Materials for organic electroluminescent devices

Abstract

The present invention relates to compounds represented by formula (1), mixtures and electronic devices comprising these compounds, in particular organic electroluminescent devices comprising a compound of formula (1) as a matrix material, optionally in combination with another compound.

Description

Materials for organic electroluminescent devices Technical Field

[0001] The present invention relates to compounds represented by formula (1) and electronic devices containing these compounds, particularly organic electroluminescent devices containing these compounds as matrix materials, optionally in combination with another compound. Background Technology

[0002] Phosphorescent organometallic complexes are commonly used in organic light-emitting diodes (OLEDs). Generally, there is still room for improvement in OLEDs, such as in terms of efficiency, operating voltage, and lifetime. The properties of phosphorescent OLEDs are not solely determined by the triplet emitter used. Other materials, such as the matrix material, are also particularly important. Therefore, improvements to these materials can also lead to significant improvements in OLED properties.

[0003] According to existing technology, 7H-diindolo[3,2-c2',3'-g]carbazole derivatives have been discovered and used as matrix materials.

[0004] Such derivatives substituted with cyano groups have been disclosed in US 2019 / 315760 A, and derivatives substituted at the 2 and 7 positions of the carbazole group have been described, for example, in CN 1053999748 A and CN 113943300 A.

[0005] Unfortunately, these substituents have a negative impact on the lifetime and voltage properties of the matrix material.

[0006] WO 2017 / 105040 A1 discloses such derivatives, wherein the two N atoms of the indole group utilize substituted or unsubstituted (C6-C) atoms. 30 )Aryl or substituted or unsubstituted (3 to 30) heteroaryl groups are linked together.

[0007] Unfortunately, these connectors negatively impact the T1 level of the matrix material, leading to reduced efficiency, especially in green OLED devices.

[0008] However, improvements are still needed in the use of these materials, or in mixtures thereof, particularly in the efficiency, operating voltage, and / or lifetime of electronic devices, especially organic electroluminescent devices.

[0009] Therefore, the problem solved by the present invention is to provide a host material suitable for use in electronic devices, especially in fluorescent or phosphorescent organic electroluminescent devices, and to produce good device properties, especially improved lifetime; and to provide corresponding electronic devices.

[0010] It has now been found that this problem is solved by compounds according to formula (1), and the disadvantages of the prior art are eliminated. The use of such compounds in the manufacture of electronic devices results in very good properties of these devices, especially in terms of lifespan, and particularly improved efficiency and / or operating voltage. These advantages are also particularly evident in the presence of at least one compound of formula (1) as a first host material and other compounds as a second host material, such as one or more compounds of formula (eTMM1), (eTMM2), (eTMM3), (eTMM4), or (eTMM5). Summary of the Invention

[0011] Therefore, the present invention first provides a compound represented by formula (1):

[0012] Equation (1)

[0013] The groups and markings that appear are as follows: R, in each appearance, either the same or different, preferably the same, represents H or D; R 1 Each occurrence may represent H, D, F, N(R) in the same or different ways. 3 )2,C(=O)R 3 , P(=O)(R 3 )2,S(=O)R 3 S(=O)2R 3 ,Si(R 3 )3,Ge(R) 3 )3, B(R) 3 )2, B(OR 3 )2, OSO2R 3 Aromatic or heteroaromatic ring systems having 5 to 60 ring atoms, wherein in each case the aromatic or heteroaromatic ring system may be substituted by one or more groups R 3 The aryloxy group may be substituted with, or have 5 to 60 cyclic atoms, an aryloxy group, which may be replaced by one or more groups R. 3 Replacement; preferably, in each occurrence, the same or different, more preferably, the same, representing H or D; R 2 Each occurrence may represent H, D, F, N(R) in the same or different ways. 4 )2,C(=O)R 4 , P(=O)(R 4 )2,S(=O)R 4 S(=O)2R 4 ,Si(R 4 )3,Ge(R) 4 )3, B(OR 4 )2, OSO2R 4Aromatic or heteroaromatic ring systems having 5 to 60 ring atoms, wherein in each case the aromatic or heteroaromatic ring system may be substituted by one or more groups R 4 The aryloxy group may be substituted with, or have 5 to 60 cyclic atoms, an aryloxy group, which may be replaced by one or more groups R. 4 Substitution; where two adjacent substituents R 2 It can form monocyclic or polycyclic aromatic or heterocyclic ring systems, wherein the aromatic or heterocyclic rings can be formed by one or more groups R. 4 Replace; R 3 and R 4 Each occurrence may represent, in the same or different manner, H, D, F, N(Ar)2, C(=O)Ar, P(=O)(Ar)2, S(=O)Ar, S(=O)2Ar, Si(R')3, Ge(R')3, B(OR')2, OSO2R', an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, wherein in each case the aromatic or heteroaromatic ring system may be substituted by one or more groups R', or an aryloxy group having 5 to 60 ring atoms, wherein the aryloxy group may be substituted by one or more groups R'; wherein R 3 and R 4 It can form monocyclic or polycyclic aromatic or heterocyclic ring systems, which can be substituted by one or more groups R'; m and n represent 0, 1, 2, 3 or 4 each time they appear, preferably 0, 1 or 2, more preferably 0 or 1; Ar 1 Ar 2 and Ar 3 Each occurrence may represent, in the same or different ways, an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably 5 to 40 ring atoms, which may in each case be substituted by one or more groups R'; wherein Ar 2 and Ar 3 They can be linked together by single bonds or by linking groups; R´ in each occurrence may represent H, D, CN, F, Si(R´´)3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, preferably 1 to 10 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, preferably 3 to 10 carbon atoms, each of which may be linked by one or more groups R. 3 Substitution, wherein in each case one or more non-adjacent CH2 groups may be replaced by R 3 C=CR 3 C≡C, Si(R) 3 )2、Ge(R 3 )2、Sn(R 3 )2. C=O, C=S, C=Se, P(=O)(R 3), SO, SO2, O, S or CONR 3 The substitution is made by replacing one or more H atoms with D, F, Cl, Br, I, or NO2, or by having an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, preferably 5 to 14 ring atoms, wherein two adjacent substituents R' can form a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system, wherein the aliphatic ring system, aromatic or heteroaromatic ring system can be replaced by one or more groups R. 3 Substitution; and R'', in each occurrence, represents, identically or differently, 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, each of which may be replaced by one or more groups R. 3 Substitution, wherein in each case one or more non-adjacent CH2 groups may be replaced by R 3 C=CR 3 C≡C, Si(R) 3 )2、Ge(R 3 )2、Sn(R 3 )2. C=O, C=S, C=Se, P(=O)(R 3 ), SO, SO2, O, S or CONR 3 The substitution is made by replacing one or more H atoms with D, F, Cl, Br, I, or NO2, wherein two adjacent substituents R'' can form a monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring system, which can be replaced by one or more groups R. 3 replace.

[0014] The present invention further provides a mixture comprising at least one compound according to formula (1) as described above or below and at least one other compound and / or at least one solvent, wherein the other compound is selected from phosphors, phosphorescents, TADF (thermally excited delayed fluorescence) emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conduction materials, hole injection materials, n-type dopants, p-type dopants, wide bandgap materials, electron blocking materials, and hole blocking materials.

[0015] The present invention further provides a mixture comprising at least one compound according to formula (1) as described above or below and at least one compound of formula (eTMM1), (eTMM2), (eTMM3), (eTMM4) or (eTMM5). Formula (eTMM1), Formula (eTMM2), Formula (eTMM3), Formula (eTMM4), Formula (eTMM5), in which the symbols and notations used are described below.

[0016] The present invention further provides an electronic device comprising at least one compound according to formula (1) as described above or in the following preferred embodiments, or at least one mixture as described above or in the following preferred embodiments.

[0017] The present invention further provides the use of compounds of formula (1) in electronic devices as described above or as described in the following preferred examples. Detailed Implementation

[0018] In the context of this invention, "D" or "D atom" refers to deuterium.

[0019] In the context of this invention, an aryl group contains 6 to 60 ring atoms, preferably carbon atoms. In the context of this invention, a heteroaryl group contains 5 to 60 ring atoms, wherein the ring atoms comprise carbon atoms and at least one heteroatom, provided that the sum of the carbon atoms and the heteroatom is at least 5. The heteroatom is preferably selected from N, O, and / or S. An aryl group or heteroaryl group should be understood herein to refer to a simple aromatic ring, i.e., a phenyl ring derived from benzene, or a simple heteroaryl ring, such as one derived from pyridine, pyrimidine, or thiophene, or a fused aryl or heteroaryl group, such as one derived from naphthalene, anthracene, phenanthrene, quinoline, or isoquinoline. Therefore, an aryl group having 6 to 18 carbon atoms is preferably phenyl, naphthyl, phenanthryl, or biphenylidene, and there is no limitation on the connection of the aryl group as a substituent. In the context of this invention, an aryl or heteroaryl group may have one or more R' groups, wherein the substituent R' is described below.

[0020] In the context of this invention, an aromatic ring system contains 6 to 60 ring atoms. The aromatic ring system also includes aryl groups as described above. An aromatic ring system having 6 to 18 carbon atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthryl, and biphenylidene.

[0021] In the context of this invention, a heteroaromatic ring system contains 5 to 60 ring atoms and at least one heteroatom. A preferred heteroaromatic ring system has 10 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system also includes a heteroaryl group as described above. The heteroatom in the heteroaromatic ring system is preferably selected from N, O, and / or S.

[0022] In the context of this invention, aromatic or heteroaromatic ring systems should be understood to refer to systems that do not necessarily contain only aryl or heteroaromatic groups, but in which multiple aryl or heteroaromatic groups may also be interrupted by non-aromatic units (preferably less than 10% of non-H atoms), such as carbon, nitrogen, or oxygen atoms or carbonyl groups. For example, in the context of this invention, systems such as 9,9'-spirodifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, piracene, etc., should therefore also be considered aromatic or heteroaromatic ring systems, as should systems in which two or more aryl groups are interrupted, for example, by straight-chain or cyclic alkyl groups or by silyl groups. In addition, systems in which two or more aryl or heteroaromatic groups are directly bonded to each other, such as biphenyl, terphenyl, tetraphenyl, or bipyridine, are also covered by the definition of aromatic or heteroaromatic ring systems.

[0023] Aromatic or heteroaromatic ring systems having 5 to 60 ring atoms and being able to be attached to aromatic or heteroaromatic systems at any desired position should be understood to refer to groups derived, for example, from the following substances: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, celestine, perylene, fluoranthene, benzo[a]fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, diphenylenexide, terphenyl, terphenylenexide, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorene, cis or trans monobenzo[a]indo[a]fluorene, cis or trans dibenzo[a]indo[a]fluorene, trimer indo[a]fluorene, isotriphenylene Polyindene, 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, β-azole, benzo[β-azole], naphtho[β-azole], anthraxo[β-azole], phenanthrene[β-azole], iso[β-azole], 1,2-thiazole, 1,3-thiazole, benzo[β-thiazole], pyridazine, benzo[β-pyridazine], pyrimidine, benzo[β-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, phenothiazine, fluorescein ring, naphthidine, azacarbazole, benzo[β-carbline], phenanthrene, 1,2,3- Triazoles, 1,2,4-triazoles, benzotriazoles, 1,2,3-diazoles, 1,2,4-diazoles, 1,2,5-diazoles, 1,3,4-diazoles, 1,2,3-thiadiazoles, 1,2,4-thiadiazoles, 1,2,5-thiadiazoles, 1,3,4-thiadiazoles, 1,3,5-triazines, 1,2,4-triazines, 1,2,3-triazines, tetrazolium, 1,2,4,5-tetraazines, 1,2,3,4-tetraazines, 1,2,3,5-tetraazines, purines, pteridines, indoleazines, and benzothiadiazoles.

[0024] Each instance of the abbreviation Ar independently refers to an aromatic or heteroaromatic ring system having 5 to 60 ring atoms that can be substituted by one or more R' groups, or a heteroaromatic ring system having 5 to 40 ring atoms that can be substituted by one or more R' groups, wherein details regarding the aromatic or heteroaromatic ring system apply accordingly. The one or more R' groups have the definitions described above or below. Each instance of the abbreviation Ar preferably independently refers to an aryl group having 6 to 40 ring atoms that can be substituted by one or more R' groups, or a heteroaromatic group having 5 to 40 ring atoms and containing O or S as a heteroatom, wherein the heteroaromatic group can be substituted by one or more R' groups, wherein details regarding the aryl group or heteroaromatic group and R' as described above and below apply accordingly.

[0025] In the context of this invention, cyclic alkyl, alkoxy, or thioalkyl groups should be understood to mean monocyclic, bicyclic, or polycyclic groups.

[0026] In the context of this invention, straight-chain alkyl groups having 1 to 40 carbon atoms, and branched or cyclic alkyl groups having 3 to 40 carbon atoms, should be understood to 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, and cyclohexyl. 1-Methylcyclopentyl, 2-Methylpentyl, 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-hexyl-1- 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-heptane-1-yl, 1,1-Diethyl-n-octane-1-yl - 1,1-diethyl-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.

[0027] A straight-chain alkoxy group having 1 to 40 carbon atoms or a branched alkoxy group having 3 to 40 carbon atoms shall be understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, or 2-methylbutoxy.

[0028] A straight-chain thioalkyl group having 1 to 40 carbon atoms should be understood to mean, for example, an S-alkyl group, such as thiomethyl, 1-thioethyl, 1-thioisopropyl, 1-thion-propyl, 1-thioisobutyl, 1-thion-butyl or 1-thiotert-butyl.

[0029] An aryloxy or heteroaryloxy group having 5 to 60 ring atoms refers to an O-aryl or O-heteroaryl group, and refers to an aryl or heteroaryl group bonded by an oxygen atom, wherein the aryl or heteroaryl group is as defined above.

[0030] An aryl or heteroaryl group having 5 to 40 ring atoms means an alkyl group as described above that is replaced by an aryl or heteroaryl group, wherein the aryl or heteroaryl group is as defined above.

[0031] In the context of this specification, the phrase "two or more groups together can form a ring" should be understood to mean, in particular, that the two groups are connected to each other by chemical bonds. This is illustrated by the following scheme:

[0032] 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:

[0033] In one preferred embodiment of the compound of formula (1) or the host material of formula (1), the compound is represented by at least one of formulas (1-1) to (1-4): Equation (1-1) Equation (1-2) Equation (1-3) Equation (1-4) In Equations (1-1) to (1-4), Ar 1 Ar 2 and Ar 3 and R 2 It has the definition given above or below.

[0034] In a preferred embodiment of the present invention, Ar in formula (1) or formulas (1-1) to (1-4) 2and Ar 3 Same. However, in another preferred embodiment of the invention, Ar in formula (1) or formulas (1-1) to (1-4) 2 and Ar 3 different.

[0035] In another preferred embodiment of the invention, Ar 2 and Ar 3 They are linked together by single bonds or by connecting groups, preferably by single bonds, and preferably in Ar 2 and Ar 3 The adjacent linkage. Preferably, the linking group is BR´, C(R´)2, Si(R´)2, NR´, O, or S, wherein R´ has the definition given above.

[0036] In yet another preferred embodiment, at least one carbazole group of the core structure of formula (1) or formulas (1-1) to (1-4) contains a fused aromatic or heteroaromatic group.

[0037] In another preferred embodiment of the invention, Ar 1 Ar 2 and Ar 3 Each occurrence, whether identical or different, represents an aromatic ring system having 6 to 60 ring atoms, preferably 6 to 40 ring atoms, which in each case may also be substituted by one or more groups R', wherein two adjacent substituents R' can form a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system, which may be substituted by one or more groups R'. 3 Replace, and in which Ar 2 and Ar 3 They can be linked together by single bonds or by linking groups.

[0038] In another preferred embodiment of the invention, Ar 1 This represents an aromatic ring system having 6 to 60 ring atoms, preferably 6 to 40 ring atoms, which in each case may also be substituted by one or more groups R', and Ar 2 and Ar 3 At least one or both of these, when appearing in the same or different instances, represent a heteroaromatic ring system having 5 to 60 ring atoms, preferably 5 to 40 ring atoms, which in each case may also be substituted by one or more groups R', wherein two adjacent substituents R' can form a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system, which may be substituted by one or more groups R'. 3 Replace, and in which Ar 2 and Ar 3They can be linked together by single bonds or by linking groups.

[0039] Examples of such fused structures are shown in structures (2) through (10) below:

[0040] In structures (2) to (10): X represents O, S, NR 5 or C(R) 5 )2, preferably O and NR 5 or C(R) 5 )2, preferably O or NR 5 ;R 5 Each occurrence may represent, in the same or different manner, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, preferably 5 to 14 ring atoms, which may in each case be substituted by one or more groups R'; and R' may have the meaning of formula (1) as described above.

[0041] If X is NR 5 or C(R) 5 )2, then R 5 The preferred group is a phenyl group.

[0042] This means C(R) 5 )2 is or .

[0043] Ar in equations (1-1) to (1-4) 1 Ar 2 and Ar 3 In each case, an aromatic or heteroaromatic ring system is preferred, and the groups are preferably the same or different each time they appear and selected from Ar-1 to Ar-45:

[0044] The dashed lines represent bonds connected to the basic skeleton, wherein each of the groups in the above formulas Ar-1 to Ar-45 can be substituted by one or more substituents R', and furthermore: A is the same or different each time it appears and is NAr. 4 O, S, or C(R')2; n is 0 or 1, where n = 0 means no A group is bonded to that position; Ar 4 It is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms that can be substituted by one or more R' groups; R' in each occurrence may represent H, D, CN, F, Si(R'')3, 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, each of which can be substituted by one or more R' groups. 3 Substitution, wherein in each case one or more non-adjacent CH2 groups may be replaced by R 3 C=CR 3 C≡C, Si(R) 3 )2、Ge(R 3 )2、Sn(R 3 )2. C=O, C=S, C=Se, P(=O)(R 3 ), SO, SO2, O, S or CONR 3 The substitution is made by replacing one or more H atoms with D, F, Cl, Br, I, or NO2, or by an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, wherein two adjacent substituents R' can form a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system, wherein the aliphatic ring system, aromatic or heteroaromatic ring system can be replaced by one or more groups R. 3 Replace. R´´ and R 3 The definition is as described above.

[0045] The preferred embodiment of the compound of formula (1) or the main material of formula (1) preferably contains at least one deuterium atom as a substituent.

[0046] In one preferred embodiment of the compound of formula (1) or the main material of formula (1), R 1 At least one of them represents H or D in each occurrence, either the same or different.

[0047] In one preferred embodiment of the compound of formula (1) or the main material of formula (1), R 2 Each occurrence may represent, in the same or different ways, an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which in each case may be unsubstituted or substituted with one or more D atoms.

[0048] In one preferred embodiment of the compound of formula (1) or the main material of formula (1), R 3 Or R 4 It may represent H or D in the same or different ways each time it appears.

[0049] In one preferred embodiment of the compound of formula (1) or the host material of formula (1), R' represents H or D in the same or different ways each time it appears.

[0050] In one preferred embodiment of the compound of formula (1) or the main material of formula (1), the degree of deuteration of the compound is about 1 mol% to 100 mol%, preferably at least 10 mol% to 100 mol%, more preferably 50 mol% to 95 mol%, and most preferably 70 mol% to 90 mol.

[0051] In one preferred embodiment of the compound of formula (1) or the main material of formula (1), R 1 Each occurrence may represent H, D, F, Si(R) in the same or different ways. 3 )3, N(R 3 )2, B(R) 3 )2, aromatic ring systems having 6 to 40 ring atoms and heteroaromatic ring systems having 5 to 40 ring atoms, wherein the aromatic ring system and the heteroaromatic ring system may in each case be purported to ... 3 Substitution; or an aryloxy group having 6 to 40 ring atoms, wherein in each case the aryloxy group may be replaced by one or more groups R 3 Replace, R 3 It has the definition given above or below.

[0052] In one preferred embodiment of the compound of formula (1) or the main material of formula (1), R 2Each occurrence may represent H, D, F, Si(R) in the same or different ways. 4 )3, N(R 4 )2,Si(R 4 3, aromatic ring systems having 6 to 40 ring atoms and heteroaromatic ring systems having 5 to 40 ring atoms, wherein in each case the aromatic ring system and the heteroaromatic ring system may be purported to be formed by one or more groups R. 4 Substitution; or an aryloxy group having 6 to 40 ring atoms, wherein in each case the aryloxy group may be replaced by one or more groups R 4 Replace; more preferably, R 2 Each occurrence may refer to an aromatic ring system having 6 to 40 ring atoms and a heteroaromatic ring system having 5 to 40 ring atoms, respectively, wherein the aromatic ring system and the heteroaromatic ring system may in each case be represented by one or more groups R. 4 Replace, R 4 It has the definition given above or below.

[0053] In one preferred embodiment of the compound of formula (1) or the main material of formula (1), R 3 and R 4 Each occurrence may represent, in the same or different manner, H, D, F, Si(R')3, N(R')2, an aromatic ring system having 6 to 40 ring atoms and a heteroaromatic ring system having 5 to 40 ring atoms, wherein the aromatic ring system and the heteroaromatic ring system may be substituted by one or more groups R' in each case; or an aryloxy group having 6 to 40 ring atoms, wherein the aryloxy group may be substituted by one or more groups R' in each case, R' having the definition given above or below.

[0054] Examples of preferred compounds of formula (1) are the structures listed in Table 1 below.

[0055] Table 1

[0056] The particularly preferred compounds of formula (1) are compounds H1 to H12 in Table 2.

[0057] Table 2

[0058] In one embodiment, compounds 1 to 72 and compounds H1 to H12 in Table 1 have the same degree of deuteration as the compounds of formula (1) above.

[0059] The compounds according to the invention can be prepared by known synthetic methods as follows. The following synthetic schemes show compounds with a small number of substituents to simplify the structure. This does not exclude the presence of any other substituents in the procedure.

[0060] The methods shown for synthesizing the compounds according to the invention should be understood as illustrative. Those skilled in the art can develop alternative synthetic methods within the framework of their common sense.

[0061] The compound (6) according to the invention can be prepared by known synthetic methods, see Scheme 1. Carbazole-3,6-diboronic acid or ester (1) is known in the literature to undergo a Suzuki coupling reaction with 2-halononitrobenzene (2) in aqueous or anhydrous conditions with the aid of a base (usually an alkali metal carbonate or phosphate), a palladium source (usually Pd(OAc)2 or Pd2(dba)3), a phosphine ligand (PPh3, S-Phos, X-Phos, RuPhos, AmPhos, BiNap, DPPF, etc.), a phosphine ligand (PPh3, S-Phos, X-Phos, RuPhos, AmPhos, BiNap, DPPF, etc.), see step 1. The intermediate dinitrocarbazole (3) is cyclized under Cadogan conditions with the assistance of phosphine or phosphite (e.g., PPh3, P(OEt)3, P(OBu)3) or carbon monoxide to generate the desired indole-indole-carbazole (4), with a regioselectivity typically between 50% and 80%, see step 2. Under Ullmann conditions 1 (CuI, TMEDA, K2CO3, o-xylene, reflux), it is cyclized with aryl iodide Ar 2 -I was used for the first N-arylation reaction to give mono-N-arylated carbazole (5), see step 3. Under Ullmann conditions 2 (Cu, K2CO3, Na2SO4, 1,2-dichlorobenzene, reflux), aryl iodide Ar was used. 3 -I undergoes a second N-arylation reaction to obtain the di-N-arylated carbazole (6) of this invention, see step 4. The aromatic group Ar to be introduced... 2 and Ar 3 Under similar conditions, the Ullmann coupling reaction scheme 2 can be used. The crude product obtained is purified by standard procedures such as chromatography, crystallization, and fractional sublimation.

[0062] Option 1:

[0063] The detailed reaction conditions are known to those skilled in the art or are described in the Examples section.

[0064] By following these procedures, and if necessary, by purification such as recrystallization or sublimation, high purity, preferably greater than 99.9%, can be obtained. 1 Compounds of formula (1) as determined by ¹H NMR and / or HPLC.

[0065] To process the compounds of the present invention from the liquid phase, 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 required. These formulations can be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents are preferably used. Suitable and preferred solvents include, for example, toluene, anisole, o-, m-, or p-xylene, methyl benzoate, mesitylene, naphthalene, veratrine, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenazine, 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, cumene, cyclohexanol, and cyclohexanone. Cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indene, NMP, p-cymene, 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.

[0066] Preferred embodiments of the compounds of formula (1) of the present invention or the main materials of formula (1) as described above (optionally one of formulas (1-1) to (1-4)) are suitable for use in organic electroluminescent devices, especially as matrix materials.

[0067] When the compounds of the present invention are used as matrix materials (or, synonymously, host materials) in the light-emitting layer, they are preferably used in combination with other compounds.

[0068] Therefore, the present invention further provides a mixture comprising at least one compound of formula (1) or at least one of the preferred formulas (1-1) to (1-4) or compounds from Table 1 or Table 2 and at least one other compound selected from matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence). Suitable matrix materials and emitters that can be used in such mixtures of the present invention are described below.

[0069] The present invention further provides a formulation comprising at least one compound of the present invention as described above or a mixture of the present invention as described above, and at least one solvent. The solvent may be the solvents described above or a mixture of these solvents.

[0070] The present invention further provides an organic electronic device comprising an anode, a cathode and at least one organic layer, the organic layer comprising at least one compound of formula (1), or at least one of preferred formulas (1-1) to (1-4), or a compound from Table 1 or Table 2.

[0071] Organic electronic devices can be selected from, for example, organic integrated circuits (OIC), organic field-effect transistors (OFET), organic thin-film transistors (OTFT), organic electroluminescent devices, organic solar cells (OSC), organic optical detectors, and organic photosensors.

[0072] Organic electronic devices are preferably organic electroluminescent devices.

[0073] The organic electroluminescent devices (synonymous with organic electroluminescent apparatuses) of the present invention are, for example, 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.

[0074] In addition to the light-emitting layer (EML), the organic layer of the device of the present invention preferably also includes 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, an intermediate layer, for example, having exciton blocking functionality, may be introduced between two light-emitting layers.

[0075] If multiple emitting layers are present, these emitting layers preferably have a total of multiple emission peaks between 380 nm and 750 nm, resulting in white emission; in other words, multiple luminescent compounds that can fluoresce or phosphore are used in the emitting layers. Two or more fluorescent and / or phosphorescent compounds may also be present 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 example of the combination described above, the emitting layers may also exhibit yellow emission. 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 a white-emitting OLED.

[0076] The device may also include inorganic materials or other layers formed entirely of inorganic materials.

[0077] For those skilled in the art, considering the various materials known in the prior art, selecting a suitable material for use in the aforementioned layers of an organic electroluminescent device would pose no difficulty whatsoever. Those skilled in the art will describe the chemical and physical properties of the materials in a conventional manner, as they are aware that the materials interact with each other in the organic electroluminescent device. This involves, for example, orbital energy levels (HOMO, LUMO) or triplet and singlet energy levels, as well as other material properties.

[0078] Depending on the exact structure, compounds of formula (1) of the present invention, as described above or as preferably described, can be used in different layers. It is preferred that compounds comprising formula (1) or the embodiments described above be used in the luminescent layer as matrix materials for phosphorescent emitters, phosphorescent emitters, or emitters exhibiting TADF (thermally activated delayed fluorescence), particularly for organic electroluminescent devices as matrix materials for phosphorescent emitters. Furthermore, the compounds of the present invention can also be used in electron transport layers and / or hole transport layers and / or exciton blocking layers and / or hole blocking layers. It is particularly preferred to use the compounds of the present invention as matrix materials in the luminescent layer or as hole transport materials or exciton blocking materials in the hole transport layer or exciton blocking layer.

[0079] The present invention further provides an organic electronic device as described above, wherein the organic layer comprises at least one light-emitting layer, the light-emitting layer comprising at least one compound of formula (1), or at least one of the preferred formulas (1-1) to (1-4), or a compound from Table 1 or Table 2.

[0080] In one embodiment of the device of the present invention, at least one other matrix material is selected for use in the light-emitting layer and is used with a compound of formula (1) or with a compound of one of formulas (1-1) to (1-4) as described above or with a compound from Table 1 or Table 2.

[0081] Therefore, the present invention further provides an organic electronic device as described above, wherein the organic layer comprises at least one light-emitting layer, the light-emitting layer comprising at least one compound of formula (1), or at least one of the preferred formulas (1-1) to (1-4), or compounds from Table 1 or Table 2, and at least one other matrix material.

[0082] Therefore, the present invention further provides an organic electronic device as described above, wherein the organic layer comprises at least one light-emitting layer, the light-emitting layer comprising at least one compound of formula (1), or at least one of the preferred formulas (1-1) to (1-4), or compounds from Table 1 or Table 2, and two other matrix materials.

[0083] Suitable matrix materials that can be used in combination with the compounds of the present invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or aromatic sulfones, triarylamines, carbazole derivatives, biscarbazoles, indoloxacarbazole derivatives, indoxacarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, borazine or borate esters, triazine derivatives, zinc complexes, diazacyclopentane or tetrazacyclopentane derivatives, phosphonodiazacyclopentane derivatives, bridging carbazole derivatives, biphenylide derivatives, or dibenzofuran derivatives. Similarly, the mixture may contain other phosphorescent emitters with shorter emission wavelengths than the actual emitters as co-hosts, or may contain compounds that, even if they participate in charge transport, will not reach a significant level, such as wide-bandgap compounds.

[0084] Wide bandgap material is to be understood 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, and the bandgap is to be understood as the interval between the HOMO energy level and the LUMO energy level of the material.

[0085] Particularly suitable matrix materials that can be advantageously combined with compounds according to formula (1) or with compounds of formulas (1-1) to (1-4) as described above or below in a mixed matrix system may be selected from compounds of formulas (eTMM1), (eTMM2), (eTMM3), (eTMM4) or (eTMM5) as described below.

[0086] Therefore, the present invention further provides a mixture comprising at least one compound according to formula (1) as described above or one compound according to formulas (1-1) to (1-4) as described above, and at least one compound according to formulas (eTMM1), (eTMM2), (eTMM3), (eTMM4) and / or (eTMM5) as described below.

[0087] Therefore, the present invention further provides an organic electronic 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 described as a matrix material 1, and at least one compound of formula (eTMM1), (eTMM2), (eTMM3), (eTMM4), and / or (eTMM5) as a matrix material 2. Formula (eTMM1), Formula (eTMM2), Formula (eTMM3), Formula (eTMM4), Formula (eTMM5), in which the symbols and notations used are as follows: X represents N or CR in each occurrence, either the same or different. 6 N is the preferred representative; L 2 The same or different in each case, and is a single bond or has 5 to 24 ring atoms and can be one or more R in each case. 7 Aromatic or heteroaromatic ring systems with substituted groups; R# may be the same or different in each case, and is D, F, CN, or has 6 to 24 ring atoms and can be substituted by one or more R. 6 Aromatic ring systems with substituent groups, where two adjacent substituents R# together can form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems, said aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems can be formed by one or more R# groups. 7 Group substitution; Y may be the same or different in each case, and is N or CR. 7 This excludes the possibility that two adjacent Y's are both N; V 2 Is it O or S; R 6 In each case, the same or different, and is H, D, F, 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 in each case may 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 Instead, or having 5 to 60 ring atoms and in each case can be one or more R 7 Aromatic or heteroaromatic ring systems with substituted groups; here, two R groups... 6 Groups can also combine to form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; Ar 5 The same or different in each case, and having 5 to 40 ring atoms and being capable of being controlled by one or more R atoms.7 Aromatic or heteroaromatic ring systems with substituted groups; R 7 The same or different in each case, and is H, 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 in each case may be one or more R 8 Group substitution, and one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Instead, or having 5 to 40 ring atoms and in each case can be one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 7 The groups together can form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; R 8 In each case, 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, in which one or more hydrogen atoms may also be replaced by F; b1 is 0, 1, 2, 3 or 4; b2 is 0, 1, 2 or 3.

[0088] Preferred compounds of formula (eTMM1) are compounds of formulas (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), and (eTMM1f). Formula (eTMM1a), Formula (eTMM1b), Formula (eTMM1c), Formula (eTMM1d), Formula (eTMM1e), Equations (eTMM1f), where the symbols and notations of these equations are defined as follows: W, W 1 The same or different in each case, and is O, S, C(R) W )2 or N-Ar 5 ;RW In each case, the same or different, and is 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 hydrogen atoms may be replaced by D, F, or CN, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and being substituted by one or more substituents 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 hydrogen atoms in the alkyl group of the aromatic or heteroaromatic ring system may be replaced by D, F, or CN; simultaneously, two R atoms bonded to the same carbon atom W Groups can also form cyclic systems with each other; A may be the same or different in each case and is CR 7 Or N, wherein no more than two A groups in each ring are N, and wherein when L 2 When bonded to position A, A is C; a3 is the same or different in each case, and is 0, 1, 2, 3, or 4; b3 is the same or different in each case, and is 0, 1, 2, or 3; ring B Derived from aryl groups having 6 to 20 ring atoms and being substituted by one or more substituents R#; cyclic C yes or L3 is an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms, wherein the aromatic ring system and the heteroaromatic ring system can be generated by one or more R 7 Group substitution; and wherein L 2 X, Ar 5 R 7 R# has the definition given above.

[0089] The preferred compound of formula (eTMM2) is the compound of formula (eTMM2a):

[0090] Where Y and V 2 L2, R 7 a3 has the definition given above, D is deuterium, and a4 is 0, 1, or 2.

[0091] The preferred compound of formula (eTMM3) is the compound of formula (eTMM3a): Equation (eTMM3a) where the symbols and notations of this equation (eTMM3a) are defined as follows: W 1 The same or different in each case and is O, S, C(R) W )2 or N-Ar 5 #X is CR or NAr 5NAR is preferred 5 ;R W In each case, the same or different, and is 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 hydrogen atoms may be replaced by D, F, or CN, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and being substituted by one or more substituents 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 hydrogen atoms in the alkyl group of the aromatic or heteroaromatic ring system may be replaced by D, F, or CN; a3 In each case, the same or different, and is 0, 1, 2, 3, or 4; Ring B Derived from aryl groups having 6 to 20 ring atoms and being substituted by one or more substituents R#; cyclic C yes or ; where L 2 Ar 5 R# has the definition given above.

[0092] In compounds of formula (eTMM1a), W is preferably O or N-Ar. 5 .

[0093] In compounds of formula (eTMM1a), A is preferably the same or different in each case, and is CR 7 , where L 2 When bonded to position A, A is C.

[0094] In compounds of formula (eTMM1e) or (eTMM3a), W 1 The preferred options are O and C(R) W )2 or N-Ar 5 More preferably N-Ar 5 .

[0095] In compounds of formula (eTMM1f), L 3 Preferably, it has 9 to 30 ring atoms and can be converted by one or more R atoms. 7 Heteroaromatic ring systems with substituted groups.

[0096] In a preferred embodiment of compounds of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4), and (eTMM5) that can be combined with the compounds of the present invention detailed above, R7 In each case, the same or different alkyl groups selected from H, D, F, CN, are straight-chain alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, wherein the alkyl group in each case may be one or more R 8 Group substitution, or having 5 to 60 ring atoms, preferably 5 to 40 ring atoms, and in each case being substituted with one or more R groups. 8 Aromatic or heteroaromatic ring systems with substituted groups.

[0097] In a particularly preferred embodiment of compounds of formula (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4), or (eTMM5) that can be combined with the compounds of the present invention detailed above, R 7 In each case, they may be the same or different and are selected from H, D, or have 6 to 30 ring atoms and can be generated by one or more R atoms. 8 Aromatic or heteroaromatic ring systems with substituted groups.

[0098] The preparation of compounds of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4), and (eTMM5) is generally known, and some of these compounds are commercially available.

[0099] If the matrix material is a deuterated compound, the matrix material may be a mixture of deuterated compounds having the same basic chemical structure, differing only in the level of deuteration.

[0100] In a preferred embodiment of the matrix material, the matrix material is a mixture of the deuterated compounds of the present invention or compounds of the formula (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5) as described above, wherein the deuteration level of these compounds is at least 50 mol% to 90 mol%, preferably 70 mol% to 100 mol%. The corresponding deuteration methods are known to those skilled in the art and are described, for example, in KR2016041014, WO2017 / 122988, KR202005282, KR101978651 and WO2018 / 110887 or Bulletin of the Chemical Society of Japan, 2021, 94(2), 600-605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0101] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms with 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.

[0102] The platinum catalyst is preferably dry platinum / carbon, more preferably 5% dry platinum / carbon. The palladium catalyst is preferably dry palladium / carbon, more preferably 5% dry palladium / carbon. 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 herein. 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 between 100°C and 200°C. Furthermore, the reaction is preferably carried out under pressure.

[0103] Suitable compounds of formula (eTMM1) are, for example, known from the following publications: WO2007 / 077810A1, WO2008 / 056746A1, WO2010 / 136109A1, WO2011 / 057706A2, WO2011 / 160757A1, WO2012 / 023947A1, WO2012 / 048781A1, WO2013 / 077352A1, WO2013147205A1, WO2013 / 083216A1, WO2014 / 094963A1, WO2014 / 007564A1, WO2014 / 015931A1, WO2015 / 0 90504A2, WO2015 / 105251A1, WO2015 / 169412A1, WO2016 / 015810A1, WO2016 / 013875A1, WO2016 / 010402A1, WO2016 / 033167A1, WO2017 / 178311A1, WO 2017 / 076485A1, WO2017 / 186760A1, WO2018 / 004096A1, WO2018 / 016742A1 , WO2018 / 123783A1, WO2018 / 159964A1, WO2018 / 174678A1, WO2018 / 174679 A1, WO2018 / 174681A1, WO2018 / 174682A1, WO2019 / 177407A1, WO2019 / 245164A1, WO2019 / 240473A1, WO2019 / 017730A1, WO2019 / 017731A1, WO2019 / W O2021 / 101220A1, WO2021 / 037401A1, WO2021 / 180614A1, WO2021 / 239772A1, WO2022 / 015084A1, WO2022 / 025714A1, WO2022 / 055169A1, EP3575296A1, EP3591728A1, US2014 / 0361254A1, US2014 / 0361268A1, KR20210036304A, KR20210036857A, KR2021147993A, JP2011 / 160367A2 and JP2017 / 107992A2.

[0104] Suitable compounds of the formula (eTMM2) are, for example, known from the following publications: WO2015 / 182872A1, WO2015 / 105316A1, WO2017 / 109637A1, WO2018 / 060307A1, WO2018 / 151479A2, WO2018 / 088665A2, WO2018 / 060218A1, WO2018 / 234932A1, WO2019 / 058200A1, WO2019 / 017730A1, WO2019 / 017731A1, WO2019 / 066282A1, WO 2019 / 059577A1, WO2020 / 141949A1, WO2020 / 067657A1, WO2022063744A1, WO2022 / 090108A1, WO2022 / 207678A1, WO2023061998A1, KR20 170139443A, KR20190036867A, KR2019035308A, KR2021147993A, CN110294753A, CN110437241A, US2016 / 072078A1, US2019 / 148646A1.

[0105] Suitable compounds of formula (eTMM3) are known, for example, from the following publications: WO2017 / 160089A1, WO2019 / 017730A1, WO2019 / 017731A1, WO2020 / 032424A1.

[0106] Suitable compounds of formula (eTMM5) are known, for example, from the following publications: WO2015 / 093878A1, WO2016 / 033167A1, WO2017 / 183859A1, WO2017 / 188655A1, WO2018 / 159964A1.

[0107] For combinations with the compounds of the present invention as described or preferably described above, suitable compounds are particularly those of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2) and / or (eTMM2a) as described or preferably described above, or the corresponding compounds covered by these formulas in the table below. Compounds of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), and / or (eTMM1f) are particularly preferred herein.

[0108] Other examples of suitable host materials for the compounds of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4), and (eTMM5) that can be combined with the compounds of the present invention detailed above are the structures shown in Table 3.

[0109] Table 3

[0110] As described above, the particularly suitable compounds of the formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), and / or (eTMM2) that can be combined with the compounds of the present invention detailed above and used in the electroluminescent devices or mixtures of the present invention are compounds E1 to E41 in Table 4.

[0111] Table 4

[0112] The above-described main materials of the present invention and their preferred embodiments can be combined in any desired manner with the following substances in the device of the present invention: the above-described matrix / main materials, matrix / main materials of formula (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5) and their preferred embodiments as described in Table 1 or compounds H1 to H12 as described in Table 2.

[0113] The main material of formula (1) above and the compounds described in Table 1, as well as compounds H1 to H12, may be combined with the following substances in the device of the present invention as needed: the matrix material / main material above, the matrix material / main material of formula (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5) and the compounds E1 to E41 described in Table 3.

[0114] A particularly preferred mixture of the compound of formula (1) used in the device of the present invention and the main material of formula (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5) is obtained by combining compounds H1 to H12 with compounds E1 to E41, as shown in Table 5 below. The first mixture M1 is, for example, a combination of compounds E1 and H1.

[0115] Table 5:

[0116] Based on the overall composition of the mixture or the light-emitting layer, the total concentration of all the main materials of the present invention as described above or preferably described 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% to 90% by weight, preferably in the range of 10% to 85% by weight, more preferably in the range of 20% to 85% by weight, even more preferably in the range of 30% to 80% by weight, very particularly preferably in the range of 20% to 60% by weight, and most preferably in the range of 30% to 50% by weight.

[0117] Based on the overall composition of the mixture or the light-emitting layer, the total concentration of all the main materials of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4), or (eTMM5) as described above or preferably described herein 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%.

[0118] The present invention also relates to a mixture comprising, in addition to the main material of the present invention described above and at least one of the main materials of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4), and (eTMM5) as described above or preferably, at least one phosphorescent emitter.

[0119] The present invention further relates to a mixture selected from M1 to M492 and having at least one phosphorescent emitting element as described below.

[0120] The term "phosphorescent emitter" generally encompasses compounds that emit light via spin-forbidden transitions from excited states with high spin multiplicity (i.e., spin states > 1), such as from triplet states or states with even higher spin quantum numbers (e.g., quintet states). This should preferably be understood to refer to transitions from triplet states.

[0121] Suitable phosphorescent emitters (= triplet emitters) are, in particular, compounds that, when properly excited, emit light preferably in the visible light region and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially metals having this atomic number. 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.

[0122] Generally, all phosphorescent complexes, such as those used in phosphorescent OLEDs according to the prior art and those known to those skilled in the art of organic electroluminescent devices, are suitable.

[0123] The preferred phosphorescent emitters according to the present invention conform to formulas (I), (II), (III), (IV) or (V).

[0124] Formula (I) Equation (II) Equation (III) Formula (IV) Formula (V) The symbols and designations of these formulas (I), (II), (III), (IV) and (V) are defined as follows: R1 is H or D, R2 is H, D, F, CN or a branched or straight-chain alkyl group having 1 to 10 carbon atoms or a partially or fully deuterated branched or straight-chain alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms that can be partially or fully substituted by deuterium.

[0125] The preferred phosphorescent emitters according to the present invention conform to formulas (VI), (VII) or (VIII).

[0126] Formula (VI) Equation (VII) Formula (VIII) The symbols and designations of these formulas (VI), (VII) and (VIII) are defined as follows: R1 is H or D, R2 is H, D, F, CN or a branched or straight-chain alkyl group having 1 to 10 carbon atoms or a partially or fully deuterated branched or straight-chain alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms that can be partially or fully substituted by deuterium.

[0127] The preferred phosphorescent emitter according to the present invention conforms to formula (IX). Formula (IX) where the symbols and notations of Formula (IX) are defined as follows: n+m is 3, n is 1 or 2, m is 2 or 1, X is the same or different in each case and is N or CR, R is the same or different in each case and is H, D, F, CN, or a branched or straight-chain alkyl group having 1 to 10 carbon atoms or a partially or fully deuterated branched or straight-chain alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, said cycloalkyl group being partially or fully substituted with deuterium, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and being partially or fully substituted with deuterium.

[0128] Therefore, the present invention further provides an organic electroluminescent device as described above or preferably described above, characterized in that, in addition to the host materials 1 and 2, the light-emitting layer also comprises at least one phosphorescent material of formula (IX) as described above.

[0129] In the light emitter of formula (IX), n is preferably 1 and m is preferably 2.

[0130] In the luminescent body of formula (IX), preferably, one X is selected from N, and the other X are CR, or all X are the same or different in each case and are CR.

[0131] In the luminescent body of formula (IX), at least one R is preferably different from H. In the luminescent body of formula (IIIa), preferably two Rs are different from H and have one of the other definitions given above for the luminescent body of formula (IX).

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

[0133] Examples of particularly preferred phosphorescent luminescent materials are listed in Table 6 below.

[0134] Table 6:

[0135] In the mixtures of the present invention or in the light-emitting layer of the device of the present invention, any mixture selected from the sum of mixtures M1 to M492 is preferably combined with compounds of formulas (I) to (IX) or compounds from Table 6.

[0136] The light-emitting layer in the organic electroluminescent device of the present invention, which contains at least one phosphorescent light emitter, is preferably a layer that emits infrared light or emits yellow, orange, red, green, blue or ultraviolet light, more preferably a layer that emits yellow or green light, and most preferably a layer that emits green light.

[0137] Layers emitting yellow light should be understood as those with a photoluminescence peak value in the range of 540 to 570 nm. Layers emitting orange light should be understood as those with a photoluminescence peak value in the range of 570 to 600 nm. Layers emitting red light should be understood as those with a photoluminescence peak value in the range of 600 to 750 nm. Layers emitting green light should be understood as those with a photoluminescence peak value in the range of 490 to 540 nm. Layers emitting blue light should be understood as those with a photoluminescence peak value in the range of 440 to 490 nm. Here, the photoluminescence peak of each layer is determined by measuring the photoluminescence spectrum of a layer with a thickness of 50 nm at room temperature, wherein the layer comprises the host material 1 of formula (1) and the host material 2 of the present invention, which is composed of at least one of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4) and (eTMM5), and the corresponding light emitter.

[0138] The photoluminescence spectrum of the layer was recorded, for example, using a commercial photoluminescence spectrometer.

[0139] Usually in 10 -5In an oxygen-free solution of M, the photoluminescence spectrum of a selected luminescent material was measured at room temperature. A suitable solvent was any solvent in which the selected luminescent material was dissolved at the mentioned concentration. Particularly suitable solvents were typically toluene or 2-methyl-THF, and also dichloromethane. Measurements were performed using a commercial photoluminescence spectrometer. The triplet energy level T1, in eV, was determined from the photoluminescence spectrum of the luminescent material. First, the maximum peak value Plmax. (in nm) of the photoluminescence spectrum was determined. Then, the maximum peak value Plmax. (in nm) was converted to eV using the following formula: E(T1, in eV) = 1240 / E(T1, in nm) = 1240 / Plmax. (in nm).

[0140] Therefore, the preferred phosphorescent emitter is a yellow emitter, preferably a yellow emitter of formula (IX), a yellow emitter of formulas (I) to (VIII) or a yellow emitter from Table 6, with its triplet energy level T1 preferably being about 2.3 eV to about 2.1 eV.

[0141] Therefore, the preferred phosphorescent emitter is a green emitter, preferably a green emitter of formula (IX), a green emitter of formulas (I) to (VIII) or a green emitter from Table 6, wherein the triplet energy level T1 is preferably about 2.5 eV to about 2.3 eV.

[0142] Therefore, the particularly preferred phosphorescent emitter is the green emitter as described above, preferably the green emitter of formula (IX), the green emitter of formulas (I) to (VIII) or the green emitter from Table 6, whose triplet energy level T1 is preferably about 2.5 eV to about 2.3 eV.

[0143] Most preferably, the green light emitter as described above, preferably the green light emitter of formula (I) to (IX) or the green light emitter from Table 6, is selected for the mixture of the present invention or the light-emitting layer of the present invention.

[0144] 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.

[0145] Preferred fluorescent compounds are selected from the class of arylamines, wherein preferably, at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, more preferably a fused ring system having at least 14 ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyreneamines, aromatic pyrene diamines, aromatic pyrine amines, or aromatic pyrine diamines. Aromatic anthraceneamines should be understood as compounds in which a diaryl amino group is directly bonded to an anthracene group, preferably at the 9-position. Aromatic anthracene diamines should be understood as compounds 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 similarly defined, wherein the diaryl amino group is preferably bonded to pyrene at the 1- or 1,6-positions. Other preferred luminescent compounds are indenefluoreneamine or indenefluorene diamine, benzo[a]indenefluoreneamine or benzo[a]indenefluorene diamine, and dibenzo[a]indenefluoreneamine or dibenzo[a]indenefluorene diamine, as well as indenefluorene derivatives having fused aryl groups. Pyrene arylamines are also preferred. Benzo[a]indenefluoreneamine, benzo[a]fluoreneamine, extended benzo[a]indenefluorene, phenazine, and fluorene derivatives linked to furan or thiophene units are also preferred. The luminescent devices or mixtures of the present invention may further comprise materials exhibiting TADF (thermally activated delayed fluorescence).

[0146] In other preferred embodiments of the invention, the at least one light-emitting layer of the organic electroluminescent device may have three or four different matrix materials, preferably three different matrix materials. These corresponding mixed matrix systems may consist of the matrix materials described for host material 1 and host material 2, but may also include, for example, a wide-bandgap material, a bipolar host material, an electron transport material (ETM), or a hole transport material (HTM) as a third or fourth matrix material, in addition to host material 1 or host material 2.

[0147] Preferably, the mixed matrix system is optimized for the light emitters of formulas (I) to (IX) or for the light emitters from Table 6.

[0148] In one embodiment of the invention, the mixture contains no other components, i.e., functional materials, besides the composition of the host material and host material 2 of formula (1) as described above or preferably, as described above. These are material mixtures used as is to manufacture the light-emitting layer. These mixtures are also referred to as premixed systems, which serve as the sole material source in the vapor deposition of the host material for the light-emitting layer and have a constant mixing ratio in the vapor deposition. In this way, vapor deposition of a layer with uniformly distributed components can be achieved in a simple and rapid manner without the need to precisely drive multiple material sources.

[0149] In an alternative embodiment of the invention, in addition to the components of the host material and host material 2 of formula (1) as described above or preferably described, the mixture also contains the phosphorescent emitter as described above. With a suitable mixing ratio in vapor deposition, this mixture can also be used as the sole material source.

[0150] Preferred is a premixed system consisting of two matrix materials, namely a compound of formula (1) and a compound of one of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4) and (eTMM5).

[0151] Preferred is a premixed system consisting of three matrix materials, namely a compound of formula (1) and two compounds of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4) and (eTMM5).

[0152] Therefore, the components or elements of the light-emitting layer of the device of the present invention can be obtained by vapor deposition or by treatment from solution. For this purpose, a combination of materials 1 and 2 as described or preferably described above is provided in a formulation containing at least one solvent, optionally further comprising a phosphorescent emitter as described or preferably described above. Suitable formulations have been described above.

[0153] Based on the overall composition of the luminescent material and the matrix material, the luminescent layer (according to the preferred embodiment and the luminescent compound) in the device of the present invention contains preferably 99.9 vol% to 1 vol%, more preferably 99 vol% to 10 vol%, particularly preferably 98 vol% to 60 vol%, and very particularly preferably 97 vol% to 80 vol% of a matrix material. According to the preferred embodiment, the matrix material is composed of at least one compound of formula (1) and at least one compound of formula (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f), (eTMM2), (eTMM2a), (eTMM3), (eTMM3a), (eTMM4), and (eTMM5). Accordingly, based on the overall composition of the light-emitting layer consisting of the light emitter and the matrix material, the light-emitting layer in the device of the present invention preferably contains 0.1 vol% to 99 vol%, more preferably 1 vol% to 90 vol%, more preferably 2 vol% to 40 vol%, and most preferably 3 vol% to 20 vol% of the light emitter. If the compound is processed from a solution, it is preferable to use the corresponding amount in weight % rather than the amount in volume % described above.

[0154] The present invention also relates to organic electroluminescent devices as described above or preferably described, 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 category of arylamines.

[0155] The preferred layer order in the organic electroluminescent device of the present invention is as follows: anode / hole injection layer / hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0156] This layer order is a preferred order.

[0157] 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.

[0158] The material used for the electron transport layer can be any material as used as an electron transport material in the electron transport layer according to existing technology. 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.

[0159] A suitable cathode for the device of the present invention is a metal with low work function, such as a metal alloy or multilayer structure composed of various metals, including 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 a multilayer structure, in addition to the metals mentioned, other metals with relatively high work functions, such as Ag or Al, may be used. In this case, combinations of metals such as Ca / Ag, Mg / Ag, or Ba / Ag are typically used. It is also preferable to introduce a thin interlayer of material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of useful materials for this purpose are alkali metal or alkaline earth metal fluorides, and their corresponding oxides or carbonates (e.g., LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.). For this purpose, lithium quinoline (LiQ) may also be used. The thickness of this layer is preferably 0.5 to 5 nm.

[0160] 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 are suitable for this purpose, such as Ag, Pt, or Au. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are preferred. x Al / PtO x Alternatively, an anode may be preferred. For some applications, at least one electrode must be transparent or partially transparent to allow illumination of organic materials (organic solar cells) or light emission (OLEDs, O-lasers). Preferred anode materials are conductive mixed metal oxides. Indium tin oxide (ITO) or zinc indium oxide (IZO) are particularly preferred. Conductive doped organic materials, especially conductive doped polymers, are further preferred. Additionally, the anode may consist of two or more layers, for example, an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide, or vanadium oxide.

[0161] Since the lifespan of the organic electroluminescent device of the present invention is shortened in the presence of water and / or air, the device of the present invention is appropriately constructed (depending on the application) during the manufacturing process, with contact connections provided and finally sealed.

[0162] The manufacture of the device of the present invention is not limited herein. One or more organic layers, including the light-emitting layer, can be coated by a sublimation method. In this case, the material is sublimated in a vacuum sublimation system at a temperature below 10°C. -5 millibars, preferably below 10 -6 An initial pressure of millibars is applied via vapor deposition. However, in this case, the initial pressure can be even lower, for example, below 10. -7 millibar.

[0163] 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, the material is in a 10 -5 The pressure is applied at a range of millibars to 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through the nozzle and thus structured (e.g., MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0164] 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 from solution, for example by spin coating, or by any printing method such as screen printing, flexographic printing, nozzle printing, or offset printing, but more preferably by LITI (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 processing from solution is, for example, that the luminescent layer can be applied in a very simple and inexpensive manner. This technique is particularly suitable for the large-scale production of organic electroluminescent devices.

[0165] Alternatively, a hybrid approach is feasible, in which, for example, one or more layers are applied from a solution and one or more other layers are applied by vapor deposition.

[0166] These methods are well known to those skilled in the art and can be applied to organic electroluminescent devices.

[0167] Therefore, the present invention further provides a method for manufacturing an organic electroluminescent device as described above or preferably described herein, characterized in that the organic layer, preferably a light-emitting layer, a hole injection layer and / or a hole transport layer, is applied by vapor deposition, especially by sublimation and / or by OVPD (organic vapor deposition) and / or by means of a carrier gas, or from a solution, especially by spin coating or by printing.

[0168] In the case of fabrication using vapor deposition, there are, in principle, two methods to apply or vapor-deposit the organic layer, preferably the luminescent layer, of the present invention onto any substrate or existing layer. First, the materials used can initially be individually loaded into material sources and ultimately evaporated from different material sources (“co-evaporation”). Second, the various materials can be premixed (premixed system), and the mixture can initially be loaded into a single material source, from which it is ultimately evaporated (“premixed evaporation”). In this way, vapor deposition of a luminescent layer with uniformly distributed components can be achieved simply and quickly without the need for precisely driving multiple material sources.

[0169] The following method is feasible: a method for manufacturing an organic electroluminescent device of the present invention as described above or preferably, characterized in that an organic layer, preferably a light-emitting layer, an electron transport layer and / or a hole-blocking layer, is applied by vapor deposition, especially by sublimation and / or by OVPD (organic vapor deposition) and / or by means of a carrier gas, or from a solution, especially by spin coating or by printing.

[0170] A method for manufacturing an organic electroluminescent device of the present invention as described above or preferably described herein, characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein the at least one compound of formula (1) is vapor-deposited sequentially or simultaneously from at least two material sources together with other materials forming the light-emitting layer.

[0171] 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 the at least one compound of formula (1) is used as a premix with at least one other matrix material and is sequentially or simultaneously deposited from the vapor phase with a light-emitting material selected from phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0172] Compared with the prior art, the electronic devices of the present invention, especially organic electroluminescent devices, are noteworthy for one or more of the following unexpected advantages: 1. Electronic devices, especially organic electroluminescent devices, containing compounds of formula (1) described above and below, or preferred embodiments thereof, particularly as matrix materials or hole-conducting materials, have very good lifetimes. In this case, these compounds particularly cause low roll-off, i.e., a small decrease in the power efficiency of the device at high luminous density.

[0173] 2. Electronic devices, especially organic electroluminescent devices, containing compounds of formula (1) as described above and below, or preferred embodiments thereof, as hole-conducting materials and / or matrix materials, exhibit excellent efficiency. In this case, the compounds of the present invention having the structure of formula (1) as described above and below, or preferred embodiments thereof, cause low operating voltage when used in electronic devices.

[0174] 3. The compounds of formula (1) of the present invention described above and below, or the preferred embodiments thereof, exhibit very high stability and lifespan.

[0175] 4. By utilizing the compounds of formula (1) described above and below, or the preferred embodiments thereof, optical loss channels can be avoided in electronic devices, especially organic electroluminescent devices. As a result, these devices are characterized by high PL efficiency of the light emitter, thus high EL efficiency, and excellent energy transfer from the matrix to the dopant.

[0176] 5. When the compounds of formula (1) described above and below, or the preferred embodiments thereof, are used in layers in electronic devices, especially organic electroluminescent devices, they produce high mobility of electronic conductor structures.

[0177] 6. The compounds of formula (1) described above and below, or the preferred embodiments thereof, have excellent glass film formation.

[0178] 7. The compound of formula (1) described above and below, or the preferred embodiment, forms a very good film from solution.

[0179] 8. The compound of formula (1) described above and below, or the preferred embodiment, has a triplet energy level T1 that may be in the range of 2.00 eV to 2.90 eV, for example.

[0180] These advantages are not accompanied by an excessive deterioration of other electronic properties.

[0181] It should be noted that the scope of this invention covers variations of the embodiments described herein. Unless expressly excluded, any feature disclosed in this invention is interchangeable with a substitute feature serving 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.

[0182] Unless specific features and / or steps are mutually exclusive, all features of the invention can be combined with each other in any way. This is especially true of combinations of preferred features of the invention. Similarly, features that are not necessarily combined can be used individually (rather than in combination).

[0183] The technical teachings disclosed in this invention can be refined and combined with other examples.

[0184] The present invention is illustrated in detail by way of the following embodiments, but is not intended to limit the invention thereto.

[0185] Example

[0186] Unless otherwise stated, the following synthesis was performed in anhydrous solvents under a protective atmosphere. Solvents and reagents are available from, for example, Sigma-Aldrich or ABCR. The corresponding numbers in square brackets or the reference numbers for individual compounds relate to the CAS numbers of compounds known in the literature. Where compounds may have multiple enantiomers, diastereomers, or tautomers, one form is shown in a representative manner.

[0187] A: Synthesis of synthesizer S: Example S1

[0188] According to SH Kim et al., J. Mat. Chem., 2011, 21(25), 9139.

[0189] Using 40.6 g (100 mmol) of 3,6-dibromo-9-(phenyl-2,3,4,5,6-d5)-9H-carbazole [1354054-12-8]. Yield: 35.1 g (70 mmol). Purity: Approximately 98% 1 H-NMR).

[0190] The following compounds can be prepared similarly:

[0191] Example S100:

[0192] Prepared according to P. Gong et al., Tetrahedron Letters, 2016, 57, 1468.

[0193] The product was separated from the isomer mixture using 16.5 g (50 mmol) of β,B'-(9-phenyl-9H-carbazole-3,6-diyl)bisboronic acid [1135916-40-3] and 26.3 g (130 mmol) of 1-bromo-2-nitrobenzene [577-19-5]. The product was isolated from the isomer mixture by automated rapid chromatography (CombiFlashTorrent, A. Semrau). Yield: 7.2 g (17 mmol) 34%. Purity: Approximately 99% ( 1 H-NMR).

[0194] The Cadogan cyclization reaction can be performed using triphenylphosphine (4.4 equivalents) instead of triethyl phosphite [P(OEt)3] in o-dichlorobenzene at 180°C for 48 hours. The o-dichlorobenzene is removed under vacuum, and the residue is stirred with 200 ml of isopropanol to remove triphenylphosphine oxide. The crude product is purified as described above. Yield: 12.4 g (29 mmol), 58%. Purity: Approximately 99%. 1 H-NMR).

[0195] The Cadogan cyclization reaction was carried out in an autoclave using carbon monoxide (4 bar) instead of triethyl phosphite [P(OEt)3] in 1000 ml of dimethylformamide (DMF) in the presence of 450 mg (2 mmol) palladium(II) acetate and 1.49 g (8 mmol) 1,10-phenanthroline at 120 °C for 20 h. See JH Smitrovich et al., Org. Lett. (Organic Chemistry Letters), 2004, 6(4), 533. DMF was removed under vacuum, and the crude product was purified as described above. Yield: 15.1 g (35 mmol) 70%. Purity: approximately 99% ( 1 H-NMR).

[0196] The following compounds can be prepared similarly:

[0197] C: Synthesis of material M in this invention: Example M1

[0198] 1) M1A: Ullmann coupling 1

[0199] A mechanically stirred mixture of 42.1 g (100 mmol) S100, 40.8 g (200 mmol) iodobenzene [591-50-4], 41.5 g (300 mmol) potassium carbonate, 953 mg (5 mmol) cuprous iodide (I), 1.5 ml (10 mmol) tetramethylenediamine (TMEDA), 300 g glass beads (3 mm in diameter), and 800 ml o-xylene was heated under reflux for 24 hours. The hot reaction mixture was filtered through a diatomaceous earth bed eluted with o-xylene. The filtrate was evaporated to dryness, and the residue was dissolved in 700 ml dichloromethane (DCM). The organic phase was washed once with 200 ml 10% ammonia, twice with 200 ml water, once with 200 ml brine, and dried over magnesium sulfate. The mixture was filtered through a silica gel bed eluted with DCM. The filtrate was evaporated to dryness, and the residue was stirred in 200 mL of isopropanol. The product was collected by filtration and dried under reduced pressure. Further purification was performed by automated rapid chromatography (CombiFlashTorrent, A. Semrau). Yield: 45.1 g (91 mmol), 91%. Purity: Approximately 99%. 1 H-NMR).

[0200] 2) M1: Ullmann coupling 2

[0201] A mechanically stirred mixture of 49.7 g (100 mmol) M1A, 56.0 g (200 mmol) 4-iodobiphenyl [1591-31-7], 41.5 g (300 mmol) potassium carbonate, 42.6 g (300 mmol) anhydrous sodium sulfate, 636 mg (10 mmol) copper powder, 300 g glass beads (3 mm in diameter), and 600 ml 1,2-dichlorobenzene was heated under reflux for 18 hours. The hot reaction mixture was filtered through a diatomaceous earth bed eluted with 1,2-dichlorobenzene. The filtrate was evaporated to dryness, and the residue was dissolved in 600 ml DCM. The organic phase was washed once with 200 ml of 10% ammonia, twice with 200 ml of water, once with 200 ml of brine, and dried over magnesium sulfate. The mixture was filtered through a silica gel bed eluted with dichloromethane. The filtrate was evaporated to dryness, and the residue was stirred in 200 ml of isopropanol. The product was collected by filtration and dried under reduced pressure. Further purification was performed using automated rapid chromatography (CombiFlashTorrent, A. Semrau) and / or thermal extraction crystallization (using organic solvents, preferably a dichloromethane / acetonitrile mixture, 1:3 to 3:1 v / v), followed by fractional sublimation under high vacuum. Yield: 38.3 g (59 mmol), 59%. Purity: Approximately 99% ( 1 H-NMR).

[0202] If the aromatic groups to be introduced are the same, then the Ullmann coupling scheme can be carried out using 4 equivalents of aryl iodide.

[0203] The following compounds can be prepared similarly:

[0204] Example: OLED Manufacturing

[0205] Vacuum-processed devices: The OLEDs of the present invention are manufactured by a general method according to WO 2004 / 058911, adapted to suit the conditions described herein (changes in layer thickness, materials used).

[0206] In the following examples, results for various OLEDs are provided. A clean glass plate coated with a 50 nm thick structured ITO (indium tin oxide) (cleaned in a Miele laboratory glass cleaner, Merck Extran cleaner) was pretreated with UV ozone for 25 minutes (from a UVP PR-100 UV ozone generator), and within 30 minutes, to improve the treatment, 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate), from Heraeus Precious Metals GmbH, Germany, as CLEVIOS. TM Purchased from PVP Al 4083 (spin-coated from an aqueous solution), the glass was then baked at 180°C for 10 minutes. These coated glass plates form the substrate for OLED applications.

[0207] OLEDs generally have the following layer structure: a hole injection layer (HIL) composed of HTM1 doped with 5% NDP-9 (commercially available from Novaled), a 20nm hole transport layer (HTL), an electron blocking layer (EBL), an emissive layer (EML), a hole blocking layer (HBL), an electron transport layer (ETL) composed of a mixture of ETM1:ETM2 (50%:50%), a 30nm electron injection layer (EIL) composed of ETM2, a 1nm cathode composed of aluminum, and a 100nm cathode. All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emissive layer always consists of at least one matrix material (host material) and a light-emitting dopant (emitting agent), which is added to one or more matrix materials in a specific volume ratio by co-evaporation. Details given in the form of E41:H1:Ir (55%:35%:10%) refer to the presence of material E41 in the layer at a volume ratio of 55%, H1 at a volume ratio of 35%, and Ir at a volume ratio of 10%.

[0208] The precise structure of OLEDs can be seen in Table 7. The materials used to manufacture OLEDs are shown in the experimental section, in Tables 2 and 9.

[0209] OLEDs were characterized in a standard manner. To this end, the electroluminescence spectrum, current efficiency (in cd / A), power efficiency (in lm / W), and external quantum efficiency (EQE, in percentage) were determined as a function of luminous density and calculated from the current-voltage-luminous density characteristics (IUL characteristics) under the assumption of Lambertian luminescence properties.

[0210] In Table 7, the external quantum efficiency (EQE) and voltage (V) are expressed as relative EQE and relative V, respectively, with both EQE and V set to 100% for the reference embodiment. The lifetime LT90 is defined as the time to 40 mA / cm². 2 The time required for the luminous density to decrease to 90% of the initial luminous density when operating at a constant current density. In Table 7, lifetime LT90 is expressed as a relative lifetime (relative to LT90), with the lifetime of the reference embodiment set to 100%.

[0211] One use of the compound of the present invention is as a host material in phosphorescent OLEDs.

[0212] The results for OLED are collected in Table 8.

[0213] Table 7: Structure of OLED

[0214] Table 8: Results of phosphorescent OLED devices

[0215] Table 9: Materials used in the manufacture of OLEDs

Claims

1. A compound, said compound being represented by formula (1): The groups and markings appearing in formula (1) are as follows: R, in each occurrence, either the same or different, preferably the same, represents H or D; R 1 Each occurrence may represent H, D, F, N(R) in the same or different ways. 3 )2,C(=O)R 3 , P(=O)(R 3 )2,S(=O)R 3 S(=O)2R 3 ,Si(R 3 )3,Ge(R) 3 )3, B(R) 3 )2, B(OR 3 )2, OSO2R 3 Aromatic or heteroaromatic ring systems having 5 to 60 ring atoms, wherein in each case the aromatic or heteroaromatic ring system may be substituted by one or more groups R 3 The aryloxy group may be substituted with, or have 5 to 60 cyclic atoms, an aryloxy group, which may be replaced by one or more groups R. 3 Replacement; preferably, in each occurrence, the same or different, more preferably, the same, representing H or D; R 2 Each occurrence may represent H, D, F, N(R) in the same or different ways. 4 )2,C(=O)R 4 , P(=O)(R 4 )2,S(=O)R 4 S(=O)2R 4 ,Si(R 4 )3,Ge(R) 4 )3, B(OR 4 )2, OSO2R 4 Aromatic or heteroaromatic ring systems having 5 to 60 ring atoms, wherein in each case the aromatic or heteroaromatic ring system may be substituted by one or more groups R 4 The aryloxy group may be substituted with, or have 5 to 60 cyclic atoms, an aryloxy group, which may be replaced by one or more groups R. 4 Substitution; where two adjacent substituents R 2 It can form monocyclic or polycyclic aromatic or heterocyclic ring systems, wherein the aromatic or heterocyclic rings can be formed by one or more groups R. 4 Replace; R 3 and R 4 Each occurrence may represent, in the same or different manner, H, D, F, N(Ar)2, C(=O)Ar, P(=O)(Ar)2, S(=O)Ar, S(=O)2Ar, Si(R')3, Ge(R')3, B(OR')2, OSO2R', an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, wherein in each case the aromatic or heteroaromatic ring system may be substituted by one or more groups R', or an aryloxy group having 5 to 60 ring atoms, wherein the aryloxy group may be substituted by one or more groups R'; wherein R 3 and R 4 It can form monocyclic or polycyclic aromatic or heterocyclic ring systems, which can be substituted by one or more groups R'; m and n represent 0, 1, 2, 3 or 4 each time they appear, preferably 0, 1 or 2, more preferably 0 or 1; Ar 1 Ar 2 and Ar 3 Each occurrence may represent, in the same or different ways, an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably 5 to 40 ring atoms, which may in each case be substituted by one or more groups R'; wherein Ar 2 and Ar 3 They can be linked together; R´ in each occurrence represents, either identically or differently, H, D, F, CN, Si(R´´)3, 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, each of which can be represented by one or more groups R. 3 Substitution, wherein in each case one or more non-adjacent CH2 groups may be replaced by R 3 C=CR 3 C≡C, Si(R) 3 )2、Ge(R 3 )2、Sn(R 3 )2. C=O, C=S, C=Se, P(=O)(R 3 ), SO, SO2, O, S or CONR 3 The substitution is made by replacing one or more H atoms with D, F, Cl, Br, I, or NO2, or by an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, wherein two adjacent substituents R' can form a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system, wherein the aliphatic ring system, aromatic or heteroaromatic ring system can be replaced by one or more groups R. 3 Substitution; and R'', in each occurrence, represents, identically or differently, 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, each of which may be replaced by one or more groups R. 3 Substitution, wherein in each case one or more non-adjacent CH2 groups may be replaced by R 3 C=CR 3 C≡C, Si(R) 3 )2、Ge(R 3 )2、Sn(R 3 )2. C=O, C=S, C=Se, P(=O)(R 3 ), SO, SO2, O, S or CONR 3 The substitution is made by replacing one or more H atoms with D, F, Cl, Br, I, or NO2, wherein two adjacent substituents R'' can form a monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring system, which can be replaced by one or more groups R. 3 replace.

2. The compound according to claim 1, characterized in that... The compound is represented by at least one of formulas (1-1) to (1-4): Equation (1-1) Equation (1-2) Equation (1-3) Equation (1-4) In Equations (1-1) to (1-4), Ar 1 Ar 2 and Ar 3 and R 2 It has the definition given in claim 1.

3. The compound according to claim 1 or 2, characterized in that... In equation (1) or equations (1-1) to (1-4), Ar 2 and Ar 3 different.

4. The compound according to one or more of claims 1 to 3, characterized in that... Ar 2 and Ar 3 They are linked together by a single bond or by a linking group, preferably by a single bond.

5. The compound according to one or more of claims 1 to 4, characterized in that... At least one carbazole group in the core structure of formula (1) or formulas (1-1) to (1-4) contains a fused aromatic or heteroaromatic group.

6. The compound according to one or more of claims 1 to 5, characterized in that... The compounds of formula (1) or formulas (1-1) to (1-4) contain at least one deuterium atom as a substituent.

7. The compound according to one or more of claims 1 to 6, characterized in that... R 1 Each occurrence is either identical or different and selected from H, D, F, Si(R) 3 )3, N(R 3 )2, B(R) 3 )2, aromatic ring systems having 6 to 40 ring atoms and heteroaromatic ring systems having 5 to 40 ring atoms, wherein the aromatic ring system and the heteroaromatic ring system may in each case be purported to ... 3 Substitution; or an aryloxy group having 6 to 40 ring atoms, wherein in each case the aryloxy group may be replaced by one or more groups R 3 Replace, R 3 It has the definition given in claim 1.

8. The compound according to one or more of claims 1 to 7, characterized in that... R 2 Each occurrence is either identical or different and selected from H, D, F, Si(R) 4 )3, N(R 4 )2, aromatic ring systems having 6 to 40 ring atoms and heteroaromatic ring systems having 5 to 40 ring atoms, wherein the aromatic ring system and the heteroaromatic ring system may in each case be purported to ... 4 Substitution; or an aryloxy group having 6 to 40 ring atoms, wherein in each case the aryloxy group may be replaced by one or more groups R 4 Replace, R 4 It has the definition given in claim 1.

9. The compound according to one or more of claims 1 to 8, characterized in that... R 3 and R 4 The aromatic ring system and the heteroaromatic ring system having 5 to 40 ring atoms are selected from H, D, F, Si(R')3, N(R')2, respectively, in each occurrence, and may be substituted by one or more groups R' in each case; or an aryloxy group having 6 to 40 ring atoms, which may be substituted by one or more groups R' in each case, R' having the definition given in claim 1.

10. A mixture comprising at least one compound according to any one of claims 1 to 9 and at least one other compound and / or at least one solvent, wherein the other compound is selected from phosphors, phosphorescent materials, TADFs, host materials, matrix materials, electron transport materials, electron injection materials, hole conduction materials, hole injection materials, n-type dopants, p-type dopants, wide bandgap materials, electron blocking materials, and hole blocking materials.

11. A mixture comprising at least one compound according to any one of claims 1 to 9 and at least one compound of the formula (eTMM1), (eTMM2), (eTMM3), (eTMM4), or (eTMM5). Formula (eTMM1), Formula (eTMM2), Formula (eTMM3), Formula (eTMM4), Formula (eTMM5), in which the symbols and notations used are as follows: X represents N or CR in each occurrence, either the same or different. 6 N is the preferred representative; L 2 The same or different in each case, and is a single bond or has 5 to 24 ring atoms and can be one or more R in each case. 7 Aromatic or heteroaromatic ring systems with substituted groups; R# may be the same or different in each case, and is D, F, CN, or has 6 to 24 ring atoms and can be substituted by one or more R. 6 Aromatic ring systems with substituent groups, where two adjacent substituents R# together can form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems, said aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems can be formed by one or more R# groups. 7 Group substitution; Y may be the same or different in each case, and is N or CR. 7 This excludes the possibility that two adjacent Y's are both N; V 2 Is it O or S; R 6 In each case, the same or different, and is H, D, F, 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 in each case may 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 Instead, or having 5 to 60 ring atoms and in each case can be one or more R 7 Aromatic or heteroaromatic ring systems with substituted groups; here, two R groups... 6 Groups can also combine to form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; Ar 5 The same or different in each case, and having 5 to 40 ring atoms and being capable of being controlled by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; R 7 The same or different in each case, and is H, 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 in each case may be one or more R 8 Group substitution, and one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Instead, or having 5 to 40 ring atoms and in each case can be one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 7 The groups together can form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; R 8 In each case, 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, in which one or more hydrogen atoms may also be replaced by F; b1 is 0, 1, 2, 3 or 4; b2 is 0, 1, 2 or 3.

12. An electronic device comprising at least one compound according to one or more of claims 1 to 9 or a mixture according to claim 10 or 11.

13. The electronic device according to claim 12, characterized in that... The electronic device is an organic electroluminescent device and includes an anode, a cathode and at least one light-emitting layer, and is characterized in that the compound is present in the hole transport layer or the light-emitting layer of the device.

14. Use of the compound according to one or more of claims 1 to 9 or the mixture according to claim 10 or 11 in an electronic device.

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