bonds and 6 to 25 ring atoms, or heteroaromatic ring systems with 5 to 18 ring atoms. Particularly preferred is L... 3It is an aromatic ring system with a single bond and 6 to 18 ring atoms, or a heteroaromatic ring system with 5 to 18 ring atoms. In the case of a heteroaromatic ring system, the ring system is preferably dibenzofuran or dibenzothiophene. These ring systems are optionally partially or completely substituted with D.

[0037] The substituent R is preferably selected from: H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl or alkynyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein one or more non-adjacent CH2 groups can be replaced by O or S, and wherein at least one hydrogen atom can be replaced by D, F or CN, or an aromatic ring system having 6 to 24 ring atoms or a heteroaromatic ring system having 5 to 24 ring atoms, wherein at least one hydrogen atom can be replaced by D, F, Cl, Br, I or CN, and said aromatic ring system or heteroaromatic ring system can be replaced by one or more alkyl groups each having 1 to 4 carbon atoms; more preferably, R is selected from: H, D, F, CN, a straight-chain alkyl group having 1 to 6 carbon atoms or a branched or cyclic alkyl group having 2 to 10 carbon atoms. The alkyl or alkenyl group having 6 carbon atoms or a branched or cyclic alkyl group having 3 to 8 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S, and wherein at least one hydrogen atom may be replaced by D, F or CN; or an aromatic ring system having 6 to 18 ring atoms or a heteroaromatic ring system having 5 to 18 ring atoms, wherein at least one hydrogen atom may be replaced by D, F, Cl, Br, I or CN, and said aromatic ring system or heteroaromatic ring system may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, wherein R is more preferably selected from H, D, F, CN, an aromatic ring system having 6 to 12 ring atoms or a heteroaromatic ring system having 5 to 18 ring atoms, and R is most preferably selected from H, D, F, CN or an aromatic ring system having 6 to 12 ring atoms.

[0038] Substituent R 1 Preferably selected from: H, D, F, CN; straight-chain alkyl groups having 1 to 10 carbon atoms, or alkenyl or alkynyl groups having 2 to 10 carbon atoms, or branched or cyclic alkyl groups having 3 to 10 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S, and wherein at least one hydrogen atom may be replaced by D, F, or CN; or aromatic ring systems having 6 to 24 ring atoms, or heteroaromatic ring systems having 5 to 18 ring atoms, wherein at least one hydrogen atom may be replaced by D, F, Cl, Br, I, or CN, and said aromatic ring systems or heteroaromatic ring systems may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; more preferably, R 1 Selected from H, D, F, CN, aromatic ring systems with 6 to 12 ring atoms, or heteroaromatic ring systems with 5 to 18 ring atoms.

[0039] Substituent R2 Preferably, it is selected from aromatic ring systems having 6-24 ring atoms or heteroaromatic ring systems having 5-18 ring atoms, wherein either ring system is optionally and independently controlled by R. 4 Partial or complete replacement. More preferably, R 2 Selected from aromatic ring systems with 6-18 ring atoms or heteroaromatic ring systems with 5-18 ring atoms. Each ring system can be independently determined by R. 4 To partially or completely replace.

[0040] Substituent R 3 Preferably selected from: H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms, or an alkenyl or alkynyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein one or more non-adjacent CH2 groups can be replaced by O or S, and wherein at least one hydrogen atom can be replaced by D, F, or CN, or an aromatic ring system having 6 to 24 carbon atoms or a heteroaromatic ring system having 5 to 18 ring atoms, wherein at least one hydrogen atom can be replaced by D, F, Cl, Br, I, or CN, and said aromatic ring system or heteroaromatic ring system can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; simultaneously, two or more adjacent substituents R can together form an aliphatic, aromatic, or heteroaromatic ring system; more preferably, R 3 Selected from H, D, F, CN, straight-chain alkyl groups having 1 to 6 carbon atoms, aromatic ring systems having 6 to 12 ring atoms, or heteroaromatic ring systems having 5 to 18 ring atoms.

[0041] Substituent R 4 H or D are preferred.

[0042] In the context of this invention, the above preferred embodiments can be combined with each other as needed within the limitations of claim 1.

[0043] The present invention also provides a mixture comprising at least one compound of formula (1) and at least one other compound selected from matrix materials, phosphors, fluorescents and / or luminescent materials exhibiting TADF (thermally activated delayed fluorescence).

[0044] The present invention further provides a formulation comprising at least one compound or mixture of formula (1) as described above and at least one solvent.

[0045] The present invention also provides an organic electroluminescent device comprising an anode, a cathode and at least one organic layer comprising at least one compound of formula (1).

[0046] The preferred embodiments described above for the compounds of formula (1) are also applicable to the mixtures of the present invention, the formulations of the present invention, and the organic electroluminescent devices of the present invention.

[0047] Examples of compounds of formula (1) of the present invention are listed in Table (1) below.

[0048] Table 1:

[0049] The particularly suitable compounds of formula (1) are compounds E1 to E27 in Table 2 below:

[0050] The compounds of the present invention can be prepared using methods known to those skilled in the art, such as Suzuki coupling. The compounds of formula (1) of the present invention can be prepared according to the following scheme 1: Option 1:

[0051] Example: Unless otherwise stated, all the following synthesis was carried out in a dry solvent under a protective atmosphere. Potassium fluoride (spray-dried), tri-tert-butylphosphine, and palladium(II) acetate were available from ALDRICH. 3-Chloro-5,6-diphenyl-1,2,4-triazine was prepared according to a method similar to EP 577559. 2',7'-di-tert-butyl-spiro-9,9'-difluorene-2,7-diborate glycol ester was prepared according to WO 02 / 077060, and 2-chloro-4,6-diphenyl-1,3,5-triazine was prepared according to US 5,438,138. Spiro-9,9'-difluorene-2,7-bis(borate glycol ester) was prepared according to a method similar to WO 02 / 077060. The numbers of the reactants known in the literature (some of which are indicated in square brackets) are the corresponding CAS numbers.

[0052] a) 2,4-Dichloro-6-dibenzofuran-2-yl-1,3,5-triazine

[0053] 1.5 g (61 mmol, 1.12 equivalent) of magnesium shavings were heated in a four-necked flask for several minutes. Then, a few mL of a solution of 14.8 g (60 mmol, 1.10 equivalent) of 2-bromodibenzofuran in 100 mL of anhydrous THF was added until the Grignard reaction began. The remaining solution was then added gradually to maintain the Grignard reaction under reflux. Once the addition was complete, the mixture was immediately cooled to approximately 0 °C in an ice bath. In a second apparatus, a solution of 10.9 g (60 mmol, 1.0 equivalent) of 2,4,6-trichloro-1,3,5-triazine in 60 mL of anhydrous THF was cooled in an ice bath. The Grignard reagent was placed in a dropping funnel and gradually added to this solution. After stirring overnight at room temperature, the mixture was diluted with 100 mL of THF and 50 mL of 1 M HCl was added. The resulting precipitate was washed with water, ethanol, and heptane and recrystallized in toluene.

[0054] Yield: 12.7 g (40.4 mmol), 67% of theoretical value. 1 H The purity determined by NMR was approximately 98%.

[0055] The following compounds were prepared in a similar manner:

[0056] b) 2-Chloro-4-dibenzofuran-2-yl-6-bitriphenylide-2-yl-1,3,5-triazine

[0057] 1.5 g (61 mmol, 1.12 equivalent) of magnesium shavings were heated in a four-necked flask for several minutes. Then, 18.6 g (60 mmol, 1.10 equivalent) of a solution of 2-bromotriphenylide in 100 mL of anhydrous THF was added until the Grignard reaction began. The remaining solution was then added gradually to maintain the Grignard reaction under reflux. Once the addition was complete, the mixture was immediately cooled to approximately 0 °C in an ice bath. In a second apparatus, 18.9 g (60 mmol, 1.0 equivalent) of a solution of 2,4-dichloro-6-dibenzofuran-2-yl-1,3,5-triazine in 60 mL of anhydrous THF was cooled in an ice bath. The Grignard reagent was placed in a dropping funnel and gradually added to this solution. After stirring overnight at room temperature, the mixture was diluted with 100 mL of THF and 50 mL of 1 M HCl was added. The resulting precipitate was washed with water, ethanol, and heptane and recrystallized in toluene.

[0058] Yield: 21 g (42.5 mmol), 70% of theoretical value. 1 The purity determined by H NMR is approximately 98%.

[0059] The following compounds were prepared in a similar manner:

[0060] c) 2-[3-(4-dibenzofuran-2-yl-6-bitriphenylide-2-yl-1,3,5-triazin-2-yl)phenyl]-1-phenylbenzimidazole

[0061] 48.6 g (96 mmol, 1.0 equivalent) of 2-chloro-4-dibenzofuran-2-yl-6-bitriphenylide-2-yl-1,3,5-triazine, 34 g (108 mmol, 1.1 equivalent) of [3-(1-phenylbenzimidazol-2-yl)phenyl]boronic acid and 20.4 g (192 mmol, 2.0 equivalent) of sodium carbonate were dissolved in 400 ml toluene, 250 ml water and 190 ml ethanol under an inert atmosphere. Then 1.11 g (0.96 mmol, 0.01 equivalent) of tetrakis(triphenylphosphine)palladium was added, and the mixture was refluxed overnight at 110 °C. After the reaction was complete, 350 ml of water was added and the precipitated solid was filtered off. The organic layer was separated, washed with water and dried over sodium sulfate. After evaporation of the solvent, 5.1 g of crude product was obtained. The combined solids were subjected to thermal extraction with toluene / heptane, followed by recrystallization twice with toluene / heptane, and finally subjected to high vacuum (p=5×10). -5 Purification was achieved by sublimation at mbar.

[0062] Yield: 5.3 g (71 mmol), 75% of theoretical value. 1 The purity determined by H NMR was approximately 97%.

[0063] The following compounds were prepared in a similar manner:

[0064] d) 1-(4-Dibenzofuran-1-yl-6-bitriphenylide-2-yl-1,3,5-triazin-2-yl)-2-phenylbenzimidazole

[0065] 9.8 g (51 mmol) of 2-phenyl-1H-benzimidazole and 25.3 g (50 mmol) of 2-chloro-4-dibenzofuran-1-yl-6-bitriphenylide-2-yl-1,3,5-triazine were dissolved in 400 mL of toluene under an argon atmosphere. 1.0 g (5 mmol) of tri-tert-butylphosphine was added, and the mixture was stirred under an argon atmosphere. 0.6 g (2 mmol) of Pd(OAc)₂ was added, and the mixture was stirred under an argon atmosphere, followed by the addition of 9.5 g (99 mmol) of sodium tert-butoxide. The reaction mixture was stirred under reflux for 24 hours. After cooling, the organic phase was separated, washed three times with 200 mL of water, dried over MgSO₄, filtered, and the solvent was removed under reduced pressure. The residue was purified by column chromatography using silica gel (eluent: DCM / heptane (1:4)). The residue was recrystallized from toluene and finally purified under high vacuum (p=5×10⁻⁶). -5 Sublimation at mbar. Purity is 99.9%.

[0066] The yield was 21.9 g (33 mmol), which is 66% of the theoretical value.

[0067]

[0068] A suitable method for partially or completely deuterating a compound of formula (1) of the present invention by exchanging one or more hydrogen atoms for deuterium atoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more deuterium atoms and capable of releasing these deuterium atoms under suitable conditions.

[0069] The platinum catalyst is preferably carbon-supported dry platinum, more preferably 5% carbon-supported dry platinum. The palladium catalyst is preferably carbon-supported dry palladium, more preferably 5% carbon-supported dry palladium. Suitable deuterium sources are D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, or toluene-d8. Preferred deuterium sources are D2O or a combination of D2O and a fully deuterated organic solvent. Particularly preferred deuterium sources are combinations of D2O and fully deuterated organic solvents, wherein the fully deuterated solvent is not limited. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. Particularly preferred deuterium sources are combinations of D2O and toluene-d8. The reaction is preferably carried out under heating, more preferably at a temperature of 100°C-200°C. Furthermore, the reaction is preferably carried out under pressure.

[0070] Using the methods detailed above, further purification such as recrystallization or sublimation can be performed if necessary to obtain high purity, preferably at least 90% purity (through...). 1 Compounds of formula (1) (determined by ¹H NMR and / or HPLC).

[0071] For the purpose of processing the compounds of the present invention from a liquid state, for example by spin coating or printing, formulations of the compounds of the present invention, or mixtures of the compounds of the present invention with other functional materials such as matrix materials, fluorescent emitters, phosphorescent emitters, and / or emitters exhibiting TADF, are desired. These formulations may be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents may be preferred. Suitable and preferred solvents include, for example: toluene; anisole; o-, m-, or p-xylene; methyl benzoate; mesitylene; tetrahydronaphthalene; veratrine ether; THF; methyl-THF; THP; chlorobenzene; dimethylbenzene; phenoxytoluene, especially 3-phenoxytoluene; (-)-fenone; 1,2,3,5-tetramethylbenzene; 1,2,4,5-tetramethylbenzene; 1-methylnaphthalene; 2-methylbenzothiazole; 2-phenoxyethanol; 2-pyrrolidone; 3-methyl anisole; 4-methyl anisole; 3,4-dimethyl anisole; 3,5-dimethyl anisole; acetophenone; α-terpineol; benzothiazole; butyl benzoate; isopropylbenzene; cyclohexanol; cyclohexanone; cyclohexyl Benzene; decahydronaphthalene; dodecylbenzene; ethyl benzoate; indene; NMP; p-methylisopropylbenzene; phenethyl ether; 1,4-diisopropylbenzene; dibenzyl ether; diethylene glycol butyl methyl ether; triethylene glycol butyl methyl ether; diethylene glycol dibutyl ether; triethylene glycol dimethyl ether; diethylene glycol monobutyl ether; tripropylene glycol dimethyl ether; tetraethylene glycol dimethyl ether; 2-isopropylnaphthalene; pentylbenzene; hexylbenzene; heptylbenzene; octylbenzene; 1,1-bis(3,4-dimethylphenyl)ethane; 2-methylbiphenyl; 3-methylbiphenyl; 1-methylnaphthalene; 1-ethylnaphthalene; ethyl octanoate; diethyl sebacate; octyl octanoate; heptylbenzene; menthyl isovalerate; cyclohexyl hexanoate; or mixtures of these solvents.

[0072] The compounds of formula (1) of the present invention described above, preferably compounds of formula (1a) or compounds E1 to E27, are suitable for use in organic electroluminescent devices, preferably in organic light-emitting transistors (OLETs), organic field quenching devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers), or organic light-emitting diodes (OLEDs). The organic electroluminescent devices of the present invention are particularly organic light-emitting diodes or organic light-emitting electrochemical cells. The devices of the present invention are more preferably OLEDs.

[0073] The organic layer of the device of the present invention preferably includes, in addition to the light-emitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), an exciton blocking layer, an electron blocking layer, and / or a charge generation layer. The device of the present invention may also include two or more layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. Similarly, for example, an intermediate layer with exciton blocking function may be introduced between two light-emitting layers.

[0074] If multiple emitting layers are present, these emitting layers preferably have multiple emission peaks in the general range of 380 nm to 750 nm, resulting in overall white emission; in other words, various luminescent or phosphorescent compounds can be used in the emitting layers. A system with three emitting layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. As an alternative to this combination, a single emitting layer may also emit yellow light. Such combinations are known to those skilled in the art. The organic electroluminescent device of the present invention can also be a tandem electroluminescent device, especially for white-emitting OLEDs. The device may also contain other layers of inorganic materials or materials entirely composed of inorganic materials.

[0075] For those skilled in the art, there is no difficulty in selecting a suitable material for the layer of the aforementioned organic electroluminescent device by considering the various materials known in the prior art. Those skilled in the art will consider the chemical and physical properties of the materials in a conventional manner, as they are aware that materials interact with each other in organic electroluminescent devices. This involves, for example, the energy levels of orbitals (HOMO, LUMO) or triplet and singlet energy levels, but also other material properties.

[0076] The compounds of formula (1) of the present invention, as described above or preferably, or listed in Tables 1 or 2, can be used in different layers depending on the specific structure. Preferably, organic electroluminescent devices contain compounds of formula (1) or the preferred embodiments described above in at least one emitting layer as matrix materials (synonymous with host materials) for phosphorescent emitters, phosphorescent emitters, or emitters exhibiting TADF (thermally activated delayed fluorescence), especially for phosphorescent emitters. Furthermore, the compounds of the present invention can also be used in at least one electron transport layer and / or at least one hole transport layer and / or at least one exciton blocking layer and / or at least one hole blocking layer. It is particularly preferred to use the compounds of the present invention as matrix materials in at least one emitting layer or as electron transport materials or hole blocking materials in electron transport layers or hole blocking layers.

[0077] In a preferred embodiment of the present invention, the compounds of formula (1), preferred formula (1a) of the present invention, or the compounds listed in Table 1 or Table 2 can be used as matrix materials in at least one light-emitting layer, wherein the layer contains at least one other matrix material (referred to as a mixed matrix system).

[0078] Suitable matrix materials that can be used in combination with the compounds of this invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, bicarbazoles, indoloxacarbazole derivatives, indoxacarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, borazine or borate esters, triazine derivatives, zinc complexes, diazacyclopentane or tetrazacyclopentane derivatives, phosphazacyclopentane derivatives, bridged carbazole derivatives, biphenylide derivatives, or dibenzofuran derivatives. Similarly, other phosphorescent emitters with shorter emission wavelengths than the actual emitters may be present in the mixture as co-hosts, or compounds that do not participate significantly in charge transport, such as wide-bandgap compounds, may be present as needed.

[0079] Wide bandgap material is defined herein as a material within the scope of the disclosure of US 7,294,849, characterized in that the bandgap is at least 3.5 eV, the bandgap being the gap between the HOMO and LUMO energies of the material.

[0080] Other particularly suitable matrix materials that can be advantageously combined in the system with compounds of formula (1) as described above or preferably, may be selected from compounds of formulas (2) to (12) as described below.

[0081] Therefore, the present invention also provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode and at least one organic layer comprising at least one light-emitting layer, wherein the at least one light-emitting layer comprises at least one compound of formula (1) as described above or preferably as matrix material 1 and at least one compound of formula (2) to (12) as matrix material 2.

[0082] Equation (2)

[0083] Equation (3)

[0084] Equation (4)

[0085] Equation (5)

[0086] The symbols and markings used are as follows: A 1 For C(R)7 2. NR 7 , O or S; A is independently a group of formula (6) or (7) in all cases.

[0087] Equation (6)

[0088] Equation (7);

[0089] Equation (8)

[0090] Equation (9)

[0091] Equation (10)

[0092] Equation (11)

[0093] Equation (12)

[0094] X2 may be the same or different in various situations, and is CH, CR 6 Or N, where no more than two of the symbols X2 can be N; Indicates the bonding site with equation (5); R 6 In various cases, they may be the same or different and are: D, CN, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group may in various cases be one or more R 7 The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 7 2. C=O, NR 7 O, S or CONR 7 Replacement, or having 5 to 60 ring atoms and in various cases can be replaced by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two R groups... 6 Groups can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems together; Ar can be the same or different in various cases, and can have 5 to 40 ring atoms and can be converted by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; Ar 1 They may be the same or different in various cases, and are for those with 5 to 40 ring atoms and can be generated by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; R 7 They may be the same or different under various conditions and are: D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 )3, B(OR 8 )2,C(=O)R 8 , P(=O)(R 8 )2,S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group may, in various cases, be one or more R 8 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Replacement, or having 5 to 40 ring atoms and in various cases can be replaced by one or more R atoms. 8 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 7 The groups can together form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; preferably, R 7 The group does not form any such ring system; R 8 In various cases, they may be the same or different and are: H, D, F, or an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 carbon atoms, especially a hydrocarbon group, wherein one or more hydrogen atoms may be replaced by F; c, c1, and c2 are each independently 0 or 1 in various cases, and the sum of the markings in all cases, c+c1+c2, is 1; d, d1, and d2 are each independently 0 or 1 in various cases, and the sum of the markings in all cases, d+d1+d2, is 1; q, q1, and q2 are each independently 0 or 1 in various situations; s can be the same or different in various cases and can be 0, 1, 2, 3 or 4; t can be the same or different in various cases and can be 0, 1, 2 or 3; u is the same or different in various cases and is 0, 1, or 2; and v is 0 or 1.

[0095] In the compounds of formulas (2), (3), (4) and (8) to (12), when R 6 When the group is not D, s is preferably 0 or 1, more preferably 0.

[0096] In compounds of formula (2), (3) or (4), when R 6 When the group is not D, t is preferably 0 or 1, more preferably 0.

[0097] In the compounds of formulas (2), (3), (4) and (8) to (12), when R 6 When the group is not D, u is preferably 0 or 1, more preferably 0.

[0098] The sum of the labels s, t, and u in the compounds of formulas (2), (3), (4), and (8) to (12) preferably does not exceed 6, particularly preferably does not exceed 4, and more preferably does not exceed 2. When R 6 If it is not D, then this is the preferred option.

[0099] In the compound of formula (5), c, c1, and c2 are each independently 0 or 1 in various cases, wherein the sum of c + c1 + c2 is 1 in various cases. c2 is preferably defined as 1.

[0100] In a preferred embodiment of the invention, compounds of formulas (2) to (5) and (8) to (12) may be combined with compounds of formula (1) of the invention, wherein R 6 In various cases, they may be the same or different and are selected from: D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group may in various cases be one or more R 7 Group substitution, or having 5 to 60 ring atoms, preferably 5 to 40 ring atoms, and in various cases can be replaced by one or more R groups. 7 Aromatic or heteroaromatic ring systems with substituted groups.

[0101] In other preferred embodiments of the invention, compounds of formulas (2) to (5) and (8) to (12) may be combined with compounds of formula (1) of the invention, wherein R 6 They may be the same or different in various cases, and are selected from D or have 6 to 30 ring atoms and can be generated by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups.

[0102] Preferably, the Ar in the compounds of formulas (2), (3), (4) and (8) to (12) 1Selected from: phenyl; biphenyl, especially ortho-, meta-, or para-biphenyl; terphenyl, especially ortho-, meta-, or para-terphenyl or branched terphenyl; tetraphenyl, especially ortho-, meta-, or para-tetraphenyl or branched tetraphenyl; fluorenyl groups that may be linked at positions 1, 2, 3, or 4; spirodifluorenyl groups that may be linked at positions 1, 2, 3, or 4; naphthyl, especially 1- or 2-bonded naphthyl; or groups derived from indole, benzofuran, benzothiophene, carbazole groups that may be linked at positions 1, 2, 3, or 4, dibenzofuran groups that may be linked at positions 1, 2, 3, or 4, dibenzothiophene groups that may be linked at positions 1, 2, 3, or 4, indocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or terphenylidene groups, each of which may be linked by one or more R 7 Group substitution. Ar1 is preferably unsubstituted.

[0103] When A in equation (3) or (4) 1 For NR 7 When the substituent R is bonded to the nitrogen atom 7 Preferably, it has 5 to 24 aromatic ring atoms and can also be divided by one or more R 8 Aromatic or heteroaromatic ring systems substituted with a substituent group. In a particularly preferred embodiment, the substituent R... 7 In various cases, they may be the same or different and are aromatic or heteroaromatic ring systems with 6 to 24 aromatic ring atoms, especially with 6 to 18 aromatic ring atoms. R 7 Preferred embodiments include: phenyl, biphenyl, terphenyl, and tetraphenyl, wherein the group is preferably unsubstituted; and groups derived from triazine, pyrimidine, and quinazoline, wherein the groups may be substituted by one or more R... 8 Group substitution.

[0104] When A in equation (3) or (4) 1 For C(R) 7 At 2, the substituent R bonded to the carbon atom 7 In various cases, it is preferred that the same or different linear alkyl groups having 1 to 10 carbon atoms, or branched or cyclic alkyl groups having 3 to 10 carbon atoms, or aromatic or heteroaromatic ring systems having 5 to 24 aromatic ring atoms, wherein the groups may also be composed of one or more R 8 Group substitution. Most preferably, R 7 It is a methyl group or a phenyl group. In this case, R 7 Groups can also form ring systems together, thus forming spirocyclic systems.

[0105] In a preferred embodiment of the compounds of formulas (2) to (5) and (8) to (12), these compounds are partially or completely deuterated, more preferably completely deuterated.

[0106] The preparation of compounds of formulas (2) to (5) and (8) to (12) is generally known, and some compounds are commercially available.

[0107] The compounds of formula (5) are disclosed in the examples on pages 110 to 119, and especially on pages 120 to 127, of WO 2021 / 180614. Their preparation is disclosed in the synthetic examples on pages 128 and 214 to 218 of WO 2021 / 180614.

[0108] If the other matrix materials are deuterated compounds, then the other matrix materials can be a mixture of deuterated compounds with the same basic chemical structure but different degrees of deuteration.

[0109] In a preferred embodiment of other matrix materials, it is a mixture of deuterated compounds of formulas (2) to (5) and (8) to (12) as described above, wherein the degree of deuteration of these compounds is at least 50% to 90%, preferably 70% to 100%. The corresponding deuteration methods are known to those skilled in the art and have been described, for example, in KR2016041014, WO2017 / 122988, KR202005282, KR101978651 and WO2018 / 110887, or in the Bulletin of the Chemical Society of Japan, 2021, Vol. 94 (No. 2), pp. 600-605, or in the Asian Journal of Organic Chemistry, 2017, Vol. 6 (No. 8), pp. 1063-1071.

[0110] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for deuterium atoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more deuterium atoms and capable of releasing them under suitable conditions.

[0111] The platinum catalyst is preferably carbon-supported dry platinum, more preferably 5% carbon-supported dry platinum. The palladium catalyst is preferably carbon-supported dry palladium, more preferably 5% carbon-supported dry palladium. Suitable deuterium sources are D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, or toluene-d8. Preferred deuterium sources are D2O or a combination of D2O and a fully deuterated organic solvent. Particularly preferred deuterium sources are combinations of D2O and fully deuterated organic solvents, wherein the fully deuterated solvent is not limited. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. Particularly preferred deuterium sources are combinations of D2O and toluene-d8. The reaction is preferably carried out under heating, more preferably at a temperature of 100°C-200°C. Furthermore, the reaction is preferably carried out under pressure.

[0112] Examples of other suitable matrix materials that can be combined with the compounds of formula (1) as described above or preferably described are: the compounds described in Table 3 on pages 137 to 203 of WO2019 / 229011, which may also be partially or completely deuterated; or the compounds described in Table 3 on pages 131 to 127 and Table 4 on pages 137 to 139 of WO2021 / 180625; or the compounds [2-1] to [2-110] on pages 42 to 47 of KR20230034896A or the compounds [3-1] to [3-26] on pages 49 to 51, which may also be partially or completely deuterated.

[0113] Other examples of host materials suitable for combination with compounds of formula (1) as described above or preferably, or compounds of formula (1a) as preferred, are the structures given in Tables 3 and 4 below.

[0114] Table 3:

[0115] The compounds listed in Table 4 are particularly suitable host materials for use in the electroluminescent devices of the present invention, selected according to the invention and preferably in combination with at least one compound of formula (1) or preferably a compound of formula (1a).

[0116] Table 4:

[0117] The preferred description of the foregoing formula (1) and its embodiments or the compounds in Table 1, as well as the host materials of compounds E1 to E27, can be combined with the foregoing matrix materials / host materials, the matrix materials / host materials of formulas (2) to (5) and (8) to (12), and the preferred description of their embodiments or compounds H1 to H30 in Table 3, as needed, in the device of the present invention.

[0118] The very particularly preferred mixtures of the compound of formula (1) used in the device of the present invention with the main materials of formulas (2) to (5) and (8) to (12) are obtained by combining compounds E1 to E27 with compounds H1 to H27, as shown in Table 5 below. For example, the first mixture M1 is a combination of compound E1 and H1.

[0119] Table 5:

[0120] Based on the entire mixture or the entire composition of the light-emitting layer, the concentration of the main material of formula (1) as described above or preferably in the mixture of the present invention or in the light-emitting layer of the device of the present invention is generally in the range of 5 wt% to 90 wt%, preferably in the range of 10 wt% to 85 wt%, more preferably in the range of 20 wt% to 85 wt%, even more preferably in the range of 30 wt% to 80 wt%, very particularly preferably in the range of 20 wt% to 60 wt%, and most preferably in the range of 30 wt% to 50 wt%.

[0121] Based on the entire mixture or the entire composition of the light-emitting layer, the total concentration of all the main materials of formulas (2) to (5) and (8) to (12) as described above or preferably in the light-emitting layer of the device of the present invention is generally in the range of 10 wt% to 95 wt%, preferably in the range of 15 wt% to 90 wt%, more preferably in the range of 15 wt% to 80 wt%, even more preferably in the range of 20 wt% to 70 wt%, very particularly preferably in the range of 40 wt% to 80 wt%, and most preferably in the range of 50 wt% to 70 wt%.

[0122] The present invention also relates to a mixture comprising, in addition to the host material of formula (1) referred to as host material 1 below as described above or preferably described, and at least one host material of formulas (2) to (5) and (8) to (12) referred to as host material 2 below, at least one phosphorescent material.

[0123] The present invention also relates to mixtures selected from M1 to M729, wherein the mixture further comprises at least one phosphorescent luminescent material.

[0124] Therefore, the present invention also provides an organic electroluminescent device comprising an anode, a cathode, and at least one organic layer, the organic layer comprising at least one light-emitting layer, wherein the at least one light-emitting layer comprises at least one compound of formula (1) as described above or preferably as a matrix material 1 and at least one compound of formula (13):

[0125] Equation (13)

[0126] The symbols and markings used are as follows: W represents O, S, C(R) 9 2. N-Ar 2 ; R 9 Independently, in various cases, it refers to: a straight-chain or branched alkyl group having 1 to 4 carbon atoms and being partially or fully deuterated, or an unsubstituted or partially or fully deuterated aromatic ring system having 6 to 18 carbon atoms, wherein two substituents R 9 Together with the carbon atoms they are bonded to, they can form monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic unsubstituted, partially deuterated, or fully deuterated ring systems, which can be substituted by one or more substituents R. 12 replace; Ar 2 They may be the same or different in various cases, and are for those with 5 to 30 ring atoms and can be generated by one or more R atoms. 12 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two Ar atoms bonded to the same nitrogen, phosphorus, or boron atom. 2 Groups can also be formed via single bonds or selected from C(R) 12 2. The bridging bases in O or S are interconnected; R 10 They may be the same or different in various cases, and are selected from: F, Cl, Br, I, CN, NO2, C(=O)R', P(=O)(Ar1)2, P(Ar 2 )2, B(Ar 2)2, Si(Ar1)3, Si(R')3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of which may be substituted by one or more R' groups, wherein one or more non-adjacent CH2 groups may be substituted by R'C=CR', Si(R')2, C=O, C=S, C=NR', P(=O)(R'), SO, SO2, NR', O, S, or CONR', and wherein one or more hydrogen atoms may be substituted by D, F, Cl, Br, I, CN, or NO2; R' may be the same or different in various cases and is selected from: D, F, Cl, Br, I, CN, NO2, N(Ar1)2, NH2, N(R'')2, C(=O)Ar1, C(=O)H, C(=O)R'', P(=O)(Ar1)2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R'' groups, wherein one or more non-adjacent CH2 groups may be HC=CH, R''C=CR'', C≡C, Si(R')2, Ge(R'')2, Sn (R'')2, C=O, C=S, C=Se, C=NR'', P(=O)(R''), SO, SO2, NH, NR'', O, S, CONH or CONR'', wherein one or more hydrogen atoms may be replaced by F, Cl, Br, I, CN or NO2, having 5 to 60 aromatic ring atoms and being substituted by one or more R'' groups in various cases, having 5 to 60 aromatic ring atoms and being substituted by one or more R'' groups, or combinations of these systems, wherein two or more adjacent substituents R' may optionally form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system that may be substituted by one or more R'' groups; R'' may be the same or different in various cases and is selected from: D, F, CN, aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and said aromatic or heteroaromatic ring system may be replaced by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more adjacent R'' 3 Substituents can together form monocyclic or polycyclic aliphatic ring systems; R' may be the same or different in various cases, and is an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 carbon atoms, especially a hydrocarbon group, in which one or more hydrogen atoms may also be replaced by F; R 11 They may be the same or different under various conditions, and are selected from: F, Cl, Br, I, CN, NO2, N (Ar) 2 )2,NH2,N(R 12 )2,C(=O)Ar 2 C(=O)H, C(=O)R 12 , P(=O)(Ar 2 )2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted with one or more R 12 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by HC=CH, R 12 C=CR 12 C≡C, Si(R) 12 )2、Ge(R 12 )2、Sn(R 12 )2. C=O, C=S, C=Se, C=NR 12 P(=O)(R) 12 SO, SO2, NH, NR 12 O, S, CONH or CONR 12 Replacement, and one or more of the hydrogen atoms can be replaced by D, F, Cl, Br, I, CN or NO2, having 5 to 60 ring atoms and in various cases can be replaced by one or more R 12 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 60 ring atoms and being substituted by one or more R groups. 12 A group-substituted aryloxy or heteroaryloxy group, or a combination of these systems, wherein two or more adjacent substituents R 11 Optionally formed that can be generated by one or more R 12 Monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring systems with substituted groups; R 12In various cases, the same or different, and selected from: D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S and wherein one or more hydrogen atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 30 ring atoms and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, wherein the aromatic or heteroaromatic ring system may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; and simultaneously, two or more adjacent substituents R 12 They can form monocyclic or polycyclic aliphatic ring systems together; x and x1 are independently 0, 1, 2, 3 or 4 in various cases; y and z are each independently 0, 1, or 2; a1 and a2 are each independently 0, 1, 2, 3, 4 or 5; a3 can be 0, 1, 2, or 3; a4 can be 0, 1, 2, 3 or 4.

[0127] Compounds of formula (13) are described, for example, on pages 110 to 119 of WO2021180614, particularly as examples on pages 120 to 127. Their preparation is disclosed in the synthetic examples on pages 128 and 214 to 218 of WO202118.

[0128] When the compounds of formula (1) of the present invention, or preferred embodiments thereof, are used alone as matrix materials or in a mixed matrix system of luminescent compounds in the luminescent layer, they are preferably used in combination with one or more phosphorescent materials (triple emitters). The term "phosphorescent emitter" generally includes compounds that emit light via spin-forbidden transitions from excited states with higher spin multiplicity, i.e., spin states > 1, such as by transitions from triplet states or states with even higher spin quantum numbers, such as quintet states. This means that triplet transitions are preferred.

[0129] Suitable phosphorescent emitters (= triplet emitters) are in particular compounds that emit light when properly excited, preferably in the visible light region, and further contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially metals having such atomic numbers. Preferred phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, especially compounds containing iridium or platinum. In the context of this invention, all luminescent compounds containing the aforementioned metals are considered phosphorescent emitters.

[0130] Generally, all phosphorescent complexes known to those skilled in the art in the field of phosphorescent OLEDs and organic electroluminescent devices are suitable.

[0131] Therefore, the present invention also provides an organic electroluminescent device as described above or preferably, characterized in that the light-emitting layer contains at least one phosphorescent material in addition to the host materials 1 and 2.

[0132] Preferred examples of phosphorescent emitters are described in Table 5 on pages 120 to 126 and Table 6 on pages 127 to 129 of WO2019 / 007867. These emitters are incorporated herein by reference.

[0133] Table 6 below lists examples of particularly preferred phosphorescent emitters.

[0134] Table 6:

[0135] The light-emitting layer of the organic electroluminescent device of the present invention, which contains at least one phosphorescent light-emitting element, is preferably an infrared light-emitting layer or a yellow-, orange-, red-, green-, blue-, or ultraviolet-light-emitting layer, more preferably a yellow- or green-light-emitting layer, and most preferably a green-light-emitting layer.

[0136] The yellow emitting layer here refers to a layer with a maximum photoluminescence value in the range of 540 to 570 nm. The orange emitting layer refers to a layer with a maximum photoluminescence value in the range of 570 to 600 nm. The red emitting layer refers to a layer with a maximum photoluminescence value in the range of 600 to 750 nm. The green emitting layer refers to a layer with a maximum photoluminescence value in the range of 490 to 540 nm. The blue emitting layer refers to a layer with a maximum photoluminescence value in the range of 440 to 490 nm. Here, the maximum photoluminescence value of the layer is determined by measuring the photoluminescence spectrum of a layer with a thickness of 50 nm at room temperature, wherein the layer comprises a combination of the host material 1 of formula (1), especially formula (1a) of the present invention, and a host material 2 composed of at least one of (2) to (5) and (8) to (13), and a corresponding emitting body.

[0137] For example, a commercial photoluminescence spectrometer is used to record the photoluminescence spectrum of the layer.

[0138] The photoluminescence spectrum of the selected luminescent material is typically in the range of 10 at room temperature. -5Measurements are taken in an oxygen-free solution, with the suitable solvent being any solvent in which the selected luminescent material is dissolved at the stated concentration. Particularly suitable solvents are typically toluene or 2-methyl-THF, but dichloromethane may also be used. Measurements are performed using a commercial photoluminescence spectrometer. The triplet energy T1, in eV, is determined from the photoluminescence spectrum of the luminescent material. First, the peak maximum value Plmax of the photoluminescence spectrum is determined (in nm). Then, the peak maximum value Plmax (in nm) is converted to eV using the following formula: E(T1, in eV) = 1240 / E(T1, in nm) = 1240 / PLmax (in nm).

[0139] Therefore, the preferred phosphorescent emitter is a yellow emitter, preferably derived from Table 6, wherein the triplet energy T1 of the yellow emitter is preferably about 2.3 eV to about 2.1 eV.

[0140] Therefore, the preferred phosphorescent emitter is a green emitter, preferably derived from Table 6, wherein the triplet energy T1 of the green emitter is preferably about 2.5 eV to about 2.3 eV.

[0141] Most preferably, the green light emitter described above, preferably the green light emitter in Table 6, is selected for use in the mixture of the present invention or the light-emitting layer of the present invention.

[0142] The fluorescent light emitter may also be present in the light-emitting layer of the device of the present invention or in the mixture of the present invention.

[0143] Preferred fluorescent compounds are selected from arylamines, wherein at least one of the aromatic or heteroaromatic ring systems of the arylamine is preferably a fused ring system, more preferably a fused ring system having at least 14 ring atoms. Preferred examples are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyreneamines, aromatic pyrene diamines, aromatic pyrine amines, or aromatic pyrine diamines. An aromatic anthraceneamine is a compound in which one diaryl amino group is directly bonded to an anthracene group, preferably at the 9-position. An aromatic anthracene diamine is a compound in which two diaryl amino groups are directly bonded to an anthracene group, preferably at the 9 and 10 positions. Aromatic pyreneamines, pyrene diamines, pyrine amines, and pyrine diamines are defined similarly, wherein the diaryl amino groups are preferably bonded to the 1-position or the 1-6-position of pyrene. Also preferred luminescent compounds are indoxfluoreneamine or indoxfluorene diamine, benzo[a]indoxfluoreneamine or benzo[a]indoxfluorene diamine and dibenzo[a]indoxfluoreneamine or dibenzo[a]indoxfluorene diamine, and indoxfluorene derivatives having fused aryl groups. Also preferred are pyrene arylamines. Also preferred are benzo[a]indoxfluoreneamine, benzo[a]fluoreneamine and extended benzo[a]indoxfluorene, phenazine, and fluorene derivatives linked to furan or thiophene units. The luminescent device of the present invention or the mixtures of the present invention may further comprise materials exhibiting TADF (thermally activated delayed fluorescence).

[0144] In other preferred embodiments of the invention, at least one light-emitting layer of the organic electroluminescent device may contain other host materials or matrix materials besides the host materials (matrix materials) 1 and 2 as described or preferably as described above, referred to as a hybrid matrix system. These hybrid matrix systems preferably contain three or four different matrix materials, more preferably three different matrix materials (in other words, in addition to host materials 1 and 2 as described above, they also contain one other matrix component). Matrix materials particularly suitable for use as matrix components in hybrid matrix systems are selected from wide-bandgap materials, bipolar host materials, electron transport materials (ETM), and hole transport materials (HTM).

[0145] In another embodiment of the invention, the mixture contains no other components besides the main material and main material 2 of formula (1) as described above, i.e., functional materials. These substances are therefore material mixtures used to manufacture the luminescent layer. These mixtures are also called premixed systems, which are used as the sole material source in the vapor deposition of the main material of the luminescent layer and have a constant mixing ratio in the vapor deposition. In this way, vapor deposition of a layer with a uniform component distribution can be achieved simply and quickly without the need to precisely activate multiple material sources.

[0146] In an alternative embodiment of the invention, the mixture, in addition to the components of the host material and host material 2 of formula (1) as described above, also contains the phosphorescent emitter as described above. When the mixing ratio is appropriate during vapor deposition, the mixture can also be used as the sole material source as described above.

[0147] The preferred premixed system consists of two matrix materials, namely compounds of formula (I), especially formula (Ia), and compounds of one of formulas (2) to (5) and (8) to (13).

[0148] It is also preferred that the premixed system consists of three matrix materials, namely compounds of formula (1), especially formula (1a), and two of formulas (2) to (5) and (8) to (13).

[0149] Therefore, the components or composition of the light-emitting layer of the device of the present invention can be processed by vapor deposition or from solution. For this purpose, the host materials 1 and 2, as described above or preferably, are provided in a formulation containing at least one solvent, optionally in combination with the materials of the phosphorescent emitter as described above or preferably. Suitable formulations have been described above.

[0150] Based on the overall composition of the luminescent material and the matrix material, the luminescent layer and luminescent compound in the device of the present invention according to a preferred embodiment preferably contain 99.9 vol%-1 vol%, more preferably 99 vol%-10 vol%, particularly preferably 98 vol%-60 vol%, and very particularly preferably 97 vol%-80 vol% of a matrix material, said matrix material being composed of at least one compound of formula (1) and at least one compound of formulas (2) to (5) and (8) to (13) according to a preferred embodiment. Accordingly, based on the overall composition of the luminescent layer composed of the luminescent material and the matrix material, the luminescent layer in the device of the present invention preferably contains 0.1 vol%-99 vol%, more preferably 1 vol%-90 vol%, more preferably 2 vol%-40 vol%, and most preferably 3 vol%-20 vol% of a luminescent material. If the compound is processed by solution, it is preferable to use the corresponding weight % rather than the above-mentioned volume % amount.

[0151] The present invention also relates to an organic electroluminescent device as described above or preferably, wherein the organic layer comprises a hole injection layer (HIL) and / or a hole transport layer (HTL), wherein the hole injection material and the hole transport material belong to the arylamine class.

[0152] The preferred order of the layers in the organic electroluminescent device of the present invention is as follows: Anode / hole injection layer / hole transport layer / light emission layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0153] This order of the layers is a preferred order.

[0154] At the same time, it should be pointed out again that not all of the mentioned layers need to exist and / or other layers may exist.

[0155] The material used for the electron transport layer, in addition to the compounds of formula (1) of the present invention, may be any material used in the prior art as an electron transport material in an electron transport layer. Particularly suitable are: aluminum complexes such as Alq3, zirconium complexes such as Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, diazole derivatives, aromatic ketones, lactams, boranes, phosphazacyclopentane derivatives, and phosphine oxide derivatives.

[0156] Suitable cathodes for the devices of the present invention are metals, metal alloys, or multilayer structures composed of multiple metals, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Yb, Sm, etc.). Also suitable are alloys composed of alkali metals or alkaline earth metals and silver, such as alloys composed of magnesium and silver. In the case of multilayer structures, in addition to the aforementioned metals, other metals with relatively high work functions, such as Ag or Al, may be used; in this case, combinations of the aforementioned metals are typically used, such as Ca / Ag, Mg / Ag, or Ba / Ag. It is also preferable to introduce a thin interlayer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of useful materials for this purpose are alkali metal fluorides or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.). Furthermore, lithium hydroxyquinoline (LiQ) can also be used for this purpose. The thickness of this layer is preferably 0.5 nm to 5 nm.

[0157] The preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, metals with high redox potentials, such as Ag, Pt, or Au, are suitable for this purpose. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are preferred. x Al / PtO x Alternatively, a conductive mixed metal oxide may be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to allow irradiation of organic materials (organic solar cells) or coupling of output light (OLEDs, O-lasers). The preferred anode material here is a conductive mixed metal oxide. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Conductive doped organic materials, especially conductive doped polymers, are also preferred. Furthermore, the anode may also consist of two or more layers, such as an inner ITO layer and an outer metal oxide layer, preferably tungsten oxide, molybdenum oxide, or vanadium oxide.

[0158] The organic electroluminescent device of the present invention requires appropriate structuring, contact connection and final sealing during manufacturing (depending on the application) because the lifespan of the device will be shortened in the presence of water and / or air.

[0159] The fabrication of the device of the present invention is not limited herein. One or more organic layers, including a light-emitting layer, can be coated by sublimation. In this case, the material is sublimated in a vacuum sublimation system at a temperature of less than 10... -5 mbar, preferably less than 10 -6An initial pressure of mbar is applied via vapor deposition. However, in this case, it is also feasible to use a much lower initial pressure, for example, below 10 mbar. -7 mbar.

[0160] The organic electroluminescent device of the present invention is preferably characterized in that one or more layers are coated by an OVPD (organic vapor deposition) method or by means of carrier gas sublimation. In this case, at 10 -5 The material is applied under a pressure of mbar-1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and thereby structured (e.g., MS Arnold et al., Appl. Phys. Lett., 2008, 92, 053301).

[0161] The organic electroluminescent device of the present invention is further preferably characterized in that one or more organic layers comprising the composition of the present invention are manufactured by solution processing, for example by spin coating or by any printing method such as screen printing, flexographic printing, nozzle printing, or offset printing, but more preferably by LITI (photoinduced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble host materials 1 and 2 and a phosphorescent emitter are required. The advantage of solution processing is, for example, that the light-emitting layer can be applied in a very simple and inexpensive manner. This technique is particularly suitable for the mass production of organic electroluminescent devices.

[0162] Furthermore, hybrid approaches are feasible, where, for example, one or more layers are applied from a solution and one or more other layers are applied via vapor deposition.

[0163] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

[0164] Therefore, the present invention also provides a method for manufacturing the organic electroluminescent device of the present invention as described above or preferably, characterized in that the organic layer, preferably the light-emitting layer, the hole injection layer and / or the hole transport layer, is applied by vapor deposition, especially by sublimation and / or by OVPD (organic vapor deposition) and / or by means of carrier gas sublimation, or by solution, especially by spin coating or by printing.

[0165] In the case of fabrication via vapor deposition, there are, in principle, two methods in which the organic layer, preferably the luminescent layer, of the present invention can be applied or vapor-deposited onto any substrate or prior layer. First, the initial charge of the various materials used in the material sources can ultimately be evaporated from different material sources (“co-evaporation”). Second, the various materials can be premixed (premixed system), and the initial charge of the mixture can ultimately be evaporated from a single material source (“premixed evaporation”). In this way, vapor deposition of a luminescent layer with uniformly distributed components can be achieved simply and quickly without precisely starting multiple material sources.

[0166] Therefore, the present invention also provides a method for manufacturing the device of the present invention, characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein at least one compound of formula (1) is deposited from the vapor phase, either sequentially or simultaneously, from at least two material sources together with other materials forming the light-emitting layer.

[0167] In a preferred embodiment of the invention, the light-emitting layer is applied by vapor deposition, wherein the components of the composition are premixed and evaporated from a single material source.

[0168] Therefore, the present invention also provides a method for manufacturing the device of the present invention, characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein at least one compound of formula (1) and at least one other matrix material are deposited sequentially or simultaneously from the vapor phase with a light-emitting material selected from phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermal activated delayed fluorescence).

[0169] Compared with the prior art, the electronic device of the present invention, especially the organic electroluminescent device, has one or more of the following surprising advantages: 1. Electronic devices, particularly organic electroluminescent devices, containing compounds of formula (1) described above and below, or preferred embodiments thereof, exhibiting excellent lifetime characteristics, especially as matrix materials or as electron-conducting materials. In this context, these compounds particularly contribute to low roll-off, i.e., a smaller decrease in power efficiency at high luminous densities.

[0170] 2. Electronic devices comprising compounds of formula (1) or preferred embodiments described above and below as electronic conductive materials and / or matrix materials, particularly organic electroluminescent devices, exhibit excellent efficiency. In this context, the compounds of formula (1) or preferred embodiments of the present invention described above and below result in low operating voltages when used in electronic devices.

[0171] 3. The inventive compounds or preferred embodiments of formula (1) described above and below exhibit very high stability and lifetime.

[0172] 4. By utilizing the compounds of formula (1) or preferred embodiments described above and below, the formation of light loss channels in electronic devices, especially organic electroluminescent devices, can be avoided. Therefore, these devices are characterized by high PL efficiency and thus high EL efficiency of the light emitter, as well as excellent energy transfer to the dopant by the matrix.

[0173] 5. The use of the compound of formula (1) described above and below, or the preferred embodiment, in the layers of electronic devices, especially organic electroluminescent devices, results in high mobility of the electronic conductor structure.

[0174] 6. The compound of formula (1) or the preferred embodiment described above and below has excellent glass film forming properties.

[0175] 7. The compound of formula (1) described above and below, or the preferred embodiment, forms a very good film from the solution.

[0176] 8. The compound of formula (1) or the preferred embodiment described above and below has a low triplet energy level T1, which may be in the range of 2.50 eV to 2.90 eV, for example.

[0177] These advantages are not accompanied by excessive degradation of other electronic properties.

[0178] It should be noted that variations of the embodiments described in this invention are included within the scope of this invention. Unless expressly excluded, any feature disclosed in this invention may be replaced by an alternative feature having the same or equivalent or similar purpose. Therefore, unless otherwise stated, any feature disclosed in this invention should be considered an example of a general series or an equivalent or similar feature.

[0179] Unless specific features and / or steps are mutually exclusive, all features of the invention can be combined with each other in any way. This applies in particular to preferred features of the invention. Similarly, features that are not necessarily combined can be used individually (not in combination). Detailed Implementation

[0180] The technical teachings disclosed in this invention can be refined and combined with other examples. The invention is illustrated in detail by means of the following embodiments, but is not intended to limit the invention thereon.

[0181] Example

[0182] General method: In all quantum chemical calculations, the Gaussian16 (version B.01) software package was used. The neutral singlet ground state was optimized at the B3LYP / 6-31G(d) level. For the B3LYP / 6-31G(d) optimized ground state energy, the HOMO and LUMO values ​​were determined at the B3LYP / 6-31G(d) level. TD-DFT singlet and triplet excitations (vertical excitations) were then calculated using the same method (B3LYP / 6-31G(d)) and optimized ground state geometry. Standard settings for SCF and gradient convergence were used.

[0183] Based on energy calculations, the HOMO is obtained as the last orbital occupied by two electrons (alpha occ. eigenvalues), and the LUMO is obtained as the first unoccupied orbital (alpha virt. eigenvalues), in Hartree units, where HEh and LEh represent the HOMO and LUMO energies in Hartree units, respectively. This is used to determine the HOMO and LUMO values ​​in electron volts as follows, calibrated by cyclic voltammetry measurements: HOMOcorr=0.90603×HOMO-0.84836, LUMOcorr=0.99687×LUMO-0.72445.

[0184] The triplet energy level T1 of a material is defined as the relative excitation energy (in eV) of the lowest-energy triplet state discovered through quantum chemical energy calculations.

[0185] The singlet energy level S1 of a material is defined as the relative excitation energy (in eV) of the second lowest singlet state discovered through quantum chemical energy calculations.

[0186] The singlet state with the lowest energy is called S0.

[0187] The method described in this paper is independent of the software package used and always yields the same results. Examples of programs frequently used for this purpose are "Gaussian09" (Gaussian Inc.) and Q-Chem 4.1 (Q Chem, Inc.). In this case, the software package "Gaussian16 (version B.01)" is used to calculate the energy.

[0188] OLED manufacturing

[0189] In the subsequent embodiments V1 to V10 and E1 to E15 (see Tables 7 and 8), data for various OLEDs are provided.

[0190] Pretreatment of Examples V1 to V10 and E1 to E15: To improve process performance, a 20 nm thick layer of PEDOT:PSS (poly(3,4-ethylenedioxythiophene)poly(styrene sulfonate), sourced as CLEVIOS™ P VPAI 4083 from Heraeus Precious Metals GmbH, Germany, spun from aqueous solution) was coated onto a glass substrate coated with a 50 nm thick layer of structured ITO (indium tin oxide). These coated glass substrates form the substrate for applying the OLED.

[0191] The basic layer structure of an OLED is as follows: substrate / hole transport layer (HTL) / optional intermediate layer (IL) / electron blocking layer (EBL) / emitting layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally the cathode. The cathode is formed of an aluminum layer with a thickness of 100 nm. The specific structure of the OLED is shown in Table 4. The materials required to manufacture the OLED are shown in Table 5.

[0192] All materials are applied in a vacuum chamber via thermal vapor deposition. In this case, the luminescent layer always consists of at least one matrix material (also called the host material) and a luminescent dopant (emitting agent), which is added to the matrix material in a specific volume ratio via co-evaporation. Details given in the form of IC1:IC3:TEG1 (55%:35%:10%) indicate that the volume proportion of material IC1 in the layer is 55%, the proportion of IC3 is 35%, and the proportion of TEG1 is 10%. Similarly, the electron transport layer can also be composed of a mixture of the two materials.

[0193] OLEDs are characterized in a standard manner. To this end, the electroluminescence spectrum, current efficiency (measured in cd / A), power efficiency (measured in lm / W), and external quantum efficiency (EQE, measured in %) were determined as functions of luminous density, calculated from the current-voltage-luminous density characteristics (IUL characteristics) under the assumption of Lambertian light emission characteristics. The lifetime was also determined. The electroluminescence spectrum was measured at 1000 cd / m². 2 The value was determined at a specific luminous density and used to calculate the CIE 1931 x and y color coordinates. The parameter U1000 in Table 2 refers to a value reaching 1000 cd / m². 2 The voltage required to achieve a certain luminous density. CE1000 and PE1000 refer to the voltage required at 1000 cd / m². 2 The achieved current and power efficiency. Finally, EQE1000 refers to the operating brightness of 1000 cd / m².2 The external quantum efficiency at that time. The lifetime LD is defined as the time interval during which the brightness decreases from its initial value to a certain proportion L1 while operating under constant current. The values ​​in Table 2 are L0;j0 = 4000 cd / m². 2 L1=70% means that the lifetime reported in the LD column corresponds to an initial luminance of 4000 cd / m². 2 Dropped to 2800 cd / m 2 The time period experienced. Similarly, L0;j0=20 mA / cm², L1=80% means that at 20 mA / cm², 2 During the operation, the brightness drops to 80% of its initial value after the LD time.

[0194] Table 5 summarizes the data for various OLEDs. Examples V1-V5 are comparative examples of the prior art; Examples E1-E15 show the data for the OLEDs of the present invention.

[0195] Some embodiments will be described in detail below to illustrate the advantages of the OLED of the present invention.

[0196] Use of the mixture of the present invention in the light-emitting layer of a phosphorescent OLED

[0197] The material of this invention, when used as a matrix material for phosphorescent OLEDs, exhibits a significant improvement in component lifespan compared to existing technologies. (Comparison of Examples V1 / V2 with E1, E3, and E5; Comparison of V3 with E2; Comparison of V4 with E3; Comparison of V5 with E4; Comparison of V6 with E2; Comparison of V7 with E6; Comparison of V8 with E10; Comparison of V9 with E7; Comparison of V10 with E8). Furthermore, it serves as an electronic conductor (Comparison of Example V1 with E1, E14, and E15).

[0198]

[0199] Table 9: Structural Formulas of OLED Materials

Claims

1. A compound of formula (1), The symbols and markings used have the following meanings: L 1 Selected from single bonds or aromatic ring systems having 6-18 ring atoms, wherein the aromatic ring system is optionally partially or completely substituted by D; L 2 Aromatic ring systems consisting of single bonds or having 6-40 ring atoms, optionally partially or completely substituted by D; L 3 Selected from single-bonded aromatic ring systems with 6-40 ring atoms or heteroaromatic ring systems with 5-40 ring atoms, wherein either ring system is optionally and independently partially or completely substituted by D. Het is selected from: or ; Indicates with L 2 The key to the connection; Het 1 Selected from aromatic ring systems having 6 to 40 ring atoms, wherein the aromatic ring system is optionally divided by R 3 Partial or complete substitution, or a heteroaromatic ring system having 5 to 40 ring atoms, said heteroaromatic ring system being selected from the formula Het(1) ) to Het (5 ) or Het (6) to Het (17); ， in Indicates with L 3 The connection, The dashed line represents L. 3 The key to the connection, and R 5 The meaning is the same as R; R may be the same or different in various cases and is selected from: H, D, F, CN; a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S, and wherein at least one hydrogen atom may be replaced by D, F or CN; or an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms, wherein at least one hydrogen atom may be replaced by D, F, Cl, Br, I or CN, and said aromatic ring system or heteroaromatic ring system may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more adjacent substituents R may together form an aliphatic, aromatic or heteroaromatic ring system; R 1 In various cases, the same or different, and selected from: H, D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S, and wherein at least one hydrogen atom may be replaced by D, F or CN, or an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms, wherein at least one hydrogen atom may be replaced by D, F, Cl, Br, I or CN, and said aromatic ring system or heteroaromatic ring system may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more adjacent substituents R may together form an aliphatic, aromatic or heteroaromatic ring system; R 2 In various cases, they may be the same or different, and are selected from aromatic ring systems having 6 to 40 ring atoms or heteroaromatic ring systems having 5 to 40 ring atoms, wherein the two ring systems are optionally and independently determined by R. 4 To partially or completely replace; R 3 In various cases, the same or different, and selected from: H, D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S, and wherein at least one hydrogen atom may be replaced by D, F or CN, or an aromatic ring system having 6 to 40 carbon atoms or a heteroaromatic ring system having 5 to 40 ring atoms, wherein at least one hydrogen atom may be replaced by D, F, Cl, Br, I or CN, and said aromatic ring system or heteroaromatic ring system may be replaced by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more adjacent substituents R may together form an aliphatic, aromatic or heteroaromatic ring system; R 4 They may be the same or different in various situations, and are selected from H, D, F, CN; When m is 4, n is 3, or When n is 4, m is 3, and The following compounds are excluded from this invention: 。 2. The compound according to claim 1, wherein the compound is a compound of formula (1a): Equation (1a) The symbols and markings used herein have the meaning as claimed in claim 1.

3. The compound according to claim 1 or 2, wherein Het 1 Selected from aromatic ring systems having 6-25 ring atoms or heteroaromatic ring systems having 5 to 18 ring atoms and selected from the structures of formulas Het (6) to Het (17).

4. The compound according to one or more of claims 1 to 3, wherein L 3 Selected from single-bonded aromatic ring systems with 6 to 24 ring atoms or heteroaromatic ring systems with 5 to 18 ring atoms, wherein either ring system is optionally and independently partially or completely substituted by D.

5. A mixture comprising at least one compound according to one or more of claims 1 to 4 and at least one other compound selected from matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

6. A formulation comprising at least one compound according to one or more of claims 1 to 4 or a mixture according to claim 5 and at least one solvent.

7. An organic electroluminescent device comprising an anode, a cathode, and at least one organic layer, the organic layer comprising at least one compound according to one or more of claims 1 to 4.

8. The organic electroluminescent device according to claim 7, wherein the organic layer comprises at least one electron transport layer, the electron transport layer containing a compound according to one or more of claims 1 to 4.

9. The organic electroluminescent device according to claim 7 or 8, wherein the organic layer comprises at least one light-emitting layer, the light-emitting layer containing a compound according to one or more of claims 1 to 4 as a matrix material.

10. The organic electroluminescent device according to claim 9, wherein the light-emitting layer contains at least one other matrix material.

11. The organic electroluminescent device according to claim 10, wherein the at least one other matrix material is a compound of formulas (2) to (5) and (8) to (12): Equation (2) Equation (3) Equation (4) Equation (5) The symbols and markings used are as follows: A 1 For C(R) 7 2. NR 7 , O or S; A is independently a group of formula (6) or (7) in all cases. Equation (6) Equation (7); Equation (8) Equation (9) Equation (10) Equation (11) Equation (12) X2 may be the same or different in various situations, and is CH, CR 6 Or N, where no more than two of the symbols X2 can be N; Indicates the bonding site with equation (5); R 6 In various cases, they may be the same or different and are: D, CN, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group may in various cases be one or more R 7 The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 7 2. C=O, NR 7 O, S or CONR 7 Replacement, or having 5 to 60 ring atoms and in various cases can be replaced by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two R groups... 6 Groups can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems together; Ar can be the same or different in various cases, and can have 5 to 40 ring atoms and can be converted by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; Ar 1 They may be the same or different in various cases, and are for those with 5 to 40 ring atoms and can be generated by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; R 7 They may be the same or different under various conditions and are: D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 )3, B(OR 8 )2,C(=O)R 8 , P(=O)(R 8 )2,S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group may, in various cases, be one or more R 8 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Replacement, or having 5 to 40 ring atoms and in various cases can be replaced by one or more R atoms. 8 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 7 The groups can together form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; preferably, R 7 The group does not form any such ring system; R 8 In various cases, they may be the same or different and are: H, D, F, or an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 carbon atoms, especially a hydrocarbon group, wherein one or more hydrogen atoms may be replaced by F; c, c1, and c2 are each independently 0 or 1 in various cases, and the sum of the markings in all cases, c+c1+c2, is 1; d, d1, and d2 are each independently 0 or 1 in various cases, and the sum of the markings in all cases, d+d1+d2, is 1; q, q1, and q2 are each independently 0 or 1 in various situations; s can be the same or different in various cases and can be 0, 1, 2, 3 or 4; t can be the same or different in various cases and can be 0, 1, 2 or 3; u is the same or different in various cases and is 0, 1, or 2; and v is 0 or 1.

12. The organic electroluminescent device according to claim 10, wherein the other matrix material is a compound of formula (13): Equation (13) The symbols and markings used are as follows: W is O, S, C(R 9 )2, N-Ar 2 ; R 9 Independently, in various cases, it refers to: a straight-chain or branched alkyl group having 1 to 4 carbon atoms and being partially or fully deuterated, or an unsubstituted or partially or fully deuterated aromatic ring system having 6 to 18 carbon atoms, wherein two substituents R 9 Together with the carbon atoms they are bonded to, they can form monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic unsubstituted, partially deuterated, or fully deuterated ring systems, which can be substituted by one or more substituents R. 12 replace; Ar 2 They may be the same or different in various cases, and are for those with 5 to 30 ring atoms and can be generated by one or more R atoms. 12 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two Ar atoms bonded to the same nitrogen, phosphorus, or boron atom. 2 Groups can also be formed via single bonds or selected from C(R) 12 2. The bridging bases in O or S are interconnected; R 10 They may be the same or different in various cases, and are selected from: F, Cl, Br, I, CN, NO2, C(=O)R', P(=O)(Ar1)2, P(Ar 2 )2, B(Ar 2 )2, Si(Ar1)3, Si(R')3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of which may be substituted by one or more R' groups, wherein one or more non-adjacent CH2 groups may be substituted by R'C=CR', Si(R')2, C=O, C=S, C=NR', P(=O)(R'), SO, SO2, NR', O, S, or CONR', and wherein one or more hydrogen atoms may be substituted by D, F, Cl, Br, I, CN, or NO2; R' may be the same or different in various cases and is selected from: D, F, Cl, Br, I, CN, NO2, N(Ar1)2, NH2, N(R'')2, C(=O)Ar1, C(=O)H, C(=O)R'', P(=O)(Ar1)2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R'' groups, wherein one or more non-adjacent CH2 groups may be HC=CH, R''C=CR'', C≡C, Si(R')2, Ge(R'')2, Sn (R'')2, C=O, C=S, C=Se, C=NR'', P(=O)(R''), SO, SO2, NH, NR'', O, S, CONH or CONR'', wherein one or more hydrogen atoms may be replaced by F, Cl, Br, I, CN or NO2, having 5 to 60 aromatic ring atoms and being substituted by one or more R'' groups in various cases, having 5 to 60 aromatic ring atoms and being substituted by one or more R'' groups, or combinations of these systems, wherein two or more adjacent substituents R' may optionally form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system that may be substituted by one or more R'' groups; R'' may be the same or different in various cases and is selected from: D, F, CN, aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and said aromatic or heteroaromatic ring system may be replaced by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more adjacent R'' 3 Substituents can together form monocyclic or polycyclic aliphatic ring systems; R' may be the same or different in various cases, and is an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 carbon atoms, especially a hydrocarbon group, in which one or more hydrogen atoms may also be replaced by F; R 11 They may be the same or different under various conditions, and are selected from: F, Cl, Br, I, CN, NO2, N (Ar) 2 )2,NH2,N(R 12 )2,C(=O)Ar 2 C(=O)H, C(=O)R 5 , P(=O)(Ar 2 )2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted with one or more R 12 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by HC=CH, R 12 C=CR 12 C≡C, Si(R) 12 )2、Ge(R 12 )2、Sn(R 12 )2. C=O, C=S, C=Se, C=NR 12 P(=O)(R) 12 SO, SO2, NH, NR 12 O, S, CONH or CONR 12 Replacement, and one or more of the hydrogen atoms can be replaced by D, F, Cl, Br, I, CN or NO2, having 5 to 60 ring atoms and in various cases can be replaced by one or more R 12 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 60 ring atoms and being substituted by one or more R groups. 12 A group-substituted aryloxy or heteroaryloxy group, or a combination of these systems, wherein two or more adjacent substituents R 11 Optionally formed that can be generated by one or more R 12 Monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring systems with substituted groups; R 12 In various cases, the same or different, and selected from: D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S and wherein one or more hydrogen atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 30 ring atoms and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, wherein the aromatic or heteroaromatic ring system may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; and simultaneously, two or more adjacent substituents R 12 They can form monocyclic or polycyclic aliphatic ring systems together; x and x1 are independently 0, 1, 2, 3 or 4 in various cases; y and z are each independently 0, 1, or 2; a1 and a2 are each independently 0, 1, 2, 3, 4 or 5; a3 can be 0, 1, 2, or 3; a4 can be 0, 1, 2, 3 or 4.

13. The organic electroluminescent device according to one or more of claims 9 to 12, wherein the light-emitting layer contains a phosphorescent material.

14. The organic electroluminescent device according to one or more of claims 6 to 13, wherein the organic electroluminescent device is an electroluminescent device selected from organic light-emitting transistors (OLET), organic field quenching devices (OFQD), organic light-emitting electrochemical cells (OLEC, LEC, LEEC), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs).

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