Materials for organic electroluminescent devices

Abstract

The present invention relates to specific deuterated spirocarbazole-triazine derivatives, mixtures and formulations comprising the same, and to electronic devices comprising these compounds, in particular organic electroluminescent devices comprising these compounds as matrix material, electron transport material or hole blocking material.

Description

Technical Field

[0001] This invention relates to specific deuterated spirocarbazole-triazine derivatives, mixtures and formulations comprising these compounds, and electronic devices comprising these compounds, particularly organic electroluminescent devices comprising these compounds as matrix materials, electron transport materials or hole blocking materials. Background Technology

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

[0003] WO 2014 / 094963 A1 describes specific undeuterated spirocarbazole-triazine derivatives and their suitability for organic electronic devices.

[0004] There is still a need to improve these materials, particularly those used as matrix materials. Therefore, the problem addressed by this invention is to provide compounds that are particularly suitable for use as matrix materials, electron transport materials, electron injection materials, or hole blocking materials in phosphorescent OLEDs. More specifically, an object of this invention is to provide matrix materials that result in improved lifetime. This is particularly applicable when using low to moderate emitter concentrations, i.e., 3% to 20%, especially on the order of 3% to 15%, because device lifetime is particularly limited at these emitter concentrations.

[0005] More specifically, an object of the present invention is to provide an electronic transport material that results in improved lifespan.

[0006] It has been found that electroluminescent devices containing compounds of formula (1) or formula (1A) have improvements over the prior art, especially when the compounds are used as matrix materials for phosphorescent dopants.

[0007] It has also been found that this problem is solved and the disadvantages of the prior art are eliminated by combining at least one compound of formula (1) or formula (1A) as a first host material with at least one hole transport compound as one or more other host materials, such as with one or more compounds of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) in the light-emitting layer of organic electronic devices, especially organic electroluminescent devices. Summary of the Invention

[0008] The present invention first provides a compound of formula (1) or formula (1A),

[0009] The symbols and markings used are as follows: Y is the same or different in each case, and is CR 1 Or N, provided that at least one Y group is N; X is the same or different in every case, and is CR 1 Or N; or two adjacent X's are S, O, or NR. 1 To form a five-membered ring; or two adjacent X's are groups of formula (2), (3) or (4) below.

[0010] Where ^ indicates the corresponding adjacent X group in formula (1) or formula (1A); V is the same or different in every case, and is C(R) 1 2. NR 1 O, S, BR 1 Si(R) 1 )2 or C=O; Z is the same or different in every case, and is CR 1 Or N; Ar may be the same or different in each case, and is a ring with 5 to 40 aromatic atoms and can be substituted by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; R may be the same or different in each case, and is selected from H, D, F, Cl, Br, I, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of said groups being soluble in one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C=CR 2 The atoms are C≡C or O, and one or more of the hydrogen atoms may be replaced by D or F, or the atoms have 6 to 60 aromatic ring atoms and may be replaced by one or more R atoms. 2 Aromatic ring systems with substituted groups; here, two adjacent substituents R can also form a ring system that can be substituted by one or more R groups. 2 Monocyclic or polycyclic aliphatic or aromatic ring systems with substituted groups; R 1 The same or different in each case, and selected from H, D, F, Cl, Br, I, CN, NO2, N (Ar) 1 )2,N(R 2)2,C(=O)Ar 1 C(=O)R 2 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, Si(Ar 1 )3,Si(R 2 )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, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of said groups being capable of being formed by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C=CR 2 C≡C, Si(R) 2 2. C=O, C=S, C=NR 2 P(=O)(R) 2 SO, SO2, NR 2 O, S or CONR 2 The atoms are replaced by D, F, Cl, Br, I, CN, or NO2, and the ring has 5 to 60 aromatic ring atoms, each of which can be replaced by one or more R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 60 aromatic ring atoms and being substituted by one or more R groups. 2 A group-substituted aryloxy or heteroaryloxy group; optionally, two adjacent substituents R 1 It can be formed by one or more R 2 Monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring systems with substituted groups; Ar 1 In each case, they may be the same or different, and they are aromatic rings with 5 to 30 atoms and can be separated by one or more non-aromatic R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups; here, two Ar atoms bonded to the same nitrogen or phosphorus atom. 1 Groups can also be formed via single bonds or selected from N(R) 2 ), C(R 2 2. The bridge bases of O or S are bridged to each other; R 2 In each case, they may be the same or different, and are selected from H, D, F, CN, aliphatic hydrocarbon groups having 1 to 20 carbon atoms, or aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, wherein two or more adjacent R atoms 2 Substituents can together form monocyclic or polycyclic aliphatic ring systems; m and n are the same or different in each case, and are 0 or 1, provided that m + n ≥ 1; p is the same or different in each case, and is 0, 1, 2, 3 or 4; q is 0, 1, or 2. The compound of formula (1) or formula (1A) is characterized by containing at least one deuterium atom as a substituent.

[0011] The present invention also provides a mixture comprising at least one compound of the preferred formula (1) or formula (1A) as described above or subsequently described, and at least one other compound selected from matrix materials, phosphorescent emitters, fluorescent emitters, and / or emitters exhibiting TADF (thermally activated delayed fluorescence) and / or solvents.

[0012] The present invention also provides a mixture comprising at least one compound of formula (1) or formula (1A) preferred as described above or subsequently described, and at least one other compound selected from electron transport materials, electron injection materials, hole blocking materials, materials having a high dielectric constant, and / or solvents.

[0013] The present invention also provides an organic electronic device, preferably an organic electroluminescent device, the 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 formula (1A) preferred as described above or subsequently described.

[0014] The present invention also provides a method for manufacturing an organic electronic device, preferably an organic electroluminescent device, as described above or below, characterized in that the organic layer is applied by vapor deposition or from a solution. Detailed Implementation

[0015] In this patent application, "D" or "D atom" refers to deuterium. The degree of deuteration (expressed as mol%) refers to the proportion of hydrogen atoms replaced by deuterium. Since deuterated compounds are typically mixtures of compounds that differ in exact positions and exact proportions of deuterium atoms, the degree of deuteration refers to the average proportion of hydrogen atoms replaced by deuterium. Therefore, a degree of deuteration of 50 mol% means that an average of 50 mol% of hydrogen atoms in the compound have been replaced by deuterium; thus, this is the average degree of deuteration.

[0016] In a first preferred embodiment, the spirocarbazole basic framework has at least one deuterium atom. Here, the spirocarbazole basic framework comprises a spirodifluorene group and a fused carbazole group (including a 6-membered ring formed by an X group). Therefore, at least one R group of the spirodifluorene group and / or one R group of the 6-membered ring formed by the X group... 1 The group is a deuterium atom.

[0017] In a second preferred embodiment, at least one R of an aromatic or heteroaromatic ring system Ar and / or a 6-membered ring formed by a Y group. 1 The group is a deuterium atom.

[0018] In a third preferred embodiment, at least one R group of the spirodifluorene group and / or one R group of a 6-membered ring formed by the X group. 1 The group is a deuterium atom, and at least one R of an aromatic or heteroaromatic ring system Ar and / or a 6-membered ring formed by a Y group. 1 The group is a deuterium atom.

[0019] When the deuterated compound of formula (1) or formula (1A) contains at least one R 2 When the group is present, then in addition to the three preferred embodiments described above, at least one R 2 The group can also be a deuterium atom.

[0020] The degree of deuteration of the compounds of formula (1) or formula (1A) is generally in the range of 1 mol% to 100 mol%, preferably in the range of 10 to 100 mol%, more preferably in the range of 50 mol% to 95 mol%, and most preferably in the range of 70 mol% to 90 mol%.

[0021] The aryl group in the sense of this invention contains 6 to 40 ring atoms, preferably carbon atoms. The heteroaryl group in the sense of this invention contains 5 to 40 ring atoms, wherein the ring atoms include carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and / or S. Here, an aryl group or heteroaryl group refers to a simple aromatic ring, i.e., a phenyl ring derived from benzene, or a simple heteroaryl ring, for example derived from pyridine, pyrimidine or thiophene, or a fused aryl or heteroaryl group, for example derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline. Therefore, an aryl group having 6 to 18 carbon atoms is preferably phenyl, naphthyl, phenanthrene or biphenylidene, and there is no limitation on the connection of aryl groups as substituents. The aryl or heteroaryl group in the sense of this invention may contain one or more groups, wherein suitable groups are described below. If no such group is described, the aryl group or heteroaryl group is unsubstituted.

[0022] The aromatic ring system in this invention contains 6 to 40 carbon atoms. The aromatic ring system also includes aryl groups as described above.

[0023] The aromatic ring system having 6 to 18 carbon atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthryl and biphenylene oxide.

[0024] The heteroaromatic ring system in this invention contains 5 to 40 ring atoms and at least one heteroatom. A preferred heteroaromatic ring system has 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system also includes the heteroaryl group as described above. The heteroatom in the heteroaromatic ring system is preferably selected from N, O, and / or S.

[0025] In this invention, an aromatic or heteroaromatic ring system refers to a system that does not necessarily contain only aryl or heteroaromatic groups, but in which multiple aryl or heteroaromatic groups are also interrupted by non-aromatic units (preferably less than 10% of atoms other than H), such as carbon or oxygen atoms or carbonyl groups. For example, systems such as 9,9'-spirodifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ethers, piracene, etc., should therefore also be considered as aromatic or heteroaromatic ring systems in the sense of this invention, 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 linked to each other, such as biphenyl, terphenyl, tetraphenyl, or bipyridine, are also covered by the definition of an aromatic or heteroaromatic ring system.

[0026] Aromatic or heteroaromatic ring systems having 5 to 40 ring atoms that can be attached to aromatic or heteroaromatic systems at any position should be understood to refer to groups derived from, for example, 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, diphenylidene, terphenyl, diphenylidene, 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], heterotrimer. Indene, spirotrimer indene, spiroisotrimer 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 Zyrazole, benzo[a]azole, naphtho[a]azole, anthraxazole, phenanthrene[a]azole, iso[a]azole, 1,2-thiazole, 1,3-thiazole, benzo[a]thiazole, pyridazine, benzo[a]pyridazine, pyrimidine, benzo[a]pyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenothiazine, fluorescein ring, naphthidine, azacarbazole, benzo[a]carbline, phenanthrene, 1,2,3-triazine Azole, 1,2,4-triazole, benzotriazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indoleazine, and benzothiadiazole.

[0027] abbreviations Ar and Ar 1 The same or different in each case, and indicates having 5 to 40 ring atoms and being able to be one or more R 1 Aromatic or heteroaromatic ring systems with substituent groups, wherein R 1 Group or R 1 Substituents are as defined above or below.

[0028] In the sense of this specification, the phrase "two or more groups can form a ring with each other" should specifically refer to two groups connected to each other by chemical bonds, formally eliminating two hydrogen atoms. This is illustrated by the following scheme: .

[0029] Furthermore, the above wording should also be interpreted as meaning that if one of the two groups is hydrogen, then the second group bonds at the position where the hydrogen atom is bonded, thus forming a ring. This will be illustrated by the following scheme: .

[0030] In the context of this invention, cyclic alkyl, alkoxy, or thioalkyl groups refer to monocyclic, bicyclic, or polycyclic groups.

[0031] Straight-chain, branched, or cyclic C1 to C1 in the sense of this invention 20 Alkyl groups refer to, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl 1-Methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl- 1,1-octyl-1-yl, 1,1-dimethyl-n-decane-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-octyl-1-yl, 1,1-diethyl-n-decane -1-yl, 1,1-diethyl-n-dodecane-1-yl, 1,1-diethyl-n-tetradecane-1-yl, 1,1-diethyl-n-hexadecane-1-yl, 1,1-diethyl-n-octadecane-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.

[0032] The compounds of formula (1) or (1A) and their preferred embodiments are described below. These preferred embodiments also apply to mixtures, formulations, and organic electronic or electroluminescent devices of the present invention.

[0033] The preferred embodiments of the compound of formula (1) are the compounds of formulas (5) to (11) below, and the preferred embodiments of the compound of formula (1A) are the compounds of formula (12) below.

[0034] The symbols and notations used have the definitions given above. In these formulas, V is preferably NR. 1 C(R) 1 2. O or S. When V = C(R) 1 When )2, two R values ​​can be preferred. 1 The groups together form a ring and thus a spiro system.

[0035] In a preferred embodiment of the invention, p may be the same or different in each case, and is 0, 1 or 2, more preferably 0 or 1, and most preferably 0.

[0036] It is also preferred that q is 0 or 1, and more preferably 0.

[0037] A particularly preferred embodiment of the structure of formulas (5) to (12) is the structure of formulas (5a) to (12a).

[0038] The symbols and markings used have the definitions given above.

[0039] In a preferred embodiment of the invention, R may be the same or different in each case, and is selected from H, D, F, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or a group having 6 to 30 aromatic ring atoms and being volatile by one or more non-aromatic R 2 Aromatic ring systems with substituent groups. In a particularly preferred embodiment of the invention, R may be the same or different in each case and is selected from H, straight-chain alkyl groups having 1 to 4 carbon atoms, or branched or cyclic alkyl groups having 3 to 8 carbon atoms, especially H. When the compounds of the invention are used as monomers for the production of polymers, it is also preferable that the two R substituents are Br or I and that polymerization is carried out via these groups.

[0040] In another preferred embodiment of the invention, R 1 The same or different in each case, and selected from H, D, F, Br, CN, N (Ar) 1 )2,C(=O)Ar 1 , P(=O)(Ar 1)2, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, or an alkenyl or alkynyl group having 2 to 10 carbon atoms, each of which may be derived from one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups may be replaced by O and one or more hydrogen atoms may be replaced by D or F, or having 5 to 30 aromatic ring atoms and in each case being replaced by one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups. More preferably, R 1 The same or different in each case, and selected from H, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 4 carbon atoms or a branched or cyclic alkyl group having 3 to 8 carbon atoms, each of said groups being capable of being generated by one or more R 2 Group substitution, or having 5 to 18 aromatic ring atoms and in each case being substituted with one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups.

[0041] When R is an aromatic ring system and / or when R 1 When it is a aromatic or hybrid aromatic cyclic system, this R and / or R 1 Preferably, they may be the same or different in each case, and are selected from the same groups as those specified below as suitable for Ar.

[0042] Meanwhile, in compounds processed by vacuum evaporation, the alkyl group preferably has no more than five carbon atoms, more preferably no more than four carbon atoms, and most preferably no more than one carbon atom. For compounds processed from solution, suitable compounds are those substituted with alkyl groups having up to 10 carbon atoms, especially branched alkyl groups, or those substituted with oligomeric aromatic subunits, such as ortho-, meta-, or para-terphenyl or branched terphenyl or tetraphenyl groups.

[0043] In one preferred embodiment of the invention, n = 1 and m = 0. In another preferred embodiment of the invention, n = 0 and m = 1. In yet another preferred embodiment of the invention, n = m = 1.

[0044] The preferred group Ar is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which can be generated by one or more R atoms. 1Group substitution. Suitable groups Ar are selected from phenyl, ortho-, meta-, or para-biphenyl, ortho-, meta-, para-, or branched terphenyl, ortho-, meta-, para-, or branched tetraphenyl, 1-, 2-, or 3-fluorenyl, 1-, 2-, 3-, or 4-spirodifluorenyl, 1-, or 2-naphthyl, pyrroleyl, furanyl, thiopheneyl, indolyl, benzofuranyl, benzothiopheneyl, 1-, 2-, or 3-carbazoleyl, 1-, 2-, or 3-dibenzofuranyl, 1-, 2-, or 3-dibenzothiopheneyl, indocarbazoleyl, indolocarbazoleyl, 2-, 3-, or 4-pyridyl, 2-, 4-, or 5-pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, anthraceneyl, phenanthreneyl, biphenylideneyl, pyreneyl, benzoanthraceneyl, and combinations of two or three of these groups, each of which may be represented by one or more R. 1 Group substitution. More preferably, Ar is an aromatic ring system, particularly selected from phenyl, ortho-, meta-, or para-biphenyl, ortho-, meta-, para-, or branched terphenyl, and ortho-, meta-, para-, or branched tetraphenyl. When other (Het-Ar) groups described in detail below are bonded to the Ar group, i.e., when n = m = 1, the (Het-Ar) group is bonded to Ar at any position.

[0045] In a preferred embodiment of the invention, Ar is an aromatic system, meaning it does not contain any heteroaryl groups. This holds true whether n = 1 and other (Het-Ar) groups as described below are bonded to Ar, or whether n = 0.

[0046] In another preferred embodiment of the invention, when Ar contains more than one aryl group, the aromatic groups in the Ar group are not para-linked, that is, the compound is preferably not p-biphenyl, p-terphenyl or p-tetraphenyl, but rather, for example, a structure with corresponding ortho- or meta-linked structures.

[0047] Preferably, when Ar contains a carbazole, pyrrole, imidazole or benzimidazole group, such group is attached to other aromatic units of Ar or to a nitrogen atom via a carbon atom rather than a nitrogen atom.

[0048] When n = 1, the compounds of the present invention contain heteroaryl groups of the following formula, which are abbreviated as (Het-Ar) below:

[0049] When n = 1, this group is present in the compounds of the present invention, and when m = 1, this group is bonded to Ar, or when m = 0, this group is bonded to nitrogen. In the (Het-Ar) group, at least one Y group, and preferably no more than three Y groups, is N, and the other Y groups are CR. 1 .

[0050] The preferred embodiment is a group of the following formula (Het-Ar-1) to (Het-Ar-10).

[0051] The dashed bond represents a bond to Ar, or a bond to nitrogen when m = 0, and the symbols used have the definitions given above.

[0052] Groups of the following formulas (Het-Ar-1a) to (Het-Ar-10b) are particularly preferred.

[0053] The dashed bond represents a bond to Ar, or a bond to nitrogen when m = 0, and the symbols used have the definitions given above.

[0054] When (Het-Ar) is a (Het-Ar-1) or (Het-Ar-1a) group, the two Rs in this group 1 The substituents are preferably aromatic or heteroaromatic ring systems having 5 to 24 aromatic ring atoms and being capable of being replaced by one or more R atoms. 2 Group substitution, especially phenyl, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched tetraphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirodifluorenyl, 1-, 2-, 3- or 4-dibenzofuranyl, or 1-, 2-, 3- or 4-carbazoleyl.

[0055] When (Het-Ar) is a (Het-Ar-2) to (Het-Ar-10) group or a (Het-Ar-2a) to (Het-Ar-10a) group, the R in these groups 1 Preferably, they are the same or different in each case, and are H, D, or have 5 to 24 aromatic ring atoms and can be substituted by one or more R atoms. 2 Aromatic or heteroaromatic ring systems substituted with groups, and especially H or phenyl, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, or ortho-, meta-, para- or branched tetraphenyl.

[0056] The above-described preferred embodiments can be freely combined with each other. In a particularly preferred embodiment of the invention, all of the above preferred options are applied simultaneously.

[0057] When compounds of formula (1) or (1A) and preferred embodiments are used as matrix materials for phosphorescent emitters or in layers directly adjacent to the phosphorescent layer, it is also preferred that the compounds do not contain any fused aryl or heteroaryl groups in which more than two six-membered rings are directly fused to each other. Whether when groups R, R 1 R 2 Ar is particularly preferred when it does not contain any fused aryl or heteroaryl groups in which two or more six-membered rings are directly fused to each other, or when the two adjacent X groups are not groups of formula (2).

[0058] When the compound of formula (1) or (1A) is a deuterated compound, in the preparation of said compound, when the preparation is carried out by reacting an undeuterated compound of formula (1) or (1A) with a deuterated source, or when a deuterated starting compound is selected, i.e. a mixture of deuterated starting compounds is used for preparation, a mixture of deuterated products with the same parent chemical structure can be formed, said deuterated products differing only in degree of deuteration and / or deuteration mode.

[0059] Mixtures of such deuterated compounds with the same parent chemical structure of formula (1) or (1A) or the parent structure of preferred embodiments are considered to be covered in the expression "at least one compound of formula (1)" in the sense of the present invention, said deuterated compounds differing only in degree of deuteration and / or deuteration mode.

[0060] In one embodiment of the present invention, (D) a (D) b (D) c (D) d and (D) e Indicates no substitution.

[0061] In one embodiment of the present invention, (D) a (D) b (D) c (D) d and (D) e This indicates the maximum substitution.

[0062] In a preferred embodiment of at least one compound of formula (1) or (1A) as described above or preferred, the average degree of deuteration is at least 10 mol% to 100 mol%, preferably 50 mol% to 95 mol%, and more preferably 70 mol% to 90 mol%.

[0063] 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 in Bulletin of the Chemical Society of Japan, 2021, 94(2), 600-605, or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0064] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for deuterium atoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more deuterium atoms and capable of releasing them under suitable conditions.

[0065] 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.

[0066] Examples of preferred compounds according to the embodiments detailed above are the compounds detailed in Table 1 below.

[0067] Table 1:

[0068] The particularly preferred compounds of formula (1) or formula (1A) are compounds E1 to E36 in Table 2 below.

[0069] Table 2:

[0070] The compounds of the present invention can be prepared by synthetic steps known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc.

[0071] In the synthetic schemes below, compounds with a small number of substituents are shown to simplify the structure. This does not preclude the presence of any other desired substituents in the methods described. The methods shown for the synthesis of the compounds of this invention should be considered exemplary. Those skilled in the art will be able to develop alternative synthetic routes within the scope of common knowledge in the art.

[0072] The basic structure of the compound of this invention can be prepared by the route outlined in Scheme 1. Functionalization can be carried out according to Scheme 2.

[0073] Option 1:

[0074] Option 2: .

[0075] The synthesis typically begins with 4-bromospirobifluorene as known in the literature (Organic Letters 2009, 11(12), 2607-2610), or with a correspondingly substituted 4-bromospirobifluorene. This is then coupled with an ortho-haloaminobenzene in a CN coupling reaction, for example under Pd or Cu catalysis, wherein the halogen is preferably Cl, Br, or I. In a completely similar manner, for example, naphthalene, fluorene, dibenzofuran, or dibenzothiophene derivatives can be used, which yields compounds containing groups of formula (2) or (3). Ring closure is then carried out via an intramolecular Pd-catalyzed coupling reaction to obtain the corresponding carbazole derivative.

[0076] The compound of formula (1A) can be synthesized in a completely similar manner from 4,4'-dibromospirodifluorene, which is known from the literature.

[0077] The compound of formula (1) (where n = 0 and m = 1) is obtained by coupling with a suitably functionalized aromatic or heteroaromatic compound, such as Hartwig-Buchwald coupling or Ullmann coupling, wherein the reactive group is preferably Cl, Br or I.

[0078] The compound of formula (1) (where n = 1 and m = 0) is obtained by nucleophilic aromatic substitution reaction or by Pd-catalyzed coupling reaction with a (Het-Ar) group substituted with a suitable leaving group, especially Cl or Br.

[0079] The compound of formula (1) (where n = 1 and m = 1) is obtained by coupling with a bifunctionalized aromatic or heteroaromatic compound, such as Hartwig-Buchwald coupling or Ullmann coupling, wherein the reactive groups are preferably bromine and iodine groups, and optionally, after converting the halogen group to a boric acid derivative, a Pd-catalyzed coupling reaction is followed, such as Suzuki coupling, Negishi coupling, Yamamoto coupling, Grignard cross coupling or Stille coupling.

[0080] The present invention also provides a method for preparing compounds of formula (1) or formula (1A), the method comprising the following reaction steps: a) The basic skeleton of the synthetic compound (1) or (1A) which does not yet contain (Het-Ar) and / or Ar groups; and b) Reaction of the basic skeleton from a) in CC coupling, such as Suzuki coupling, Negishi coupling, Yamamoto coupling, Grignard cross coupling, or Stille coupling, or CN coupling, such as Buchwald or Ullmann coupling.

[0081] Detailed reaction conditions are described in the prior art or in the embodiments section.

[0082] These methods, followed by purification if necessary, such as recrystallization or sublimation, can yield high purity, preferably exceeding 99% (by means of purification). 1 Compounds of formula (1) or formula (1A) as determined by ¹H NMR and / or HPLC.

[0083] 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 are required, such as matrix materials, fluorescent emitters, phosphorescent emitters, and / or emitters exhibiting TADF. These formulations may be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents are preferably used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-, or p-xylene, methyl benzoate, mesitylene, naphthalene, o-dimethoxybenzene, 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 ... Hexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, 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.

[0084] The compounds of formula (1) or formula (1A) of the present invention, as described above or as preferred, are suitable for use in organic electroluminescent devices, especially as matrix materials.

[0085] When the compounds of the present invention are used as matrix materials (or, synonymously, host materials) in the luminescent layer, they are preferably used in combination with other compounds.

[0086] Therefore, the present invention also provides a mixture comprising at least one compound of formula (1) or formula (1A), or at least one of the preferred formulas (5), (6), (7), (8), (9), (10), (11), and (12), or one of the compounds from Table 1 or compounds E1 to E36, and at least one other compound selected from matrix materials, phosphorescent emitters, fluorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), and / or solvents. Suitable matrix materials and emitters that can be used in such mixtures of the present invention are described below.

[0087] If the other material is a solvent, then the mixture is synonymous with a formulation comprising at least one of the compounds 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.

[0088] The present invention also provides an organic electronic device comprising an anode, a cathode and at least one organic layer comprising at least one compound of formula (1) or formula (1A), or at least one of the preferred formulas (5), (6), (7), (8), (9), (10), (11) and (12), or one of the compounds from Table 1 or compounds E1 to E36.

[0089] 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.

[0090] Organic electronic devices are preferably organic electroluminescent devices.

[0091] The organic electroluminescent device of the present invention (synonymous with organic electroluminescent device) is, for example, an organic light-emitting transistor (OLET), an organic field quenching device (OFQD), an organic light-emitting electrochemical cell (OLEC), an organic laser diode (O-laser), or an organic light-emitting diode (OLED). The organic electroluminescent device of the present invention is particularly an organic light-emitting diode or an organic light-emitting electrochemical cell. More preferably, the device of the present invention is an OLED.

[0092] 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 the group above, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. For example, an intermediate layer with exciton blocking function can also be introduced between two light-emitting layers.

[0093] If multiple light-emitting layers are present, these layers preferably have a total of multiple emission peaks between 380 nm and 750 nm, resulting in an overall white light emission; in other words, multiple luminescent or phosphorescent compounds are used in the light-emitting layers. Two or more fluorescent and / or phosphorescent compounds may also be present in the light-emitting layers. A system with three light-emitting layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. As an alternative to the combination described above, the light-emitting layers may also exhibit yellow emission. This combination is known to those skilled in the art. The organic electroluminescent device of the present invention can also be a tandem electroluminescent device, especially for white-light-emitting OLEDs.

[0094] The device may also include inorganic materials or another layer formed entirely of inorganic materials.

[0095] 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 these materials interact with each other in an organic electroluminescent device. This involves, for example, orbital levels (HOMO, LUMO) or other triplet and singlet levels, as well as other material properties.

[0096] Depending on the exact structure, compounds of formula (1) or (1A) of the present invention, as described above or as preferred in the description, can be used in different layers. It is preferred to include compounds of formula (1) or (1A) or the preferred embodiments listed above as matrix materials for phosphorescent emitters, phosphorescent emitters, or emitters exhibiting TADF (thermally activated delayed fluorescence), especially phosphorescent emitters, in organic electroluminescent devices. 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 light-emitting layer or in the electron transport layer.

[0097] The present invention also 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 formula (1A) or at least one of the preferred formulas (5), (6), (7), (8), (9), (10), (11) and (12) or one of the compounds from Table 1 or compounds E1 to E36.

[0098] In one embodiment of the invention, for the device of the invention, at least one other matrix material in the light-emitting layer is selected and used with a compound of formula (1) or formula (1A) as described above or as preferred, or with compounds from Table 1 or compounds E1 to E36.

[0099] Therefore, the present invention also 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 formula (1A), or at least one of the preferred formulas (5), (6), (7), (8), (9), (10), (11) and (12), or one of the compounds from Table 1 or compounds E1 to E36, and at least one other matrix material.

[0100] Therefore, the present invention also 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 formula (1A) or at least one of preferred formulas (5), (6), (7), (8), (9), (10), (11) and (12) or one of the compounds from Table 1 or compounds E1 to E36 and two other matrix materials.

[0101] 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, bicarbazoles, indole-carbazole derivatives, indo-carbazole derivatives, azacarbazole derivatives, bipolar matrix materials, borazine or borate esters, triazine derivatives, zinc complexes, diazacyclopentane or tetrazacyclopentane derivatives, phosphazacyclopentane derivatives, bridged carbazole derivatives, biphenylide derivatives, or dibenzofuran derivatives. Similarly, the mixture may contain other phosphorescent emitters with shorter emission wavelengths than the actual emitters as a co-host, or may contain compounds that, even if involved in charge transport, will not reach a significant level, for example… Wide bandwidth Compounds.

[0102] Wide bandwidth In this application, "material" refers to the material within the scope of the disclosure in US 7,294,849, characterized by a band gap of at least 3.5 eV, wherein the band gap refers to the gap between the HOMO and LUMO energy levels of the material.

[0103] Particularly suitable hole-transporting matrix materials that are advantageously combined in a mixed matrix system with compounds of the preferred formulas (5), (6), (7), (8), (9), (10), (11), and (12) as described above or below may be selected from compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), or (HH-6) as described below.

[0104] 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) or formula (1A) as described above or as preferably described, as matrix material 1, and at least one compound of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), or (HH-6) as matrix material 2. Equation (HH-1), Equation (HH-2), Formula (HH-3), Formula (HH-4), Formula (HH-5), Formula (HH-6), The symbols and markings used are as follows: A 1 It is C(R) 7 2. NR 7 , O or S; L represents the bond, O, S, C(R) 7 )2 or NR 7 ; A is independently a group of formula (HH-4-1) or (HH-4-2) in each case. ,

[0105] Equation (HH-4-1) Equation (HH-4-2); X2 is the same or different in each case, and is CH, CR 6 Or N, where no more than two symbols X2 can be N; Indicates the binding site with formula (HH-4); U 1 U 2 When they appear, they are bonds, O, S, C(R). 7 )2 or NR 7 ; R 6In each case, the same or different, and is 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 Group substitution, and one or more 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 form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems together; Ar5 may be the same or different in each case, and independently has 5 to 40 ring atoms and can be substituted 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 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, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 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; here, two or more R groups... 7 Groups can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems together, but R 7 The group preferably does not form any such ring system; R 8In each case, they may be the same or different, and are H, D, F, or aliphatic, aromatic or heteroaromatic organic groups having 1 to 20 carbon atoms, especially hydrocarbon groups, in which one or more hydrogen atoms may also be replaced by F; c, c1, and c2 are each independently 0 or 1 in each case, and the sum of these labels in each case is c + c1 + c2 = 1; d, d1, and d2 are each independently 0 or 1 in each case, and the sum of these labels in each case is d + d1 + d2 = 1; q, q1, and q2 are each independently 0, 1, 2, 3, or 4 in each case; s is the same or different in each case, and is 0, 1, 2, 3 or 4; t is the same or different in each case, and is 0, 1, 2 or 3; u is the same or different in each case, and is 0, 1 or 2; u1 and u2 are each independently 0 or 1 in each case, where the sum u1 + u2 = 1; and v can be 0, 1, 2, or 3.

[0106] Compounds of formula (HH-1) and formula (HH-5) are particularly preferred here.

[0107] The preferred compound of formula (HH-4) is the compound of formula (HH-4-A). Formula (HH-4-A) Where X2 is independently CH or CR in each case. 6 And Ar5, R 6 q, q1, q2 and v have the definitions given above or given as preferred.

[0108] The preferred compounds of formula (HH-5) are those of formulas (HH-5-A) to (HH-5-E). Formula (HH-5-A), Formula (HH-5-B), Formula (HH-5-C), Formula (HH-5-D), Formula (HH-5-E), Among them, Ar5, R 6 , s and u have the definitions given above or given as preferred.

[0109] In compounds of formula (HH-1), (HH-2), (HH-3), (HH-5) or (HH-6) or their preferred structures, when R 6 When the group is not D, s is preferably 0 or 1, or more preferably 0.

[0110] In compounds of formula (HH-1), (HH-2), or (HH-3), when R 6 When the group is not D, t is preferably 0 or 1, or more preferably 0.

[0111] In compounds of formula (HH-1), (HH-2), (HH-3) or (HH-5) or their preferred structures, when R 6 When the group is not D, u is preferably 0 or 1, or more preferably 0.

[0112] The sum of the markers s, t, and u in compounds of formulas (HH-1), (HH-2), (HH-3), (HH-5), and (HH-6) or their preferred structures is preferably not greater than 6, particularly preferably not greater than 4, and more preferably not greater than 2. When R 6 If it is not D, then this is the preferred option.

[0113] In compounds of formula (HH-4) or their preferred structures, c, c1, and c2 are each independently 0 or 1 in each case, wherein the sum of the labels c + c1 + c2 in each case is 1. c2 is preferably defined as 1.

[0114] In compounds of formula (HH-4) or their preferred structures, L is preferably a single bond or C(R) bond. 7 )2, where R 7 It has the definition given above; more preferably, L is a single bond.

[0115] In equation (HH-4-1), when R 6 When the group is not D, v is preferably 0 or 1.

[0116] In equation (HH-4-2), U 1 or U 2 When they appear, they are preferably single bonds or C(R) bonds. 7 )2, where R 7 It has the definition given above; more preferably, U 1 or U 2 They are single bonds when they appear.

[0117] In equation (HH-4-2), when R 6 When the group is not D, q, q1, and q2 are preferably 0 or 1.

[0118] In a preferred embodiment of the present invention, as described above, compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-6), or their preferred structures, which can be combined with compounds of formula (1) or (1A) or preferred compounds of formula (1) or (1A), R 6 In each case, the same or different, and selected from D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group in each case may be one or more R 7 Group substitution, or having 5 to 60 ring atoms, preferably 5 to 40 ring atoms, and in each case may be substituted with one or more R groups. 7 Aromatic or heteroaromatic ring systems with substituted groups.

[0119] In a preferred embodiment of the present invention, as described above, compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-6), or their preferred structures, which can be combined with compounds of formula (1) or (1A) or preferred compounds of formula (1) or (1A), R 6 In each case, they may be the same or different, and are selected from D or have 6 to 30 ring atoms and can be derived from one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups.

[0120] Preferably, Ar5 in compounds of formulas (HH-1), (HH-2), (HH-3), (HH-5), and (HH-6) or their preferred structures is selected from phenyl, biphenyl, especially ortho-, meta-, or para-biphenyl, terphenyl, especially ortho-, meta-, or para-terphenyl or branched terphenyl, tetraphenyl, especially ortho-, meta-, or para-tetraphenyl or branched tetraphenyl, fluorene group, which may be linked at positions 1, 2, 3, or 4, and spirodifluorene group, which may be linked at positions 1, 2, 3, or 4. The 4-position linkage is a naphthyl group, especially a 1- or 2-bonded naphthyl group, or a group derived from: indole, benzofuran, benzothiophene, carbazole, which can be linked at positions 1, 2, 3, or 4; dibenzofuran, which can be linked at positions 1, 2, 3, or 4; dibenzothiophene, which can be linked at positions 1, 2, 3, or 4; indocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or biphenylide, each of which can be linked by one or more R... 7 Group substitution. Ar5 is preferably unsubstituted.

[0121] When A in formula (HH-2) or (HH-3) or (HH-6) 1 It is NR 7 When the substituent R is bonded to the nitrogen atom 7Preferably, it has 5 to 24 aromatic ring atoms and can also be divided by one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups. In a particularly preferred embodiment, this R... 7 The substituents may be the same or different in each case, and the system is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, especially 6 to 18 aromatic ring atoms. R 7 Preferred embodiments are phenyl, biphenyl, terphenyl, and tetraphenyl, which are preferably unsubstituted, and groups derived from triazine, pyrimidine, and quinazoline, which may be substituted by one or more R 8 Group substitution.

[0122] When A in formula (HH-2) or (HH-3) or (HH-6) 1 It is C(R) 7 When )2, the substituent R bonded to this carbon atom 7 Preferably, they may be the same or different in each case, and are straight-chain alkyl groups having 1 to 10 carbon atoms, or branched or cyclic alkyl groups having 3 to 10 carbon atoms, or aromatic or heteroaromatic ring systems having 5 to 24 aromatic ring atoms, which may also be represented by one or more R 8 Group substitution. Most preferably, R 7 It is a methyl group or a phenyl group. In this case, R 7 Groups can also form ring systems together, which produces spirocyclic systems.

[0123] In a preferred embodiment of the compounds of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-6) and their preferred structures, these compounds are partially or fully deuterated, more preferably fully deuterated.

[0124] The preparation of compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), and (HH-6) and their preferred structures is generally known, and some of these compounds are commercially available.

[0125] Compounds of formula (HH-4) or their preferred structures are disclosed in the examples, for example, on pages 110 to 119, and particularly on pages 120 to 127, of WO 2021 / 180614 A1. Methods for their preparation are disclosed in the synthetic examples on page 128 of WO 2021 / 180614 A1 and on pages 214 to 218.

[0126] The preparation of triarylamines of formula (HH-6) is known to those skilled in the art, and some of these compounds are commercially available.

[0127] If the at least one other matrix material is a deuterated compound, then the at least one matrix material may be a mixture of deuterated compounds having the same basic chemical structure but differing only in degree of deuteration.

[0128] In a preferred embodiment of the at least one other matrix material, it is a mixture of deuterated compounds of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-6) as described above, or of preferred structures thereof, wherein the degree of deuteration of these compounds is at least 50% to 90%, preferably 70% to 100%. The description above relating to deuterated mixtures and the production of deuterated materials for compounds of formula (1) or (1A) is subject to necessary modifications.

[0129] In a preferred embodiment of the at least one other matrix material, it is a mixture of deuterated compounds of the formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-6) as described above and / or their preferred structures, wherein the degree of deuteration of these compounds is at least 50% to 90%, preferably 70% to 100%.

[0130] Examples of other suitable matrix materials for combination with compounds of the preferred formula (1) or formula (1A) as described above or as such are compounds described in WO2019 / 229011 A1, Table 3, pages 137 to 203, which may also be partially or fully deuterated.

[0131] Examples of suitable other matrix materials for use in combination with the preferred formula (1) or formula (1A) as described above or as such are the compounds described in WO 2021 / 180625 A1, Table 3, pages 131 to 137 and Table 4, pages 137 to 139, which may also be partially or fully deuterated.

[0132] Examples of suitable other matrix materials for use in combination with the preferred formula (1) or formula (1A) as described above or as such are the compounds described in compounds [2-1] to [2-110] on pages 42 to 47 of KR 2023 / 0034896 A or compounds [3-1] to [3-26] on pages 49 to 51.

[0133] For combinations with compounds of the preferred formulas (5), (6), (7), (8), (9), (10), (11), and (12) as described above or in the description, particularly suitable compounds are those of the preferred formulas (HH-1) and / or (HH-5) as described above or in the description.

[0134] For combinations with compounds of the preferred formulas (5), (6), (7), (8), (9), (10), (11), and (11) as described above or otherwise, particularly suitable compounds are those of formula (HH-1), wherein at least one Ar5 group is having 5 to 40 ring atoms and can be generated by one or more R... 7 Group-substituted heteroaromatic ring systems, and / or compounds of the formula (HH-5).

[0135] For combinations with compounds of the preferred formulas (5), (6), (7), (8), (9), (10), (11), and (12) as described above or otherwise, compounds of formula (HH-5) are particularly preferred.

[0136] Other examples of matrix materials of preferred formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), and (HH-6) used in combination with compounds of formula (1) or (1A) as described above or preferred are the structures in Tables 3 and 4 given below.

[0137] Table 3:

[0138] In Table 3 above, n is the number of deuterium atoms in the corresponding compound, and is 0 or D1 to D. max Preferably, it is D1 to D max n = 0 means the compound is undeuterated. n = D1 means that one hydrogen atom in the corresponding compound has been replaced by a deuterium atom. max This represents the maximum possible number of deuterium atoms in the corresponding compound. Maximum number Dmax This can vary depending on the compound. Depending on the compound, D max The following values ​​are possible: 20, 24, 26, 28, 30, 31, 32, 34, 35, 36, 37, 38, and 40.

[0139] The particularly preferred compounds of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) selected according to the invention and preferably combined with at least one compound of formula (1) or formula (1A) for use in the electroluminescent devices of the invention are the compounds in Table 4 below.

[0140] Table 4:

[0141] The host material of formula (1) or formula (1A) described above and its preferred embodiment, or the compounds from Table 1 and compounds E1 to E36 may be combined with the above-mentioned matrix material / host material, the matrix material / host material of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) described above and its preferred embodiment in Table 3, or compounds H1 to H48 in the device of the present invention as needed.

[0142] A very particularly preferred mixture of a compound of formula (1) or (1A) for use in the device of the present invention and a main material of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) is obtained by combining compounds E1 to E36 with compounds H1 to H48, as shown below in Table 5. The first mixture M1 is, for example, a combination of compounds E1 and H1.

[0143] Table 5:

[0144] Based on the overall composition of the mixture or the overall composition of the light-emitting layer, the concentration of the main material of the preferred formula (1) or formula (1A) 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%.

[0145] Based on the overall composition of the mixture or the light-emitting layer, the total concentration of all the main materials of the preferred formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), and (HH-6) in the mixture of the present invention or in the light-emitting layer of the device of the present invention, as described above or in general, is typically in the range of 10 wt% to 95 wt%, preferably in the range of 15 wt% to 90 wt%, more preferably in the range of 15 wt% to 80 wt%, even more preferably in the range of 20 wt% to 70 wt%, very particularly preferably in the range of 40 wt% to 80 wt%, and most preferably in the range of 50 wt% to 70 wt%.

[0146] The present invention also relates to a mixture comprising, in addition to the host material of the above-described or preferred formula (1) or formula (1A) (hereinafter referred to as host material 1) and the host material of at least one of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6) (hereinafter referred to as host material 2), the mixture further comprising at least one phosphorescent luminescent material.

[0147] The present invention also relates to mixtures selected from M1 to M1728, wherein the mixture further comprises at least one phosphorescent emitting agent.

[0148] It is also preferable to use a mixture of two or more triplet emitters and a matrix comprising host material 1 and host material 2. In this case, the triplet emitter with a shorter wavelength emission spectrum acts as a co-matrix for the triplet emitter with a longer wavelength emission spectrum.

[0149] The present invention also relates to an organic electroluminescent device preferred as described above or as described above, wherein, in addition to the host material of at least one of the above-mentioned formula (1) or formula (1A) and formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6) as described above or as described above, especially material combinations M1 to M1728, the light-emitting layer further comprises at least one phosphorescent material.

[0150] 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 preferably refers to transitions from triplet states.

[0151] Suitable phosphorescent emitters (= triplet emitters) are, in particular, compounds that, when properly excited, preferably emit light in the visible 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 said atomic numbers. Preferred phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, especially compounds containing iridium or platinum. For the purposes of this invention, all luminescent compounds containing the aforementioned metals are considered phosphorescent emitters.

[0152] Generally, all phosphorescent complexes for phosphorescent OLEDs, as known to those skilled in the art and as described in the field of organic electroluminescent devices, are suitable.

[0153] Preferred phosphorescent emitters according to the present invention conform to formulas (I), (II), (III), (IV) or (V): Formula (I)

[0154] Equation (II)

[0155] Equation (III)

[0156] Formula (IV)

[0157] Formula (V)

[0158] The symbols and notations for these equations (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.

[0159] Preferred phosphorescent emitters according to the present invention conform to formula (VI), (VII) or (VIII): Formula (VI)

[0160] Equation (VII)

[0161] Formula (VIII)

[0162] The symbols and notations for these equations (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.

[0163] According to the preferred phosphorescent emitter formula (IX) of the present invention, Equation (IX), The symbols and notations for this expression (IX) are defined as follows: When n + m is 3, n is 1 or 2, and m is 2 or 1. X is the same or different in every case, and is N or CR. R may be 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 that may be partially or fully substituted with deuterium, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms that may be partially or fully substituted with deuterium.

[0164] Therefore, the present invention also provides an organic electroluminescent device as described above or as preferred, characterized in that, in addition to the host materials 1 and 2, the light-emitting layer further comprises at least one phosphorescent material of formula (IX) as described above.

[0165] In the light emitter of formula (IX), n is preferably 1 and m is preferably 2.

[0166] In the luminescent body of formula (IX), preferably, one X is selected from N and the other X is CR, or all X are the same or different in each case and are CR.

[0167] In the light emitter of formula (IX), at least one R is preferably different from H. In the light emitter of formula (IX), preferably two Rs are different from H and have one of the other definitions given above for the light emitter of formula (IX).

[0168] 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 WO 2019 / 007867 A1. These luminescent materials are incorporated herein by reference.

[0169] Examples of particularly preferred phosphorescent luminescent materials are listed in Table 6 below.

[0170] Table 6:

[0171] 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 M1728 is preferably combined with compounds of formulas (I) to (IX) or compounds from Table 6.

[0172] The light-emitting layer of the organic electroluminescent device of the present invention, which contains at least one phosphorescent light source, is preferably a layer that emits infrared light or 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.

[0173] A yellow-emitting layer refers to a layer having a photoluminescence peak value in the range of 540 to 570 nm. An orange-emitting layer refers to a layer having a photoluminescence peak value in the range of 570 to 600 nm. A red-emitting layer refers to a layer having a photoluminescence peak value in the range of 600 to 750 nm. A green-emitting layer refers to a layer having a photoluminescence peak value in the range of 490 to 540 nm. A blue-emitting layer refers to a layer having a photoluminescence peak value in the range of 440 to 490 nm. Here, the photoluminescence peak value 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 a combination of a host material 1 of formula (5), (6), (7), (8), (9), (10), (11), or (12) of the present invention and a host material 2 of at least one of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), and (HH-6), and a corresponding luminescent body.

[0174] The photoluminescence spectrum of the layer was recorded, for example, using a commercial photoluminescence spectrometer.

[0175] Usually in 10 -5 In an oxygen-free solution of M, the photoluminescence spectrum of the selected luminescent material was measured at room temperature. A suitable solvent is any solvent in which the selected luminescent material is dissolved at the mentioned concentration. Particularly suitable solvents are typically toluene or 2-methyl-THF, and also dichloromethane. The spectra were measured using a commercial photoluminescence spectrometer. The triplet energy 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 as follows: E(T1, in eV) = 1240 / E(T1, in nm) = 1240 / PLmax. (in nm).

[0176] Therefore, the preferred phosphorescent emitter is a yellow emitter, preferably having formulas (I) to (IX) or from Table 6, and its triplet energy T1 is preferably about 2.3 eV to about 2.1 eV.

[0177] Therefore, the preferred phosphorescent emitter is a green emitter, preferably having formulas (I) to (IX) or from Table 6, and its triplet energy T1 is preferably about 2.5 eV to about 2.3 eV.

[0178] Therefore, a particularly preferred phosphorescent emitter is a green emitter, preferably having formulas (I) to (IX) as described above or from Table 6, with its triplet energy T1 preferably being about 2.5 eV to about 2.3 eV.

[0179] Most preferably, for the mixture of the present invention or the light-emitting layer of the present invention, the preferred formulas (I) to (IX) as described above or the green light emitters from Table 6 are selected.

[0180] 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.

[0181] 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 pyrithionemines, or aromatic pyrithionemines. An aromatic anthraceneamine is a compound in which one of the diarylamino groups is directly bonded to an anthracene group, preferably at the 9-position. An aromatic anthracene diamine is a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably at the 9- or 10-position. Aromatic pyreneamines, pyrene diamines, pyrithionemines, and pyrithionemines are defined in a similar manner, wherein the diarylamino groups are bonded to pyrene, preferably at the 1- or 1- or 6-position. Other preferred luminescent compounds are indoxfluoreneamine or indoxfluorene diamine, benzo[a]indoxfluoreneamine or benzo[a]indoxfluorene diamine, and dibenzo[a]indoxfluoreneamine or dibenzo[a]indoxfluorene diamine, as well as indoxfluorene derivatives having fused aryl groups. Pyrene arylamines are also preferred. Benzo[a]indoxfluoreneamine, benzo[a]fluoreneamine, extended benzo[a]indoxfluorene, phenazine, and fluorene derivatives linked to furan or thiophene units are also preferred. The luminescent devices or mixtures of the present invention may additionally contain materials exhibiting TADF (thermally activated delayed fluorescence).

[0182] In another preferred embodiment 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 hybrid 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. Preferably, the hybrid matrix system is optimized for a light emitter of one of formulas (I) to (IX) or for a light emitter from Table 6.

[0183] In one embodiment of the invention, the mixture contains no other components, i.e., functional materials, besides the components of the host material and host material 2 as described above or as preferably of formula (1) or formula (1A). 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.

[0184] In an alternative embodiment of the invention, in addition to the components of the host material and host material 2 as described above or as preferably of formula (1) or formula (1A), the mixture also contains the phosphorescent emitter as described above. Where the mixing ratio in the vapor deposition is appropriate, this mixture can also be used as the sole material source.

[0185] Preferred is a premixed system consisting of two matrix materials, namely a compound of formula (5), (6), (7), (8), (9), (10), (11) or (12) and a compound of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6).

[0186] Preferred is a premixed system consisting of three matrix materials, namely a compound of formula (5), (6), (7), (8), (9), (10), (11) or (12) and two compounds of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6).

[0187] The components or ingredients of the light-emitting layer of the device of the present invention can therefore be processed by vapor deposition or from solution. For this purpose, a combination of materials, preferably the host materials 1 and 2 as described above or as preferred, and optionally the phosphorescent light-emitting materials as described above or as preferred, is provided in a formulation containing at least one solvent. Suitable formulations have been described above.

[0188] Based on the overall composition of the luminescent material and the matrix material, the luminescent layer in the device of the present invention according to the preferred embodiment and the luminescent compound contains a matrix material comprising at least one compound of formula (5), (6), (7), (8), (9), (10), (11) or (12) according to the preferred embodiment and at least one compound of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) according to the preferred embodiment, preferably between 99.9 vol% and 1 vol%, more preferably between 99 vol% and 10 vol%, particularly preferably between 98 vol% and 60 vol%, and very particularly preferably between 97 vol% and 80 vol%.

[0189] Accordingly, based on the overall composition of the light-emitting layer comprising the luminescent material and the matrix material, the light-emitting layer in the device of the present invention preferably contains between 0.1 vol% and 99 vol%, more preferably between 1 vol% and 90 vol%, more preferably between 2 vol% and 40 vol%, and most preferably between 3 vol% and 20 vol%. If the compound is processed from solution, it is preferable to use the corresponding amount in weight % rather than the amount specified above in volume %

[0190] The present invention also relates to organic electroluminescent devices as described above or as preferred, 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.

[0191] Preferred hole injection and / or hole transport materials are shown in the table below. The materials in this table may also be partially or fully deuterated.

[0192] Table: The following compounds may also be partially or fully deuterated.

[0193] The preferred layer order in the organic electroluminescent device of the present invention is as follows: Anode / hole injection layer / hole transport layer / light emission layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0194] This layer order is a preferred order. However, it should be reiterated that not all of the mentioned layers are required and / or additional layers may exist.

[0195] The material used for the electron transport layer can be any material 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.

[0196] The present invention also relates to organic electroluminescent devices preferred as described above or in other descriptions, wherein the organic layer comprises an electron injection layer (EIL) and / or an electron transport layer (ETL) and / or a hole blocking layer, wherein the electron injection material and the electron transport material are selected from compounds of formula (5), (6), (7), (8), (9), (10), (11) or (12) preferred as described above or in other descriptions.

[0197] Also preferred is an electronic device, preferably an organic electroluminescent device, which includes one or more compounds of the present invention in combination with a material having a high dielectric constant in one or more electron transport layers.

[0198] Materials with high dielectric constants include, for example, alkali metal or alkaline earth metal fluorides, alkali metal or alkaline earth metal oxides, alkali metal or alkaline earth metal carbonates, lanthanide compounds, or organoalkali metal complexes, particularly preferred being organoalkali metal complexes, and preferably combinations of lithium quinoline (LiQ) with the compounds of the present invention. Suitable materials with high dielectric constants include, for example, LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, Yb₂O₃, or lithium quinoline.

[0199] Here, the two different materials may be present in the electron transport layer at a ratio of 1:50 to 50:1, preferably 1:10 to 10:1, more preferably 1:4 to 4:1, and most preferably 1:2 to 2:1.

[0200] An electron injection layer may also be introduced between the electron transport layer and the cathode of the present invention. Suitable materials for the electron injection layer are, for example, LiF, lithium quinoline, CsF, Cs2CO3, Li2O, LiBO2, K2SiO3, Cs2O, or Al2O3.

[0201] Suitable cathodes for the devices of the present invention are metals with low work function, metal alloys composed of multiple metals, or multilayer structures, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Yb, Sm). Also suitable are alloys composed of alkali metals or alkaline earth metals and silver, such as alloys composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, other metals with relatively high work function, 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 corresponding oxides or carbonates (e.g., LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃). For this purpose, lithium quinoline (LiQ) may also be used. The thickness of this layer is preferably between 0.5 and 5 nm.

[0202] 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, at least one electrode 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 also 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.

[0203] The organic electroluminescent device of the present invention is appropriately structured (depending on the application) during the manufacturing process, contacted and finally sealed, because the lifespan of the device of the present invention is shortened in the presence of water and / or air.

[0204] The manufacture of the device of the present invention is not limited herein. One or more organic layers comprising 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 less than 10 -6 An initial pressure of millibars is applied via vapor deposition. However, in this case, the initial pressure can also be even lower, for example, below 10. -7 millibar.

[0205] 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 between millibar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jetting) 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).

[0206] The organic electroluminescent device of the present invention is further preferably characterized by manufacturing one or more organic layers comprising the composition of the present invention from a 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) 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 light-emitting layer can be applied in a very simple and inexpensive manner. This technique is particularly suitable for the mass production of organic electroluminescent devices.

[0207] 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.

[0208] These methods are well known to those skilled in the art and can be applied to organic electroluminescent devices.

[0209] The present invention also provides a method for manufacturing an organic electroluminescent device of the present invention as described above or as preferred thereof, the method being 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 sublimation, or from solution, especially by spin coating or by printing.

[0210] In the case of fabrication via vapor deposition, there are, in principle, two methods in which the organic layer, preferably the luminescent layer, of the present invention can be applied or vapor-deposited onto any substrate or prior layer. First, the materials used can initially be individually loaded into material sources and ultimately evaporated from different material sources (“co-evaporation”). Second, multiple materials can be premixed (premixed system), and the initially loaded mixture can ultimately evaporate from a single material source (“premixed evaporation”). In this way, vapor deposition of a luminescent layer with uniformly distributed components can be achieved in a simple and rapid manner without the need for precisely driving multiple material sources.

[0211] The following methods are feasible: The method for manufacturing the organic electroluminescent device of the present invention as described above or preferred is 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.

[0212] The method for manufacturing an organic electroluminescent device of the present invention as described above or as preferred is characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein at least one compound of formula (5), (6), (7), (8), (9), (10), (11) or (12) is deposited from the vapor phase sequentially or simultaneously from at least two material sources together with other materials forming the light-emitting layer.

[0213] The method for manufacturing the device of the present invention is characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein at least one compound of formula (5), (6), (7), (8), (9), (10), (11) or (12) is deposited from the vapor phase as a premix with at least one other matrix material and the light-emitting material sequentially or simultaneously, the light-emitting material being selected from phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0214] Compared with the prior art, the electronic device of the present invention, especially the organic electroluminescent device, is noteworthy due to one or more of the following unexpected advantages: 1. Electronic devices, particularly organic electroluminescent devices, exhibit excellent lifetimes, said electronic devices comprising compounds of formula (1) or formula (1A) and the preferred embodiments listed above and below, especially as matrix materials or as electronically conductive materials. In this case, these compounds particularly induce low roll-off, i.e., minimal decrease in power efficiency of the device at high brightness.

[0215] 2. Electronic devices, particularly organic electroluminescent devices, exhibit excellent efficiency, wherein the electronic devices comprise compounds of formula (1) or formula (1A) and the preferred embodiments listed above and below, as electronic conductive materials and / or matrix materials. In this case, when used in the electronic devices, the compounds of formula (1) or formula (1A) and the preferred embodiments listed above and below of the present invention provide low operating voltages.

[0216] 3. The compounds of formula (1) or formula (1A) of the present invention and the preferred embodiments listed above and below exhibit very high stability and lifetime.

[0217] 4. By using compounds of formula (1) or formula (1A) and the preferred embodiments listed above and below, the formation of light loss channels in electronic devices, especially organic electroluminescent devices, can be avoided. As a result, these devices are characterized by high PL efficiency and therefore high EL efficiency of the light emitter, as well as excellent energy transfer from the matrix to the dopant.

[0218] 5. The use of compounds of formula (1) or formula (1A) and the preferred embodiments listed above and below in the layers of electronic devices, especially organic electroluminescent devices, results in high mobility of the electronic conductor structure.

[0219] 6. The compounds of formula (1) or formula (1A) and the preferred embodiments listed above and below have excellent glass film formation.

[0220] 7. The compounds of formula (1) or formula (1A) and the preferred embodiments listed above and below form very good films from solution.

[0221] 8. The compounds of formula (1) or formula (1A) and the preferred embodiments listed above and below have a triplet energy level T1, which may be in the range of 2.50 eV to 2.90 eV, for example.

[0222] These advantages are not accompanied by an excessive deterioration of other electronic properties.

[0223] 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 alternative features serving the same, 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.

[0224] Unless specific features and / or steps are mutually exclusive, all features of the invention can be combined with each other in any manner. This is especially true of preferred features of the invention. Similarly, features that are not necessarily combined can be used individually (rather than in combination).

[0225] The technical teachings disclosed in this invention can be refined and combined with other embodiments.

[0226] The invention is illustrated in more detail by way of the following embodiments, but is not intended to limit the invention.

[0227] Example: Unless otherwise specified, the following synthesis shall be carried out in a dry solvent under a protective gas atmosphere. Solvents and reagents are available from Aldrich or ABCR. For reactants that are not commercially available, the numbers given are the corresponding CAS numbers.

[0228] Synthesis Examples

[0229] Example 1a: 12'-(4,6-di(phenyl-) d 5)-1,3,5-triazine-2-yl-12' H -spiro[fluorene-9,7'-indo[1,2- a Carbazole 1a

[0230] Under a protective atmosphere, 4.2 g of NaH (60% in mineral oil, 0.11 mmol) was dissolved in 300 mL of dimethylformamide. 43 g (0.106 mol) of spiro[9H-fluorene-9,7'(1'H)-indo[1,2-a]carbazole] was dissolved in 250 mL of DMF and added dropwise to the reaction mixture. After 1 hour at room temperature, 2-chloro-4,6-di(phenyl- d 5)-[1,3,5]triazine (34.5 g, 0.12 mol) was dissolved in 200 mL of THF. The reaction mixture was then stirred at room temperature for 12 hours. After this time, the reaction mixture was poured onto ice. After warming to room temperature, the precipitated solid was filtered and washed with ethanol and heptane. The residue was thermally extracted with toluene, recrystallized from toluene / n-heptane, and finally sublimated under high vacuum to a purity of 99.9%. The yield was 28.4 g (44.5 mmol; 42%).

[0231] The following compounds were prepared in a similar manner:

[0232] Example 2a: 12'-(4-([1,1'-biphenyl]-4-yl- d 9)-6-(phenyl- d 5)-1,3,5-triazine-2-yl-12' H -spiro[fluorene-9,7'-indo[1,2- a ]Carbazole]-1,1',2,2',3,3',4,4',5,5',6,6',7,8,8',9',10',11'-d 18 2a

[0233] 16g of 12'-(4-([1,1'-biphenyl]-4-yl)-6-(phenyl)-1,3,5-triazin-2-yl-12' H -spiro[fluorene-9,7'-indophen[1.2- a[Carbazole] (22.4 mmol; 1.00 equivalent) was suspended in 190 mL (80 equivalent) toluene-d8. While cooling, 20 mL (10.00 equivalent) of trifluoromethanesulfonic acid was added to this mixture. The reaction mixture was stirred at room temperature for 6 hours. Then, 40 mL (130 equivalent) of deuterium oxide was added dropwise at 0 °C. After neutralization with NaOH solution (38 mL; 20%), 150 mL of heptane was added to the reaction mixture, and the precipitated solid was filtered and washed with ethanol. The solvent was removed under reduced pressure. The product shown above (a mixture of fractions having H / D isotope isomers and H / D isotope derivatives) was subjected to high vacuum (p = 5 × 10⁻⁶). -7 Sublimed at 1 mbar (12g, 75% of theoretical value), purity 99.9%.

[0234] The following compounds were prepared in a similar manner:

[0235] OLED manufacturing

[0236] Data for various OLEDs are presented in the following comparative examples V1 to V7 and inventive examples E1 to E6 (see Tables 7 and 8).

[0237] Examples E1 to E6 illustrate data for the OLEDs of the present invention. The substrate used for the OLEDs in Table 7 is a glass plate coated with structured ITO (indium tin oxide) with a thickness of 50 nm.

[0238] The precise structure of an OLED can be seen in Table 7. The materials required to manufacture an OLED (unless described above) are shown in Table 9.

[0239] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the luminescent layer always consists of at least one matrix material (which is also the host material) and a luminescent dopant (emitting agent), which is added to one or more matrix materials by co-evaporation in a specific volume ratio. Data reported here in the form of, for example, eV2:hV1:TEG2 (32%:60%:8%) 40 nm means that material eV2 is present as host material 1 at a ratio of 32 vol%, compound hV1 is present as host material 2 at a ratio of 60 vol%, and TEG2 is present at a ratio of 8 vol% in a 40 nm thick layer. Similarly, the hole injection layer (HIL) and electron transport layer (ETL) may also be composed, for example, of a mixture of two materials.

[0240] OLEDs were characterized using standard methods. For this purpose, electroluminescence spectra and the current-voltage-luminance characteristic line (IUL characteristic line) were measured, and these were used to calculate the EQE. The calculations were performed under conditions exhibiting Lambertian emission characteristics. The electroluminescence spectrum was at 1000 cd / m². 2 The value is determined under the specified brightness. Parameter U10 in Table 8 represents the voltage required for a current density of 10 mA / cm². EQE10 refers to the voltage required for a current density of 10 mA / cm². 2 External quantum efficiency.

[0241] Lifetime LT is defined as the time taken at a constant current density j0 (in mA / cm²) 2 During operation (in units of cd / m²), the brightness increases from the initial brightness L0 (in cd / m²). 2 (in units) decreased to a specific ratio L1 (in cd / m 2 The data L1 / L0 = 90% in Table 8 refers to the lifetime reported in the LT column corresponding to the time (in hours) after the brightness has decreased to 90% of its initial value (L0).

[0242] Use of the mixture of the present invention in OLEDs

[0243] The compounds or material combinations of the present invention can be used in the light-emitting layer of phosphorescent green OLEDs.

[0244] Data for various OLEDs are summarized in Table 8. Examples V1 to V7 are comparative examples according to the prior art; Examples E1 to E6 illustrate data for the OLEDs of the present invention. The inventive examples demonstrate a particularly significant advantage in terms of device lifetime.

[0245] Table 7: Structure of OLED

[0246] Table 8: OLED Data

[0247] Table 9: Structural formulas of the OLED materials used (if not described above)

Claims

1. A compound of formula (1) or formula (1A), The symbols and markings used are as follows: Y is the same or different in each case, and is CR 1 Or N, provided that at least one Y group is N; X is the same or different in every case, and is CR 1 Or N; or two adjacent X's are S, O, or NR. 1 To form a five-membered ring; or two adjacent X's are groups of formula (2), (3) or (4) below. Where ^ indicates the corresponding adjacent X group in formula (1) or formula (1A); V is the same or different in every case, and is C(R) 1 2. NR 1 O, S, BR 1 Si(R) 1 )2 or C=O; Z is the same or different in every case, and is CR 1 Or N; Ar may be the same or different in each case, and is a ring with 5 to 40 aromatic atoms and can be substituted by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; R may be the same or different in each case, and is selected from H, D, F, Cl, Br, I, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of said groups being soluble in one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C=CR 2 The atoms are C≡C or O, and one or more of the hydrogen atoms may be replaced by D or F, or the atoms have 6 to 60 aromatic ring atoms and may be replaced by one or more R atoms. 2 Aromatic ring systems with substituted groups; here, two adjacent substituents R can also form a ring system that can be substituted by one or more R groups. 2 Monocyclic or polycyclic aliphatic or aromatic ring systems with substituted groups; R 1 The same or different in each case, and selected from H, D, F, Cl, Br, I, CN, NO2, N (Ar) 1 )2,N(R 2 )2,C(=O)Ar 1 C(=O)R 2 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, Si(Ar 1 )3,Si(R 2 )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, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of said groups being capable of being formed by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C=CR 2 C≡C, Si(R) 2 2. C=O, C=S, C=NR 2 P(=O)(R) 2 SO, SO2, NR 2 O, S or CONR 2 The atoms are replaced by D, F, Cl, Br, I, CN, or NO2, and the ring has 5 to 60 aromatic ring atoms, each of which can be replaced by one or more R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 60 aromatic ring atoms and being substituted by one or more R groups. 2 A group-substituted aryloxy or heteroaryloxy group; optionally, two adjacent substituents R 1 It can be formed by one or more R 2 Monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring systems with substituted groups; Ar 1 In each case, they may be the same or different, and they are aromatic rings with 5 to 30 atoms and can be separated by one or more non-aromatic R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups; here, two Ar atoms bonded to the same nitrogen or phosphorus atom. 1 Groups can also be formed via single bonds or selected from N(R) 2 ), C(R 2 2. The bridge bases of O or S are bridged to each other; R 2 In each case, they may be the same or different, and are selected from H, D, F, CN, aliphatic hydrocarbon groups having 1 to 20 carbon atoms, or aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, wherein two or more adjacent R atoms 2 Substituents can together form monocyclic or polycyclic aliphatic ring systems; m and n are the same or different in each case, and are 0 or 1, provided that m + n ≥ 1; p is the same or different in each case, and is 0, 1, 2, 3 or 4; q is 0, 1, or 2. Its features The compounds of formula (1) or formula (1A) contain at least one deuterium atom as a substituent.

2. The compound according to claim 1, characterized in that... At least one R group of the spirodifluorene group and / or one R group of the 6-membered ring formed by the X group. 1 The group is a deuterium atom.

3. The compound according to claim 1 or 2, characterized in that... At least one R of an aromatic or heteroaromatic ring system Ar and / or a 6-membered ring formed by a Y group. 1 The group is a deuterium atom.

4. The compound according to one or more of claims 1 to 3, characterized in that... The degree of deuteration of the compound of formula (1) or formula (1A) is in the range of 1 mol% to 100 mol%, preferably in the range of 10 mol% to 100 mol%.

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

6. A mixture comprising at least one compound of formula (1) or formula (1A) according to one or more of claims 1 to 4 and at least one other compound selected from electron transport materials, electron injection materials, hole blocking materials, materials having a high dielectric constant and / or solvents.

7. An organic electronic device comprising an anode, a cathode and at least one organic layer comprising at least one compound of formula (1) or formula (1A) according to one or more of claims 1 to 4.

8. The organic electronic device according to claim 7, wherein the electronic device is an electroluminescent device.

9. The organic electronic device according to claim 7 or 8, wherein the organic layer comprises at least one light-emitting layer, the light-emitting layer comprising at least one compound of formula (1) or formula (1A) according to any one of claims 1 to 4.

10. The organic electronic device according to one or more of claims 7 to 9, characterized in that... The light-emitting layer contains other matrix materials.

11. The organic electroluminescent device according to claim 10, characterized in that... The other matrix materials correspond to compounds of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), or (HH-6). Equation (HH-1), Equation (HH-2), Formula (HH-3), Formula (HH-4), Formula (HH-5), Formula (HH-6), The symbols and markings used are as follows: A 1 It is C(R) 7 2. NR 7 , O or S; L represents the bond, O, S, C(R) 7 )2 or NR 7 ; A is independently a group of formula (HH-4-1) or (HH-4-2) in each case. 、 Equation (HH-4-1) Equation (HH-4-2); X2 is the same or different in each case, and is CH, CR 6 Or N, where no more than two symbols X2 can be N; Indicates the binding site with formula (HH-4); U 1 U 2 When they appear, they are bonds, O, S, C(R). 7 )2 or NR 7 ; R 6 In each case, the same or different, and is 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 Group substitution, and one or more 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 form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems together; Ar5 may be the same or different in each case, and independently has 5 to 40 ring atoms and can be substituted 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 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, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 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; here, two or more R groups... 7 Groups can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems together, but R 7 The group preferably does not form any such ring system; R 8 In each case, they may be the same or different, and are H, D, F, or aliphatic, aromatic or heteroaromatic organic groups having 1 to 20 carbon atoms, especially hydrocarbon groups, in which one or more hydrogen atoms may also be replaced by F; c, c1, and c2 are each independently 0 or 1 in each case, and the sum of the labels in each case is c + c1 + c2 = 1; d, d1, and d2 are each independently 0 or 1 in each case, where the sum of the labels in each case is d + d1 + d2 = 1; q, q1, and q2 are each independently 0, 1, 2, 3, or 4 in each case; s is the same or different in each case, and is 0, 1, 2, 3 or 4; t is the same or different in each case, and is 0, 1, 2 or 3; u is the same or different in each case, and is 0, 1 or 2; u1 and u2 are each independently 0 or 1 in each case, where the sum u1 + u2 = 1; and v can be 0, 1, 2, or 3.

12. The organic electronic device according to one or more of claims 7 to 11, characterized in that... The light-emitting layer contains a phosphorescent material.

13. The organic electronic device according to claim 7 or 8, wherein the organic layer comprises at least one electron transport layer or electron injection layer or hole blocking layer, the electron transport layer or electron injection layer or hole blocking layer comprising a compound of formula (1) or formula (1A) according to any one of claims 1 to 4.

14. The organic electronic device according to one or more of claims 7 to 13, characterized in that... The organic electronic device is an electroluminescent device selected from organic light-emitting transistors (OLET), organic field quenching devices (OFQD), organic light-emitting electrochemical cells (OLEC), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs).

15. A method for manufacturing an organic electronic device according to one or more of claims 7 to 14, characterized in that... The organic layer is applied by vapor deposition or from a solution.

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