Novel materials for organic electroluminescent devices

Abstract

This invention relates to novel materials and organic electroluminescent devices, such as OLEDs (organic light-emitting diodes), comprising these materials, for example, as electron transport materials and / or optionally in combination with another matrix material. The invention also relates to mixtures and formulations containing these novel materials.

Description

Technical Field

[0001] This invention relates to novel materials and organic electronic devices, such as OLEDs (organic light-emitting diodes), that contain these materials, for example, as electron transport materials and / or optionally in combination with other matrix materials. The invention also relates to mixtures and formulations containing these novel materials. Background Technology

[0002] Structures of organic electroluminescent devices (e.g., OLEDs or OLECs (organic light-emitting electrochemical cells)) in which organic semiconductors are used as organic functional materials are described in, for example, US 4539507, US 5151629, EP 0676461, and WO 98 / 27136. The luminescent materials and phosphors used here are increasingly organometallic complexes exhibiting phosphorescence (MA Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6). For quantum mechanical reasons, using organometallic compounds as phosphorescent emitters can improve energy efficiency and power efficiency by up to four times. Generally, improvements are still needed in both singlet and triplet OLEDs, particularly in terms of efficiency, operating voltage, and lifetime.

[0003] The performance of organic electroluminescent devices depends not only on the light emitter used, but also, and perhaps more importantly, on other materials such as host and matrix materials, hole-blocking materials, electron transport materials, and electron or exciton-blocking materials. Improving these materials can lead to significant improvements in the electroluminescent device.

[0004] In the prior art, heteroaromatic compounds are particularly used as electron transport materials and as matrix materials for phosphorescent compounds. The term "matrix material" is generally used when referring to the host material of phosphorescent emitters. This use of the term "matrix material" is also used in this invention.

[0005] Compounds containing at least one substituted benzonitrile group are known and can be used in OLEDs, including as electron transport materials and / or as matrix materials (see WO 2012 / 015017, WO 2019 / 085684, WO 2022 / 065730, CN 113402525, KR 20180061074 and KR 2018 / 0010167).

[0006] However, improvements are still needed when these compounds are used, for example, as matrix materials, particularly in terms of device lifetime, efficiency, and operating voltage. Summary of the Invention

[0007] Therefore, one object of the present invention is to provide compounds suitable for use in organic electroluminescent devices and which induce good device performance when used in such devices, as well as corresponding organic electroluminescent devices. More particularly, one object of the present invention is to provide compounds that induce long lifetimes, good efficiency, and low operating voltages in phosphorescent or fluorescent OLEDs, especially fluorescent OLEDs. In particular, the properties of the matrix material also have a significant impact on the lifetime and efficiency of organic electroluminescent devices.

[0008] Furthermore, compounds, especially when used as matrix materials, hole-conducting materials, or electron-transmitting materials in organic electroluminescent devices, should enable the devices to have excellent color purity.

[0009] Furthermore, the compounds should be readily processable and exhibit particularly good solubility and film formation. For example, the compounds should exhibit increased oxidative stability and improved glass transition temperature. Additionally, the compounds should possess high thermal stability, enabling them to evaporate without decomposition, such as under high vacuum, thereby increasing the lifespan of the corresponding electroluminescent devices.

[0010] Another objective can be considered as providing electronic devices with excellent performance at the lowest cost and with constant quality.

[0011] These objectives are achieved by providing compounds of formula (I):

[0012] The markings and symbols used are as follows: L is a group of formula (II).

[0013] The dashed bond represents a bond connected to a phenyl or CN group; W is (CR) 2 )2、Si(R 2 2. NAr 2 , O or S; Ar and Ar 1 The same or different and having 5-40, preferably 25, aromatic ring atoms, and in each case can be one or more R 3 Aromatic or heteroaromatic ring systems with substituted groups, wherein the heteroaromatic ring system contains only one heteroatom; L 1 and L 2 In each case, they may be the same or different, and they are either single bonds or have 5-40 aromatic ring atoms, and in each case, they can be one or more R atoms. 4 Aromatic or heteroaromatic ring systems with substituted groups; Ar2 and Ar 3 In each case, they may be the same or different and have 5-40 aromatic ring atoms and may also be affected by one or more R... 5 Aromatic or heteroaromatic ring systems with substituted groups; R is the same or different in each case and is H and D; R 1 The same or different in each case and are H; D; F; Cl; Br; I; -OH; NO2; N(Ar) 3 )2;N(R 6 )2;C(=O)R 6 ;P(=O)(Ar 3 )2;P(Ar 3 )2;B(Ar 3 )2;Si(Ar 3 )3;Si(R 6 )3; a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which may be derived by one or more R 6 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by -R 6 C=CR 6 -、-C≡C-、Si(R 6 2. C=O, C=S, C=NR 6 -C(=O)O-, -C(=O)NR 6 -、NR 6 P(=O)(R) 6 The aromatic ring may be replaced by -O-, -S-, SO, or SO2, and one or more of the hydrogen atoms may be replaced by D, F, Cl, Br, I, or NO2; or it may have 5 to 40 aromatic ring atoms and in each case may be replaced by one or more R... 6 Aromatic or heteroaromatic ring systems with substituted groups; or having 5 to 40 aromatic ring atoms and being substituted by one or more R groups. 6 A group-substituted aryloxy or heteroaryloxy group; or having 5 to 40 aromatic ring atoms and in each case being substituted with one or more R groups. 6 A group-substituted aralkyl group; or a combination of these systems; wherein two or more adjacent substituents R 1 Optionally formed that can be generated by one or more R 6 Monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring systems with substituted groups; R 2 Same or different and is H; D; F; Cl; Br; I; NO2; -OH; NO2; N(Ar) 3 )2;N(R7 )2;C(=O)R 7 ;P(=O)(Ar 3 )2;P(Ar 3 )2;B(Ar 3 )2;Si(Ar 3 )3; a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which may be derived by one or more R 7 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by -R 7 C=CR 7 -、-C≡C-、Si(R 7 2. C=O, C=S, C=NR 7 -C(=O)O-, -C(=O)NR 7 -、NR 7 P(=O)(R) 7 The aromatic ring may be replaced by -O-, -S-, SO, or SO2, and one or more of the hydrogen atoms may be replaced by D, F, Cl, Br, I, or NO2; or it may have 5 to 40 aromatic ring atoms and in each case may be replaced by one or more R... 7 Aromatic or heteroaromatic ring systems with substituted groups; or having 5 to 40 aromatic ring atoms and being substituted by one or more R groups. 7 A group-substituted aryloxy or heteroaryloxy group; or having 5 to 40 aromatic ring atoms and in each case being substituted with one or more R groups. 7 A group-substituted aralkyl group; or a combination of these systems; wherein two substituents R 2 Optionally formed that can be generated by one or more R 7 Monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring systems with substituted groups; R 3 R 4 R 5 R 6 and R 7 In each case, the same or different and being H; D; F; -OH; a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more hydrogen atoms in these alkyl groups may be replaced by D or F; or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and wherein one or more hydrogen atoms may be replaced by D or F; wherein two or more adjacent substituents R 3 Two or more adjacent substituents R 4 Two or more adjacent substituents R 5 Two or more adjacent substituents R5 Or two or more adjacent substituents R 7 It can optionally form monocyclic or polycyclic aliphatic or aromatic ring systems. l is 0, 1, or 2; m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2; o is 0 or 1. Where, when o=0, L 1 It is an aromatic ring system with 6 to 12 aromatic ring atoms, and L 2 It is a single bond, and at least one of them is R. 4 It does not represent H, and it does not contain two or more adjacent substituents R. 4 Forming a ring system.

[0014] In the context of this invention, if any mark is 0, it means that the corresponding ring is replaced only by H in the free position.

[0015] The symbol “D” or “D atom” refers to deuterium.

[0016] In the context of this invention, an aryl group contains 6 to 40 ring atoms, preferably carbon atoms. In the context of this invention, a heteroaryl group contains 5 to 40 ring atoms, wherein the ring atoms comprise carbon atoms and at least one heteroatom, provided that the sum of the carbon atoms and the heteroatom is at least 5. The heteroatom is preferably selected from N, O, and / or S. The aryl group or heteroaryl group referred to herein means a simple aromatic ring, i.e., a phenyl ring derived from benzene, or a simple heteroaryl ring, such as one derived from pyridine, pyrimidine, or thiophene, or a fused aryl or heteroaryl group, such as one derived from naphthalene, anthracene, phenanthrene, quinoline, or isoquinoline. Therefore, an aryl group having 6 to 30 carbon atoms is preferably phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, biphenylidene, fluoranthyl, dibenzoanthryl, fulminyl, or perylene, and there is no limitation on the attachment of the aryl group as a substituent.

[0017] In the context of this invention, an aromatic ring system contains 6 to 40 carbon atoms in the ring system, and said ring system also includes the aforementioned aryl groups.

[0018] In the context of this invention, a heteroaromatic ring system 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 heteroaryl groups as described above. The heteroatom in the heteroaromatic ring system is preferably selected from N, O, and / or S.

[0019] In the context of 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 non-H atoms), such as carbon or oxygen atoms or carbonyl groups. For example, in the context of this invention, systems such as 9,9'-spirodifluorene, 9,9-diarylfluorene, 9,9-dialkylfluorene, diaryl ethers, piracene, etc., should therefore also be considered aromatic or heteroaromatic ring systems, as should systems in which two or more aryl groups are interrupted, for example, by straight-chain or cyclic alkyl groups or by silyl groups. Furthermore, systems in which two or more aryl or heteroaromatic groups are directly bonded to each other, such as biphenyl, terphenyl, tetraphenyl, or bipyridine, are also covered by the definition of an aromatic or heteroaromatic ring system.

[0020] Aromatic or heteroaromatic ring systems having 5-40 ring atoms and capable of being linked to aromatic or heteroaromatic systems at any desired position 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 indene, isotrimer indene. Spirotrimeric indene, spiroisotrimeric indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indole-carbazole, indole-carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenothiazine, pyrazole, indazole, imidazole, benzimidazole, naphthiamidazole, phenanthrenemidazole, pyridinium-imidazolium, pyrazinium-imidazolium, quinoxaline-imidazolium, pyrazole Benzo[a]azole, naphtho[a]azole, anthraxazole, phenanthrene[a]azole, iso[a]azole, 1,2-thiazole, 1,3-thiazole, benzo[a]thiazole, pyridazine, benzo[a]pyridazine, pyrimidine, benzo[a]pyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenanthrene, phenothiazine, fluorescein ring, naphthidine, azacarbazole, benzo[a]carbline, phenanthrene, 1,2,3-triazine Azole, 1,2,4-triazole, benzotriazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indoleazine, and benzothiadiazole.

[0021] Furthermore, straight-chain alkyl groups having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and branched or cyclic alkyl groups having 3 to 40 carbon atoms, preferably 3 to 20 carbon atoms, refer to, for example, the following groups: 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, Cyclohexyl, 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-hexane-1-yl, 1,1-dimethyl-n-heptane-1-yl, 1,1-dimethyl-n-octane-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-decyl-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. Here, the term "cycloalkyl group" includes monocyclic, bicyclic, or polycyclic groups.

[0022] A straight-chain alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S and at least one hydrogen atom may be replaced by D, F or CN, refers to, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methylbutoxy, thiomethyl, 1-thioethyl, 1-thioisopropyl, 1-thion-propyl, 1-thioisobutyl, 1-thion-butyl or 1-thiotert-butyl.

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

[0024] The phrase "two or more groups together can form a ring system" refers to the formation of an aliphatic, aromatic, or heteroaromatic ring system, and in the context of this specification, it should particularly refer to two groups connected to each other by chemical bonds, wherein two hydrogen atoms are formally eliminated. This is illustrated by the following scheme: .

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

[0026] The compounds of formula (I) and their preferred embodiments are described below. These preferred embodiments also apply to the mixtures and formulations of the present invention, and to the organic electronic or electroluminescent devices of the present invention.

[0027] The compounds of formula (I) of the present invention may be selected from compounds of formula (Ia), formula (Ib) or formula (Ic), preferably selected from compounds of formula (Ia):

[0028] The marks and symbols have the definitions given above.

[0029] Further preferably, in formula (I) or in formulas (Ia), (Ib) or (Ic), o=1.

[0030] In another preferred embodiment of the invention, Ar and Ar 1 The same or different and having 5-25 aromatic ring atoms, more preferably 5 to 18 aromatic ring atoms, or even more preferably 5 to 13 aromatic ring atoms and can be denoted by one or more R 3A group-substituted aromatic or heteroaromatic ring system, wherein the heteroaromatic ring system contains only one heteroatom. Here, the aromatic or heteroaromatic ring system may be selected from, for example, phenyl, ortho, meta, or para-phenyl, terphenyl, especially branched terphenyl, tetraphenyl; especially phenyl, ortho, meta, or para-phenyl, 1-, 2-, 3- or 4-fluorenyl, especially 4-fluorenyl, 1-, 2-, 3- or 4-spirodifluorenyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiopheneyl, 1-, 2-, 3- or 4-carbazoleyl, 1- or 2-naphthyl, anthraceneyl, preferably 9-anthrayl, phenanthreneyl, and / or biphenylideneyl.

[0031] More preferably, Ar and Ar 1 In each case, they may be the same or different, and are selected from phenyl, biphenyl, dibenzofuran, or dibenzothiophene, each of which may be substituented by one or more R groups. 3 Substitution. Biphenyl can be ortho, meta, or para-biphenyl; dibenzofuran can be 1-, 2-, 3-, or 4-dibenzofuranyl; and dibenzothiophene can be 1-, 2-, 3-, or 4-dibenzothiopheneyl.

[0032] R 3 The groups may be the same or different in each case and are preferably selected from H; D; F; -OH; straight-chain alkyl groups having 1-10 carbon atoms, more preferably 1-6 carbon atoms, and even more preferably 1-4 carbon atoms; branched or cyclic alkyl groups having 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms, wherein one or more hydrogen atoms in these alkyl groups may be replaced by D or F; or aromatic or heteroaromatic ring systems having 5 to 25 aromatic ring atoms, more preferably 5 to 18 aromatic ring atoms, and even more preferably 5 to 13 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D or F. Even more preferably, R 3 The functional groups may be the same or different in each case and are selected from H, D, straight-chain alkyl chains having 1-4 carbon atoms, or aromatic or heteroaromatic ring systems having 5 to 13 aromatic ring atoms. Most preferably, R 3 The functional groups may be the same or different in each case and are H or D. Here, the aromatic or heteroaromatic ring system may be selected from, for example, phenyl, ortho, meta or para-phenyl, terphenyl, especially branched terphenyl, tetraphenyl, especially branched tetraphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirodifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiopheneyl, pyrene, triazinyl, imidazolyl, benzimidazolyl, benzo[a]azolyl, benzo[a]thiazolyl, 1-, 2-, 3- or 4-carbazole, 1- or 2-naphthyl, anthraceneyl, preferably 9-anthrayl, phenanthryl and / or biphenylidene.

[0033] Similarly, R in preferred formula (II) 1 The groups may be the same or different in each case and are selected from H; D; F; -OH; straight-chain alkyl groups having 1-10 carbon atoms, more preferably 1-6 carbon atoms, and even more preferably 1-4 carbon atoms; branched or cyclic alkyl groups having 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms, wherein one or more hydrogen atoms in these alkyl groups may be replaced by D or F; or aromatic or heteroaromatic ring systems having 5 to 25 aromatic ring atoms, more preferably 5 to 18 aromatic ring atoms, and even more preferably 5 to 13 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D or F.

[0034] Optionally, two or more adjacent substituents R 1 It can be formed by one or more R 5 A monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring system with substituted groups, preferably an aromatic or heteroaromatic ring system. Even more preferably, R... 1 The functional groups may be the same or different in each case and are selected from H, D, straight-chain alkyl chains having 1-4 carbon atoms, or aromatic rings having 5 to 13 atoms and being capable of being formed by one or more R groups. 5 Aromatic or heteroaromatic ring systems with substituents, wherein two or more adjacent substituents R 1 Optionally formed can be one or more R 5 The substituted monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring systems are preferred. Here, the aromatic or heteroaromatic ring system may be selected from, for example, phenyl, ortho-, meta-, or para-phenyl, terphenyl, especially branched terphenyl, tetraphenyl, especially branched tetraphenyl, 1-, 2-, 3-, or 4-fluorenyl, 1-, 2-, 3-, or 4-spirodifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3-, or 4-dibenzofuranyl, 1-, 2-, 3-, or 4-dibenzothiopheneyl, pyrene, triazinyl, imidazolyl, benzimidazolyl, benzo[a]azolyl, benzo[a]thiazolyl, 1-, 2-, 3-, or 4-carbazole, 1-, or 2-naphthyl, anthraceneyl, preferably 9-anthracite, phenanthrene, and / or biphenylideneyl.

[0035] R 3 The above-described preferred embodiments are also applicable to R 5 .

[0036] In yet another preferred embodiment of the invention, L in formula (II) 1 and L 2 The same or different and is a single bond; or has 5 to 25 aromatic ring atoms and can be separated by one or more R 4 Aromatic or heteroaromatic ring systems with substituent groups, wherein R 4It has the definition given above.

[0037] For L 1 and L 2 Suitable examples of aromatic or heteroaromatic ring systems can be independently selected from L-1 to L-30: , Where V 1 = O, S, NR 4 ,NAr 2 O or S is preferred.

[0038] More preferably, L 1 and L 2 In each case, they may be the same or different and are single bonds; or they may have 5 to 18 aromatic ring atoms and be able to be bonded by one or more R atoms. 4 Aromatic or heteroaromatic ring systems with substituent groups, wherein R 4 It has the definition given above.

[0039] Even more preferably, L 1 and L 2 In each case, the same or different and being a single bond, phenyl (L-1 to L-3), biphenyl (L-4 to L-7), dibenzofuran, or dibenzothiophene (L-18 to L-30), wherein these ring systems can be generated by one or more R 4 Group substitution, wherein R 4 It has the definition given above.

[0040] R 3 The above-described preferred embodiments are also applicable to R 4 Group.

[0041] In yet another preferred embodiment of the present invention, W in formula (II) is NAr 2 O, S or (CR) 2 )2, where Ar 2 and R 2 It has the definition given above. More preferably, W in equation (II) is O, S, or (CR). 2 )2, the optimal choice is O or S.

[0042] Ar is preferred here 2 It is an aromatic or heteroaromatic ring system having 5-25 aromatic ring atoms, preferably an aromatic or heteroaromatic ring system having 5 to 18 ring atoms, more preferably an aromatic or heteroaromatic ring system having 5 to 13 ring atoms, and most preferably an aromatic ring system having 6 to 12 ring atoms, wherein each ring system can be converted into one or more R 5 Group substitution, wherein R 5 As defined above. Here, the aromatic or heteroaromatic ring system may be selected from, for example, phenyl, ortho, meta, or para-phenyl, terphenyl, especially branched terphenyl, tetraphenyl, especially branched tetraphenyl, 1-, 2-, 3-, or 4-fluorenyl, 1-, 2-, 3-, or 4-spirodifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3-, or 4-dibenzofuranyl, 1-, 2-, 3-, or 4-dibenzothiopheneyl, pyrene, triazinyl, imidazolyl, benzimidazolyl, benzo[a]azolyl, benzo[a]thiazolyl, 1-, 2-, 3-, or 4-carbazole, 1-, or 2-naphthyl, anthraceneyl, preferably 9-anthrayl, phenanthryl, and / or biphenylideneyl.

[0043] The R mentioned 3 The preferred implementation method is also applicable to R 5 Group.

[0044] If W is (CR) 2 If )2, then R is preferred. 2 The groups may be the same or different and are H; D; F; -OH; a straight-chain alkyl, alkoxy, or thioalkyl chain having 1 to 20 carbon atoms, or a branched alkyl, alkoxy, or thioalkoxy chain having 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, or even more preferably 3 to 6 carbon atoms, wherein one or more hydrogen atoms in these alkyl, alkoxy, or thioalkoxy chains may be replaced by D or F; or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein each ring system may be replaced by one or more R 7 Group substitution; or combinations of these systems. Two or more R groups are further preferred. 2Group formation can be achieved by one or more R 7 Monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring systems with substituted groups.

[0045] R 3 The above-described preferred embodiments of the group also apply to R. 7 Group.

[0046] In yet another preferred embodiment of the invention, in formula (II), W is O, S, or (CR). 2 )2, where R 2 The groups may be the same or different in each case, and are selected from straight-chain alkyl groups having 1-20 carbon atoms, preferably 1-10 carbon atoms, more preferably 1-6 carbon atoms; branched alkyl chains having 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms, wherein one or more hydrogen atoms in these alkyl chains may be replaced by D or F; having 6 to 24 ring atoms and being replaced by one or more R 7 Aromatic or heteroaromatic ring systems with substituted groups; or two R groups 2 The group forms an aromatic or heteroaromatic ring system of formula (III) or (IV).

[0047] in

[0048] p = 0, 1, 2, 3, or 4, preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, and other markings and symbols have the definitions given above; this also applies to R. 1 and R 7 Preferred embodiments of the group.

[0049] Ar is also preferred 3 It is an aromatic or heteroaromatic ring system having 5-24 aromatic ring atoms, preferably an aromatic or heteroaromatic ring system having 5 to 18 ring atoms, more preferably an aromatic or heteroaromatic ring system having 5 to 13 ring atoms, and most preferably an aromatic ring system having 6 to 12 ring atoms, wherein each ring system can be converted into one or more R 5 Group substitution, wherein R 5 It has the definition given above.

[0050] Examples of suitable compounds of formula (I) of the present invention are listed in Table 1 below.

[0051] Table 1 :

[0052] The particularly suitable compounds of formula (I) are compounds E1 to E27 in Table 2.

[0053] Table 2 :

[0054] The compounds of this 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. 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 general knowledge in the art.

[0055] Option 1:

[0056] Option 2:

[0057] Option 3:

[0058] The detailed reaction conditions are those known from the prior art or described in the Examples section.

[0059] To process the compounds of the present invention from the liquid phase, for example by spin coating or printing, formulations of the compounds of the present invention or mixtures of the compounds of the present invention with other functional materials such as matrix materials, fluorescent emitters, phosphorescent emitters, and / or emitters exhibiting TADF are required. These formulations can be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents are preferably used. For example, suitable and preferred solvents are toluene, anisole, o-xylene, m-xylene 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 Cyclohexanone, 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.

[0060] When the compounds of the present invention are used as matrix materials (or, synonymously, host materials) in the light-emitting layer, they are preferably used in combination with other compounds.

[0061] Therefore, the present invention also provides a mixture comprising at least one compound of formula (I) or at least one preferred compound of formula (Ia) or one of the compounds from Table 1 or compounds E1 to E27, and at least one other compound selected from matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence). Suitable matrix materials and emitters that can be used in such mixtures of the present invention are described below.

[0062] The present invention also provides a formulation comprising at least one compound of the present invention as described above or a mixture of the present invention as described above, and at least one solvent. The solvent may be the solvents described above or a mixture of these solvents.

[0063] The present invention also provides an organic electronic device comprising an anode, a cathode and at least one organic layer, the organic layer comprising at least one compound of formula (I), or at least one of the preferred formulas (Ia), or one of the compounds from Table 1 or compounds E1 to E27.

[0064] 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.

[0065] Organic electronic devices are preferably organic electroluminescent devices.

[0066] The organic electroluminescent devices of the present invention (synonymous with organic electroluminescent devices) are, for example, organic light-emitting transistors (OLETs), organic field quenching devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers), or organic light-emitting diodes (OLEDs). The organic electroluminescent devices of the present invention are particularly organic light-emitting diodes or organic light-emitting electrochemical cells. The devices of the present invention are more preferably OLEDs.

[0067] In addition to the light-emitting layer (EML), the organic layers of the device of the present invention preferably also include 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 derived from these layers, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. Similarly, an intermediate layer, for example, having exciton blocking functionality, may be introduced between two light-emitting layers.

[0068] If multiple emitting layers are present, these emitting layers preferably have multiple emission maximum values ​​between 380 nm and 750 nm, resulting in overall white emission; in other words, multiple fluorescent or phosphorescent emitting compounds are used in the emitting layers. Two or more fluorescent and / or phosphorescent compounds may also be present in the emitting layers. A system with three emitting layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. As an alternative example of the combination described above, the emitting layers may also exhibit yellow emission. Such combinations are known to those skilled in the art. The organic electroluminescent device of the present invention can also be a tandem electroluminescent device, especially a white emitting OLED. The device may also contain layers of inorganic materials or layers formed entirely of inorganic materials.

[0069] For those skilled in the art, there is no difficulty in considering the various materials known in the prior art to select a suitable material for the aforementioned layers in organic electroluminescent devices. Here, those skilled in the art will consider the chemical and physical properties of the materials in a conventional manner, as they know that materials interact with each other in organic electroluminescent devices. This involves, for example, orbital energy levels (HOMO, LUMO) or triplet and singlet energy levels, as well as other material properties.

[0070] Depending on the exact structure, compounds of formula (I) of the present invention, as described above or as preferred in the description, can be used in different layers. Preferably, an organic electroluminescent device contains compounds of formula (I) or those described in the preferred embodiments above in the luminescent layer as matrix materials for phosphorescent emitters, phosphorescent emitters, or emitters exhibiting TADF (thermally activated delayed fluorescence), particularly for phosphorescent emitters. Furthermore, the compounds of the present invention can also be used in electron transport layers and / or hole transport layers and / or exciton blocking layers and / or hole blocking layers. It is particularly preferred to use the compounds of the present invention as matrix materials in the luminescent layer or as electron transport materials or hole blocking materials in the electron transport layer or hole blocking layer.

[0071] 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 (I), or at least one preferred compound of formula (Ia), or one of the compounds from Table 1 or compounds E1 to E27.

[0072] In one embodiment of the invention, for the device of the invention, at least one other matrix material is selected for use in the light-emitting layer and is used with a compound of formula (I) as described above or as preferred, or with compounds from Table 1 or compounds E1 to E27.

[0073] 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 (I), or at least one preferred compound of formula (Ia), or one of the compounds from Table 1 or compounds E1 to E27, and at least one other matrix material.

[0074] 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 (I), or at least one preferred compound of formula (Ia), or one of the compounds from Table 1 or compounds E1 to E27, and two other matrix materials.

[0075] 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 sulfones, triarylamines, carbazole derivatives, bicarbazoles, indoloxacarbazole derivatives, indoxacarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, borazine or borate esters, triazine derivatives, zinc complexes, diazacyclopentane or tetrazacyclopentane derivatives, phosphazacyclopentane derivatives, bridging carbazole derivatives, biphenylide derivatives, or dibenzofuran derivatives. Similarly, the mixture may also contain other phosphorescent emitters with shorter emission wavelengths than the actual emitters as co-hosts, or compounds that participate in charge transport but not to a significant extent, such as wide-bandgap compounds.

[0076] Wide bandgap material refers herein to a material within the scope of the disclosure of US 7,294,849, characterized in that the bandgap is at least 3.5 eV, and the bandgap is the gap between the HOMO energy and the LUMO energy of the material.

[0077] Particularly suitable hole-transporting matrix materials that can be advantageously combined in a mixed matrix system with compounds of the formula (I) as described above or preferred are selected from compounds of the formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) as described below.

[0078] Therefore, the present invention also provides an organic electronic device, particularly 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 light-emitting layer, wherein the at least one light-emitting layer comprises at least one compound of the formula (I) described above or as preferred, as matrix material 1, and at least one compound of the formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), or (HH-6) as matrix material 2 (other matrix materials): Equation (HH-1), Equation (HH-2), Formula (HH-3), Equation (HH-4), Formula (HH-5), Formula (HH-6), The symbols and markings used are as follows: A 1 It is C(R) 9 2. NR 9 , O or S; L represents the bond, O, S, C(R). 9 )2 or NR 9 ; 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); X1 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 and U 2 In each case, they may be the same or different and are bonds, O, S, C(R). 9 )2 or NR 9 ; R 8 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) 9 2. C=O, NR 9 O, S or CONR 9 Replace; or have 5 to 40 ring atoms and in each case can be replaced by one or more R 9 Aromatic or heteroaromatic ring systems with substituted groups; here, two R groups... 6 The groups can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems together; Ar5 is the same or different in each case and independently has 5 to 40 ring atoms and can be denoted by one or more R atoms. 9 Aromatic or heteroaromatic ring systems with substituted groups; R 9 The same or different in each case and are D; F; Cl; Br; I; N(R) 8 )2;CN;NO2;OR 10 ;SR 10 ;Si(R) 10 )3;B(OR 10 )2;C(=O)R 10 ;P(=O)(R 10 )2;S(=O)R10 ;S(=O)2R 10 OSO2R 10 ; 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 10 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 10 2. C=O, NR 10 O, S or CONR 10 Replace; or have 5 to 40 ring atoms and in each case can be replaced by one or more R 10 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 9 The groups can together form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; preferably, R 9 The group does not form any such ring system; R 10 In each case, the same or different and is H, D, F, or an aliphatic, aromatic or heteroaromatic organic group, especially a hydrocarbon group, having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be replaced by F; c, c1, and c2 are each 0 or 1 independently in each case, where 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 markings in each case is d + d1 + d2 = 1; q, q1, and q2 are 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.

[0079] In compounds of formula (HH-1), (HH-2), (HH-3), (HH-5), or (HH-6), when R 8 When the group is not D, s is preferably 0 or 1, or more preferably 0.

[0080] In compounds of formula (HH-1), (HH-2), or (HH-3), when R 8When the group is not D, t is preferably 0 or 1, or more preferably 0. In compounds of formula (HH-1), (HH-2), (HH-3), or (HH-5), when R 8 When the group is not D, u is preferably 0 or 1, or more preferably 0.

[0081] In compounds of formula (HH-1), (HH-2), (HH-3), (HH-5), or (HH-6), the sum of the markings s, t, and u preferably does not exceed 6, particularly preferably not more than 4, and more preferably not more than 2. When R 8 When it is not D, this is the preferred case.

[0082] In compounds of formula (HH-4), 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.

[0083] In compounds of formula (HH-4), L is preferably a single bond or C(R) bond. 9 )2, where R 9 It has the definition given above; more preferably, L is a single bond.

[0084] In equation (HH-4-1), when R 8 When the group is not D, v is preferably 0 or 1.

[0085] In equation (HH-4-2), U 1 or U 2 In the presence of these, single bonds or C(R) bonds are preferred. 9 )2, where R 9 It has the definition given above; more preferably, U 1 or U 2 In the case of their presence, they are single bonds.

[0086] In equation (HH-4-2), when R 8 When the group is not D, q, q1, and q2 are preferably 0 or 1.

[0087] In a preferred embodiment of compounds of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), or (HH-6) that can be combined with compounds of formula (I) as described above or preferred compounds of formula (I) according to the present invention, R 8 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 9Group substitution; or having 5 to 60 aromatic ring atoms, preferably 5 to 40 ring atoms, and in each case being substituted with one or more R groups. 9 Aromatic or heteroaromatic ring systems with substituted groups.

[0088] In a preferred embodiment of compounds of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), or (HH-6) that can be combined with compounds of formula (I) as described above or preferred compounds of formula (I) according to the present invention, R 8 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 generated by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups.

[0089] Preferably, the Ar5 in compounds of formula (HH-1), (HH-2), (HH-3), (HH-5), or (HH-6) is selected from phenyl; biphenyl, especially ortho-biphenyl, meta-biphenyl, or para-biphenyl; terphenyl, especially ortho-terphenyl, meta-terphenyl, or para-terphenyl, or branched terphenyl; tetraphenyl, especially ortho-tetraphenyl, meta-tetraphenyl, or para-tetraphenyl, or branched tetraphenyl; a fluorene group that may be linked at positions 1, 2, 3, or 4; or a fluorene group that may be linked at positions 1, 2, 3, or 4. 4-linked spirodifluorenyl; naphthyl, especially 1- or 2-bonded naphthyl; or a group derived from indole; benzofuran; benzothiophene; carbazole linked at 1, 2, 3, or 4; dibenzofuran linked at 1, 2, 3, or 4; dibenzothiophene linked at 1, 2, 3, or 4; indole-carbazole; indolocarbazole; pyridine; pyrimidine; pyrazine; pyridazine; triazine; quinoline; isoquinoline, quinazoline; quinoxaline; phenanthrene or biphenylide, each of these groups may be derived from one or more R 9 Group substitution. Ar5 is preferably unsubstituted.

[0090] When A in formula (HH-2) or (HH-3) or (HH-6) 1 It is NR 9 When the substituent R is bonded to the nitrogen atom 9 Preferably, it has 5 to 24 aromatic ring atoms and can be further divided by one or more R 10 Aromatic or heteroaromatic ring systems substituted with a substituent group. In a particularly preferred embodiment, the substituent R... 9 In each case, they may be the same or different and are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, especially 6 to 18 aromatic ring atoms. R 9 Preferred embodiments are preferably unsubstituted phenyl, biphenyl, terphenyl, and tetraphenyl, and can be substituted by one or more R 10 The substituent group is derived from triazine, pyrimidine, and quinazoline groups.

[0091] When A in formula (HH-2) or (HH-3) or (HH-6) 1 It is C(R) 9 When )2, the substituent R bonded to this carbon atom 9 Preferably, in each case, the same or different, and is 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 an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, said group or ring system may also be replaced by one or more R 8 Group substitution. Most preferably, R 9 It is a methyl group or a phenyl group. In this case, R 9 Groups can also form ring systems together, thus obtaining spirocyclic systems.

[0092] In a preferred embodiment of the compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), and (HH-6), these compounds are partially or fully deuterated, more preferably fully deuterated.

[0093] The preparation of compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), and (HH-6) is generally known, and some of these compounds are commercially available.

[0094] Compounds of formula (HH-4) are disclosed, for example, on pages 110 to 119 of WO 2021 / 180614, and especially as examples on pages 120 to 127. Their preparation is disclosed on page 128 of WO 2021 / 180614 A1 and in synthetic examples on pages 214 to 218.

[0095] The preparation of triarylamines of formula (HH-6) is known to those skilled in the art, and some of the compounds are commercially available.

[0096] 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, the deuterated compounds differing only in the level of deuteration.

[0097] In a preferred embodiment of the at least one other matrix material, the at least one other matrix material is a mixture of deuterated compounds of the formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) as described above, wherein the deuteration level of these compounds is at least 50% to 90%, preferably 70% to 100%.

[0098] In a preferred embodiment of the at least one other matrix material, the at least one other matrix material is a mixture of deuterated compounds of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and / or (HH-6) as described above, wherein the deuteration level of these compounds is at least 50% to 90%, preferably 70% to 100%.

[0099] The corresponding deuteration methods are known to those skilled in the art and are described, for example, in KR 2016041014 A, WO2017 / 122988 A1, KR 2020052820 A, KR 101978651 B1 and WO 2018 / 110887 A1 or Bulletin of the Chemical Society of Japan, 2021, 94(2), 600-605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0100] 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.

[0101] 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.

[0102] Examples of other suitable matrix materials for combination with compounds described as above or preferred formula (I) are the compounds described in Table 3 on pages 137 to 203 of WO 2019 / 229011 A1, which may also be partially or fully deuterated.

[0103] Examples of suitable other matrix materials for use in combination with compounds of the preferred formula (I) as described above or as such are the compounds described in Tables 3 on pages 131 to 127 and Tables 4 on pages 137 to 139 of WO 2021 / 180625 A1, which may also be partially or fully deuterated.

[0104] Examples of suitable other matrix materials for combination with compounds of the preferred formula (I) or preferred formula (Ia) as described above or as described above are the compounds described in the table on page 30 of WO 2011 / 088877 A1, namely compounds 1 to 166, which may also be partially or fully deuterated.

[0105] Examples of suitable other matrix materials for combination with compounds of the preferred formula (I) or preferred formula (Ia) as described above or as described above are compounds 1 to 151 listed in the table on page 23 of WO 2011 / 128017 A1, wherein these compounds may also be partially or fully deuterated.

[0106] Examples of other suitable matrix materials for use in combination with compounds of the preferred formula (I) or preferred formula (Ia) as described above or as described above are compounds described on pages 42 to 47 of KR 20230034896 A, namely compounds [2-1] to [2-110], or compounds described on pages 49 to 51, namely compounds [3-1] to [3-26].

[0107] For combinations with compounds as described above or as preferably of formula (I), particularly suitable compounds are those in which at least one Ar5 group has 5 to 40 ring atoms and can be derived from one or more R groups. 9 Compounds of formula (HH-1) and / or formula (HH-4) and / or formula (HH-5) of heteroaromatic ring systems with substituted groups.

[0108] For combinations with compounds of formula (I) as described above or as preferred, especially compounds of formula (Ia), compounds of formula (HH-4) or (HH-5) are suitable and very particularly preferred.

[0109] Other examples of host materials of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), and (HH-6) suitable for combination with compounds of the preferred formula (I) or preferred formula (Ia) as described above are the structures in Tables 3 and 4 given below.

[0110] Table 3 :

[0111] The compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6) selected according to the present invention and preferably used in combination with at least one compound of formula (I) in the electroluminescent device of the present invention are the compounds in Table 4.

[0112] Table 4 :

[0113] The host material of the aforementioned formula (I) and the preferred embodiments thereof, or the compounds and compounds E1 to E27 from Table 1, may be combined in the device of the present invention, as needed, with the aforementioned matrix material / host material, the matrix material / host material of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) and the preferred embodiments thereof, or compounds H1 to H27 from Table 3.

[0114] A particularly preferred mixture of the compound of formula (I) used in the device of the present invention and the main material of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) is obtained by combining compounds E1 to E27 with compounds H1 to H27, as shown in Table 5 below. The first mixture M1 is, for example, a combination of compounds E1 and H1.

[0115] A very particularly preferred mixture of the compound of formula (1) used in the device of the present invention and the main material of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) is obtained by combining compounds E1 to E27 with compounds H1 to H27, as shown in Table 5 below. The first mixture M1 is, for example, a combination of compounds E1 and H1.

[0116] Table 5 :

[0117] Based on the overall composition of the mixture or the light-emitting layer, the concentration of the host material of the preferred formula (I) described above or in the light-emitting layer of the device of the present invention is generally in the range of 5% to 90% by weight, preferably in the range of 10% to 85% by weight, more preferably in the range of 20% to 85% by weight, even more preferably in the range of 30% to 80% by weight, very particularly preferably in the range of 20% to 60% by weight, and most preferably in the range of 30% to 50% by weight.

[0118] Based on the overall composition of the mixture or the light-emitting layer, the concentration of the sum of all the main materials of the preferred formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), and (HH-6) described above or in the light-emitting layer of the device of the present invention is generally in the range of 10 wt% to 95 wt%, preferably in the range of 15 wt% to 90 wt%, more preferably in the range of 15 wt% to 80 wt%, even more preferably in the range of 20 wt% to 70 wt%, very particularly preferably in the range of 40 wt% to 80 wt%, and most preferably in the range of 50 wt% to 70 wt%.

[0119] The present invention also relates to a mixture comprising, in addition to a host material of the aforementioned formula (I) referred to below as host material 1 and a host material of at least one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6) described above or preferred, referred to below as host material 2, the mixture further comprising at least one phosphorescent luminescent material.

[0120] The present invention also relates to a mixture selected from M1 to M729 and further comprising at least one phosphorescent emitting element.

[0121] The present invention also relates to an organic electroluminescent device as described above or as preferred, wherein, in addition to a host material comprising the aforementioned formula (I) and a host material comprising at least one of the aforementioned formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), particularly material combinations M1 to M729, the light-emitting layer further comprises at least one phosphorescent material.

[0122] The term "phosphorescent emitter" generally encompasses compounds that emit light via spin-forbidden transitions from excited states having high spin multiplicity, i.e., spin state > 1, such as via transitions from triplet states or states with even higher spin quantum numbers, such as quintet states. This preferably refers to transitions from triplet states.

[0123] Suitable phosphorescent emitters (= triplet emitters) are, in particular, compounds that emit light when properly excited, preferably in the visible light region, and further contain at least one atom with an atomic number greater than 20, preferably greater than 38 but less than 84, more preferably greater than 56 but less than 80, especially metals having such atomic numbers. Preferred phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, especially compounds containing iridium or platinum. In the context of this invention, all luminescent compounds containing the aforementioned metals are considered phosphorescent emitters.

[0124] Generally, any phosphorescent complexes known to those skilled in the art for use in phosphorescent OLEDs and organic electroluminescent devices are suitable.

[0125] According to the present invention, the preferred phosphorescent emitter conforms to formula (3a). Equation (3a), The symbols and notations for this equation (3a) are defined as follows: n+q is 3, n is 1 or 2, and q is 2 or 1. X is the same or different in each case and is N or CR. R x In each case, the same or different 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 can be partially or fully substituted by deuterium, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms that can be partially or fully substituted by deuterium.

[0126] 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 conforming to formula (3a) as described above.

[0127] In the light emitter of formula (3a), n is preferably 1 and q is preferably 2.

[0128] In the luminescent body of formula (3a), 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.

[0129] In the light emitter of formula (3a), at least one R is preferably different from H. In the light emitter of formula (3a), preferably two Rs are different from H and have one of the other definitions given above for the light emitter of formula (3a).

[0130] According to the present invention, the preferred phosphorescent emitter conforms to formula (1), (2), (3), (4) or (5). Equation (1) , Equation (2) , Equation (3) , Equation (4) , Equation (5) , The symbols and notations for these equations (1), (2), (3), (4), and (5) 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.

[0131] According to the present invention, the preferred phosphorescent emitter conforms to formula (6), (7) or (8). Equation (6) , Equation (7) , Equation (8) , The symbols and notations for these equations (6), (7), and (8) 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.

[0132] Preferred examples of phosphorescent luminescent materials are described in Tables 5 on pages 120 to 126 and Tables 6 on pages 127 to 129 of WO 2019 / 007867. These luminescent materials are incorporated herein by reference.

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

[0134] Table 6 :

[0135] In the mixtures of the present invention or in the light-emitting layer of the device of the present invention, any mixture selected from the sum of mixtures M1 to M729 is preferably combined with a compound of formula (3a) or a compound of formulas (1) to (8) or a compound from Table 6.

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

[0137] A yellow emitting layer refers to a layer having a maximum photoluminescence value in the range of 540 nm to 570 nm. An orange emitting layer refers to a layer having a maximum photoluminescence value in the range of 570 nm to 600 nm. A red emitting layer refers to a layer having a maximum photoluminescence value in the range of 600 nm to 750 nm. A green emitting layer refers to a layer having a maximum photoluminescence value in the range of 490 nm to 540 nm. A blue emitting layer refers to a layer having a maximum photoluminescence value in the range of 440 nm to 490 nm. Here, the maximum photoluminescence value of the layer is determined by measuring the photoluminescence spectrum of the layer having a layer thickness of 50 nm at room temperature, wherein the layer comprises the inventive combination and corresponding luminescent body of the host material 1 of formula (I), especially formula (Ia) and host material 2 composed of at least one of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), and (HH-6).

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

[0139] The photoluminescence spectrum of the selected luminescent organism is typically in the range of 10. -5Measurements are taken at room temperature in an oxygen-free solution of molar concentration. 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. Measurements are performed using a commercial photoluminescence spectrometer. The triplet energy T1 (in eV) is determined from the photoluminescence spectrum of the luminescent material. First, the peak maximum value Plmax. (in nm) of the photoluminescence spectrum is determined. Then, the peak maximum value Plmax. (in nm) is converted to eV using the following formula: E(T1 in eV) = 1240 / E(T1 in nm) = 1240 / PLmax. (in nm).

[0140] Therefore, the preferred phosphorescent emitter is a yellow emitter, preferably of formula (3a), formulas (1) to (8) or yellow emitters from Table 6, with a triplet energy T1 preferably of about 2.3 eV to about 2.1 eV.

[0141] Therefore, the preferred phosphorescent emitter is a green emitter, preferably of formula (3a), formulas (1) to (8) or green emitters from Table 6, with a triplet energy T1 preferably of about 2.5 eV to about 2.3 eV.

[0142] Therefore, the particularly preferred phosphorescent emitter is a green emitter as described above, preferably a green emitter of formula (3a), formulas (1) to (8) or from Table 6, whose triplet energy T1 is preferably about 2.5 eV to about 2.3 eV.

[0143] Most preferably, the green light emitter as described above, preferably of formula (3a), formulas (1) to (8) or green light emitters from Table 6, is selected for use in the mixture of the present invention or the light-emitting layer of the present invention.

[0144] The fluorescent light emitter may also be present in the light-emitting layer of the device of the present invention or in the mixture of the present invention.

[0145] Preferred fluorescent compounds are selected from arylamines, wherein preferably, at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, more preferably having at least 14 ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyreneamines, aromatic pyrene diamines, aromatic pyrine amines, or aromatic pyrine diamines. An aromatic anthraceneamine is a compound in which a diaryl amino group is directly bonded to an anthracene group, preferably at the 9-position. An aromatic anthracene diamine is a compound in which two diaryl amino groups are directly bonded to an anthracene group, preferably at the 9 and 10 positions. The definitions of aromatic pyreneamines, pyrene diamines, pyrine amines, and pyrine diamines are similar, wherein the diaryl amino groups are preferably bonded to pyrene at the 1-position or at the 1 and 6-positions. Also preferred luminescent compounds are indoxfluoreneamine or indoxfluorene diamine, benzo[a]indoxfluoreneamine or benzo[a]indoxfluorene diamine and dibenzo[a]indoxfluoreneamine or dibenzo[a]indoxfluorene diamine, and indoxfluorene derivatives having fused aryl groups. 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 further comprise materials exhibiting TADF (thermally activated delayed fluorescence).

[0146] In another preferred embodiment of the invention, 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 in addition to host material 1 or host material 2, they 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. Preferably, the hybrid matrix system is optimized for the light emitter according to formula (3a), formulas (1) to (8), or from Table 6.

[0147] 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 (I). These mixtures are material mixtures used as is for the production of the luminescent 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 of the luminescent layer and have a constant mixing ratio during vapor deposition. In this way, vapor deposition of a layer with uniformly distributed components can be achieved in a simple and rapid manner without precisely driving multiple material sources.

[0148] 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 (I), the mixture also contains the phosphorescent emitter as described above. Where the mixing ratio is suitable in vapor deposition, this mixture can also be used as the sole material source.

[0149] Preferred is a premixed system consisting of two matrix materials, namely a compound of formula (I), especially a compound of formula (Ia), and a compound of one of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), or (HH-6).

[0150] Premixed systems consisting of three matrix materials are also preferred, namely a compound of formula (I), especially a compound of formula (Ia), and a compound of one of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), or (HH-6).

[0151] Therefore, the components or elements of the light-emitting layer of the device of the present invention can be obtained by vapor deposition or by processing from solution. For this purpose, the combination of materials 1 and 2, as described above or as preferred, is provided in a formulation containing at least one solvent, optionally together with a phosphorescent emitter as described above or as preferred. Suitable formulations have been described above.

[0152] Based on the overall composition of the luminescent material and the matrix material, according to the preferred embodiment, the luminescent layer in the device of the present invention contains preferably 99.9 vol% to 1 vol%, more preferably 99 vol% to 10 vol%, particularly preferably 98 vol% to 60 vol%, and very particularly preferably 97 vol% to 80 vol% of a matrix material. According to the preferred embodiment, the matrix material is composed of at least one compound of formula (I), preferably a compound of formula (Ia), and at least one compound of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), or (HH-6). Therefore, based on the overall composition of the luminescent layer composed of the luminescent material and the matrix material, the luminescent layer in the device of the present invention preferably contains 0.1 vol% to 99 vol%, more preferably 1 vol% to 90 vol%, more preferably 2 vol% to 40 vol%, and most preferably 3 vol% to 20 vol% of the luminescent material. If the compound is processed from a solution, it is preferable to use the corresponding weight % rather than the volume % specified above.

[0153] The present invention also relates to an organic electroluminescent device as described above or as preferred, wherein the organic layer comprises a hole injection layer (HIL) and / or a hole transport layer (HTL) belonging to the arylamine class, wherein the hole injection material and the hole transport material therein are hole transport materials.

[0154] The preferred order of the layers in the organic electroluminescent device of the present invention is as follows: Anode / hole injection layer / hole transport layer / light emission layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0155] At the same time, it should be pointed out again that not all of the mentioned layers need to exist and / or other layers may also exist.

[0156] Besides the compounds of formula (I) of this invention, the material used for the electron transport layer can be any material used as an electron transport material in an electron transport layer according to the prior art. 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.

[0157] A suitable cathode for the device of the present invention is a metal with low work function, a metal alloy or multilayer structure composed of various metals such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g., Ca, Ba, Mg, Al, In, Yb, Sm, etc.). Also suitable are alloys composed of alkali metals or alkaline earth metals and silver, such as alloys composed of magnesium and silver. In the case of a multilayer structure, in addition to the metals mentioned, other metals with relatively high work functions, such as Ag or Al, can be used. In this case, combinations of metals such as Ca / Ag, Mg / Ag, or Ba / Ag are commonly 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 the corresponding oxides or carbonates (e.g., LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.). For this purpose, lithium quinoline (LiQ) can also be used. The thickness of this layer is preferably 0.5 nm to 5 nm.

[0158] The preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, metals with high redox potentials are suitable for this purpose, such as Ag, Pt, or Au. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are preferred. x Al / PtO x Alternatively, an anode may be preferred. For some applications, at least one electrode must be transparent or partially transparent to allow illumination of organic materials (organic solar cells) or coupled light output (OLEDs, O-lasers). The preferred anode material here is a conductive mixed metal oxide. Indium tin oxide (ITO) or zinc indium oxide (IZO) is particularly preferred. Conductive doped organic materials, especially conductive doped polymers, are also preferred. Furthermore, the anode may also consist of two or more layers, for example, an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide, or vanadium oxide.

[0159] Since the lifespan of the devices of the present invention is shortened in the presence of water and / or air, the organic electroluminescent devices of the present invention are appropriately structured, contact-connected and finally sealed during the manufacturing process (depending on the application).

[0160] The manufacture of the device of the present invention is not limited herein. One or more organic layers, including the light-emitting layer, can be coated by a sublimation method. In this case, the material is sublimated in a vacuum sublimation system at less than 10 -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 be even lower, for example, below 10. -7 millibar.

[0161] The organic electroluminescent device of the present invention is preferably characterized in that one or more layers are coated by an OVPD (organic vapor deposition) method or by means of carrier gas sublimation. In this case, at 10 -5 The material is applied at a pressure 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 a nozzle and thus structured (e.g., MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0162] The organic electroluminescent device of the present invention is further preferably characterized by producing 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 (photoinitiated 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 a solution is, for example, that the luminescent layer can be applied in a very simple and inexpensive manner. This technique is particularly suitable for the large-scale production of organic electroluminescent devices.

[0163] Furthermore, a hybrid approach is feasible, in which one or more layers are applied from a solution and one or more other layers are applied by vapor deposition.

[0164] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

[0165] Therefore, the present invention also provides a method for producing the organic electroluminescent device of the present invention as described above or as preferably the present invention, characterized in that an organic layer, preferably a light-emitting layer, a hole injection layer and / or a hole transport layer, is applied by vapor deposition, especially by sublimation and / or by OVPD (organic vapor deposition) and / or by means of a carrier gas, or from a solution, especially by spin coating or by printing.

[0166] In the case of production using vapor deposition, there are, in principle, two ways to apply or vapor-deposit the organic layer, preferably the luminescent layer, of the present invention onto any substrate or prior layer. First, the materials used can be initially loaded into material sources and ultimately evaporated from different material sources (“co-evaporation”). Second, the various materials can be premixed (premixed system), and the mixture can be initially loaded into a single material source and ultimately evaporated from said 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 precisely driving multiple material sources.

[0167] The following methods are feasible: A method for producing the organic electroluminescent device of the present invention as described above or as preferred thereof, 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.

[0168] A method for producing an organic electroluminescent device of the present invention as described above or as preferred thereof, characterized in that an organic light-emitting layer is applied by vapor deposition, wherein at least one compound of formula (I), especially a compound of formula (Ia), is sequentially or simultaneously vapor-deposited from at least two material sources together with other materials forming the light-emitting layer.

[0169] A method for producing the device of the present invention is characterized in that an organic light-emitting layer is applied by vapor deposition, wherein at least one compound of formula (I), especially a compound of formula (Ia), together with at least one other matrix material as a premix, is sequentially or simultaneously deposited from the vapor phase with a light-emitting material selected from phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0170] The electronic devices of the present invention, particularly organic electroluminescent devices, have one or more of the following surprising advantages compared with the prior art: 1. Compounds comprising formula (I) or preferred embodiments described above and below, especially electronic devices, particularly organic electroluminescent devices, as matrix materials or electronically conductive materials, exhibit very good lifetimes. In this case, these compounds particularly induce low roll-off, i.e., a small decrease in device power efficiency at high brightness.

[0171] 2. Compounds comprising formula (I) or preferred embodiments described above and below, as electronic conductive materials and / or matrix materials, particularly organic electroluminescent devices, exhibit excellent efficiency. In this case, the compounds of formula (I) or preferred embodiments of the present invention described above and below cause low operating voltages when used in electronic devices.

[0172] 3. The compounds of formula (I) or preferred embodiments of the present invention described above and below exhibit very high stability and lifetime.

[0173] 4. By utilizing the compounds of formula (I) or preferred embodiments described above and below, optical loss channels can be avoided in electronic devices, especially organic electroluminescent devices. Therefore, these devices exhibit the following characteristics: high PL efficiency, resulting in high EL efficiency, and excellent energy transfer from the matrix to the dopant.

[0174] 5. The use of compounds of formula (I) or preferred embodiments described above and below in the layers of electronic devices, especially organic electroluminescent devices, results in high mobility of the electronic conductor structure.

[0175] 6. The compounds of formula (I) or preferred embodiments described above and below have excellent glass film formation.

[0176] 7. The compounds of formula (I) or preferred embodiments described above and below form very good films from solution.

[0177] 8. The compounds of formula (I) or preferred embodiments described above and below have a low triplet energy level T1, for example, in the range of 2.50 eV to 2.90 eV.

[0178] These advantages were not accompanied by an unusually severe deterioration in other electronic properties.

[0179] The present invention further provides the use of compounds of formula (I), particularly compounds of formula (Ia), or mixtures or formulations of the present invention in organic electroluminescent devices.

[0180] It should be noted that variations of the embodiments described in this invention are covered by the scope of this invention. Unless expressly excluded, any feature disclosed in this invention may be exchanged for alternative features of the same or equivalent or similar purpose. Therefore, unless otherwise stated, any feature disclosed in this invention should be considered an example of a general series or an equivalent or similar feature.

[0181] Unless specific features and / or steps are mutually exclusive, all features of the invention can be combined with each other in any way. This is especially true for preferred features of the invention. Similarly, features that are not necessarily combined can be used individually (rather than in combination).

[0182] The technical teachings disclosed in this invention can be refined and combined with other embodiments.

[0183] The invention is illustrated in more detail by way of the following embodiments, but is not intended to limit the invention thereto.

[0184] Example

[0185] General method: In all quantum chemical calculations, the Gaussian16 (Rev. B.01) software package was used. The neutral singlet ground state was optimized at the B3LYP / 6-31G(d) level. HOMO and LUMO values ​​were determined for the B3LYP / 6-31G(d) optimized ground state energy at the B3LYP / 6-31G(d) level. Then, TD-DFT singlet and triplet excitations (vertical excitations) were calculated using the same method (B3LYP / 6-31G(d)) and with the optimized ground state geometry. Standard settings for SCF and gradient convergence were used.

[0186] Based on energy calculations, the HOMO is obtained as the last orbital occupied by two electrons (α-occupancy eigenvalue), and the LUMO is obtained as the first unoccupied orbital (α-virtual orbital eigenvalue), in Hartley units, where HEh and LEh represent the HOMO energy and LUMO energy in Hartley units, respectively. This is used to determine the HOMO and LUMO values ​​of an electron voltmeter calibrated by cyclic voltammetry as follows:

[0187] The triplet energy level T1 of a material is defined as the relative excitation energy (in eV) of the lowest-energy triplet state discovered through quantum chemical energy calculations.

[0188] The singlet energy level S1 of a material is defined as the relative excitation energy (in eV) of the second lowest singlet state discovered through quantum chemical energy calculations.

[0189] The singlet state with the lowest energy is called S0.

[0190] The method described herein is independent of the software package used and always yields the same results. Examples of commonly used programs for this purpose are "Gaussian09" (Gaussian Corporation) and Q-Chem 4.1 (Q-Chem Corporation). In the case of this application, the energy is calculated using the software package "Gaussian16 (Rev. B.01)".

[0191] Synthesis example : Unless otherwise specified, the following synthesis was carried out in anhydrous solvents under a protective gas atmosphere. Solvents and reagents are available from, for example, Sigma-Aldrich or ABCR. For compounds known in the literature, the corresponding CAS number is also reported in each case.

[0192] a) 3-bromo-5-chloro-[1,1'-biphenyl]-2-formonitrile:

[0193] Under an inert atmosphere, an initial feed was prepared from 58.5 g (200 mmol) of 2,6-dibromo-4-chlorobenzonitrile, 12.2 g (100 mmol) of phenylboronic acid, and 21.2 g (200 mmol) of sodium carbonate in toluene (700 ml) and water (150 ml). Tetra(triphenylphosphine)palladium(0) (2.32 g, 2.00 mmol) was then added, and the reaction mixture was stirred under reflux for 16 hours. After cooling, the reaction mixture was filtered through a filter plate packed with toluene and diatomaceous earth, and then post-treated by extraction with toluene and water. The organic phase was washed with water (200 ml) and saturated NaCl solution (100 ml) and dried over Na₂SO₄, and the solvent was evaporated on a rotary evaporator. The crude product was further purified by column chromatography. Yield: 34 g (120 mmol, 60%), according to 1 97% purity according to H NMR.

[0194] The following compounds can be prepared similarly: purified by column chromatography or recrystallized using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dimethylolpropane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0195]

[0196] b) 3-{[1,1'-biphenyl]-4-yl}-5-chloro-[1,1'-biphenyl]-2-formonitrile:

[0197] Under an inert atmosphere, an initial feed was prepared from 29 g (100 mmol) of 3-bromo-5-chloro-[1,1'-biphenyl]-2-carboxynitrile, 19.8 g (100 mmol) of 4-biphenylboronic acid, and 21.2 g (200 mmol) of sodium carbonate in toluene (700 ml) and water (150 ml). Tetra(triphenylphosphine)palladium(0) (2.32 g, 2.00 mmol) was then added, and the reaction mixture was stirred under reflux for 16 hours. After cooling, the reaction mixture was filtered through a filter plate packed with toluene and diatomaceous earth, and then post-treated by extraction with toluene and water. The organic phase was washed with water (200 ml) and saturated NaCl solution (100 ml) and dried over Na2SO4, with the solvent evaporated on a rotary evaporator. The crude product was further purified by column chromatography. Yield: 31 g (86 mmol, 87%), according to 1 99% purity according to H NMR.

[0198] The following compounds can be prepared similarly: purified by column chromatography or recrystallized using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dimethylolpropane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0199]

[0200] c) 3-{[1,1'-biphenyl]-4-yl}-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentane-2-yl)-[1,1'-biphenyl]-2-formonitrile:

[0201] In a four-necked flask, 27 g (74.0 mmol, 1.00 equivalent) of 3-{[1,1'-biphenyl]-4-yl}-5-chloro-[1,1'-biphenyl]-2-carboxynitrile was dissolved in 800 ml of dithionane with 22 g (87 mmol, 1.20 equivalent) of bis(pinacolyl)diborane and 21.4 g (219 mmol, 3.00 equivalent) of potassium acetate, and the mixture was inert with argon. Subsequently, 1.79 g (2.19 mmol, 0.03 equivalent) of the 1,1-bis(diphenylphosphine)ferrocene-dichloropalladium(II) complex [95464-05-4] was added, and the reaction mixture was stirred overnight at a bath temperature of 115 °C. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporator. The residue was treated with 250 mL of dichloromethane and extracted with 250 mL of water by shaking. The aqueous phase was extracted three times with 250 mL of dichloromethane, and the combined organic phases were dried over sodium sulfate and the solvent was removed on a rotary evaporator. The resulting solid was washed with ethanol at 60 °C. After drying, 24.6 g (54.0 mmol, 73%) of the desired product was given.

[0202] The following compounds can be prepared similarly: Alternatively, the catalyst system used can be Pd(PCy3)2Cl2, or Pd2(dba)3 and S-Phos (1:3). Purification can be achieved by column chromatography, thermal extraction, or recrystallization or thermal extraction using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, or 1,4-dimethylolpropane. Alternatively, recrystallization can be performed using high-boiling reagents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone.

[0203]

[0204] d) 4-(5-{[1,1'-biphenyl]-4-yl}-6-cyano-[1,1'-biphenyl]-3-yl)-dibenzofuran-6-formonitrile:

[0205] An initial feed consisting of 45 g (100 mmol) of 3-{[1,1'-biphenyl]-4-yl}-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborphane-2-yl)-[1,1'-biphenyl]-2-formonitrile, 27 g (100 mmol) of 4-bromo-1-dibenzofuran carboxynitrile, and K3PO4 (63.79 g, 300 mmol) in THF (1200 ml) and water (300 ml) was inert with argon for 30 min. Subsequently, Pd(OAc)2 (448 mg, 2.00 mmol) and X-Phos (1.99 g, 4.00 mmol) were added sequentially, and the mixture was stirred under reflux for 16 h. After cooling, the precipitated solids were filtered off and washed with water and ethanol. The crude product was subjected to four alkaline thermal extractions with o-xylene on alumina, and finally sublimated under high vacuum.

[0206] Yield: 35 g (68 mmol, 70%), Purity: >99.9% according to HPLC.

[0207] The following compounds can be prepared similarly using X-Phos or S-Phos catalyst systems and Pd(OAc)2 or Pd2(dba)3 or Pd(PPh3)2Cl2 or Pd(PPh3)4. The solvent used can be not only o-xylene, but especially toluene. Purification can be performed using column chromatography, thermal extraction, or recrystallization. Recrystallization or thermal extraction can be performed using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, and 1,4-dimethylolpropane, or recrystallization can be performed using high-boiling reagents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0208]

[0209] OLED manufacturing

[0210] Data for various OLEDs are presented in the following embodiments V1 to V13 and B1 to B30 (see Tables 7 and 8).

[0211] Pretreatment of Examples V1 to V13 and B1 to B30: To improve processing, a structured ITO (indium tin oxide) glass plate with a thickness of 50 nm was coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid), purchased as CLEVIOS™ PVP AI4083 from Heraeus Precious Metals GmbH, Germany, by spin coating from an aqueous solution). These coated glass plates formed the substrate for applying the OLED.

[0212] OLEDs essentially have the following layer structure: substrate / optional hole injection layer (HIL) / hole transport layer (HTL) / optional electron blocking layer (EBL) / emitting layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally, a cathode. The cathode is formed from a 100 nm thick aluminum layer. The exact structure of an OLED can be seen in Table 7. The materials required to manufacture an OLED are shown in Table 8.

[0213] All materials are applied in a vacuum chamber via thermal vapor deposition. In this case, the luminescent layer always consists of at least one matrix material (host material) and a luminescent dopant (emitter), which is added to one or more matrix materials by co-evaporation in a specific volume ratio. Details given in the form of IC1:IC3:TEG1 (55%:35%:10%) indicate that material IC1 is present in the layer at a volume ratio of 55%, IC3 at 35%, and TEG1 at 10%. Similarly, the electron transport layer can also consist of a mixture of the two materials.

[0214] OLEDs were characterized in a standard manner. For this purpose, electroluminescence spectra were measured, and current efficiency (measured in cd / A) and external quantum efficiency (EQE, measured as a percentage) were calculated from the current-voltage-luminance characteristics (IUL characteristics) under the assumption of Lambertian luminescence properties, and lifetime was determined. Electroluminescence spectra were measured at a luminance of 1000 cd / m², and these were used to calculate the CIE 1931 x and y color coordinates. The parameter U1000 in Table 8 refers to the voltage required to achieve a luminance of 1000 cd / m². SE1000 and LE1000 refer to the current efficiency and power efficiency achieved at 1000 cd / m², respectively. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd / m². Lifetime LD is defined as the time it takes for the luminance to decrease from the initial luminance to a specific proportion L1 during operation at a constant current. The figures L0;j0=4000 cd / m² and L1=70% in Table 8 refer to the lifetime reported in the LD column corresponding to the time after the initial luminance decreased from 4000 cd / m² to 2800 cd / m². Similarly, L0;j0=20 mA / cm² and L1=80% refer to the time after which the luminance decreased to 80% of its initial value during operation at 20 mA / cm².

[0215] Data for various OLEDs are summarized in Table 8. The embodiments are comparative examples based on the prior art; embodiments B1-B30 illustrate data for the OLEDs of the present invention.

[0216] The following detailed description of some embodiments illustrates the advantages of the OLED of the present invention.

[0217] Use of the compounds or mixtures of the present invention in OLEDs

[0218] The mixtures or compounds of the present invention can be used in the emissive layer or electron transport layer of phosphorescent green OLEDs, as shown in Examples B1 to B26 or B27 and B30. Examples V1 to V10 and V11 to V13 are corresponding comparative examples.

[0219] Surprisingly, it was found that when both ortho- and posterior positions of the cyano group in the benzonitrile unit of the compound of formula (I) are substituted with aromatic or heteroaromatic ring systems, the interaction of this cyano group, which has the highest LUMO density, with other molecules is prevented, resulting in improved color purity and increased stability of the cyano group, thus leading to a longer lifespan. Only with the presence of a second cyano group can the LUMO (lowest unoccupied molecular orbital) of the corresponding compound be in the range of -2.58 eV to -2.9 eV, which is particularly important for electron transport in the electron transport layer and the luminescent layer.

[0220] The OLED used has the following layer structure as described above: substrate / HIL / HTL / EBL / EML / HBL / ETL / EIL / cathode.

[0221] In the following comparative and inventive examples, the following HIL, HTL, EBL, HBL and EIL are used: HIL: SpMA1 : PD1 (95% : 5%) – 20 nm thickness; HTL: SpMA1 – 215 nm thickness; EBL: SpMA2 – 20 nm thickness; HBL: ST2 – 10 nm thickness; and EIL: LiQ – 1 nm thickness.

[0222] The EML and ETL used in the comparative and inventive examples are listed in Table 7 below.

[0223] Table 7:

[0224] Table 8 :

[0225] Table 9 Materials used

Claims

1. A compound of formula (I) wherein the symbols and signs used are as follows: L is a radical of formula (II) Formula (II) wherein the dotted bond represents the bond to the phenyl or CN group; R is identical or different in each case and is H and D; W is (CR 2 )2, Si(R 2 )2, NAr 2 , O, or S; Ar and Ar 1 the same or different and are an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which in each case can be substituted by one or more R 3 groups, wherein the heteroaromatic ring system contains only one heteroatom; L 1 and L 2 are identical or different in each case and are a single bond or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms which may, in each case, be substituted by one or more R 4 groups; Ar 2 and Ar 3 in each case identical or different and are an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms; which can in each case also be substituted by one or more R 5 groups; l is 0, 1 or 2; R 1 in each case identical or different and are H; D; F; Cl; Br; I; -OH; N(Ar 3 )2; N(R 6 )2; NO2; C(=0)R 6 ; P(=0)(Ar 3 )2; P(Ar 3 )2; B(Ar 3 )2; Si(Ar 3 )3; Si(R 6 )3; a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, each of which can be substituted by one or more R 6 groups, where one or more non-adjacent CH2 groups can be replaced by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=0, C=S, C=NR 6 , -C(=0)0-, -C(=0)NR 6 -, NR 6 , P(=0)(R 6 ), -0-, -S-, SO or S02, and where one or more hydrogen atoms can be replaced by D, F, Cl, Br, I or NO2; or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms which can in each case be substituted by one or more R 6 groups; or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms which can be substituted by one or more R 6 groups; or an aralkyl group which has 5 to 40 aromatic ring atoms which can be substituted by one or more R 6 groups; or a combination of these systems; where two or more adjacent substituents R 1 may optionally form a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more R 6 groups. R 2 identical or different and are H; D; F; -OH; NO2; C(=O)R 6 ; P(=O)(Ar 3 )2; P(Ar 3 )2; B(Ar 3 )2; Si(Ar 3 )3; a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, each of which can be substituted by one or more R 7 groups, where one or more non-adjacent CH2groups can be replaced by -NR 7 -, -C=CR 3 -, -C≡C-, Si(R 7 )2, C=O, C=S, C=NR 7 , -C(=O)O-, -C(=O)NR 7 -, NR 7 , P(=O)(R 7 ), -O-, -S-, SO or SO2, and where one or more hydrogen atoms can be replaced by D, F, Cl, Br, I or NO2; or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms which can in each case be substituted by one or more R 7 groups; or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms which can be substituted by one or more R 7 groups; or an aralkyl group with 5 to 60 aromatic ring atoms which can in each case be substituted by one or more R 7 groups; or combinations of these systems; where two substituents R 2 may optionally form a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more R 7 groups. R 3 , R 4 , R 5 , R 6 and R 7 are identical or different in each case and are H; D; F; -OH; a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more hydrogen atoms in these alkyl groups can be replaced by D or F; or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms can be replaced by D or F; wherein two or more adjacent substituents R 3 , two or more adjacent substituents R 4 , two or more adjacent substituents R 5 , two or more adjacent substituents R 6 or two or more adjacent substituents R 7 may optionally form a mono- or polycyclic aliphatic or aromatic ring system, m is 0, 1, 2, 3 or 4; o is 0 or 1, 2. The compound according to claim 1, which is selected from the compounds of formula (la) wherein the symbols and signs have the definitions given in claim 1. wherein, L is -CH2- when o = 0 1 is an aromatic ring system having 6 to 12 aromatic ring atoms, and Ar 3 is a single bond, and wherein at least one R 4 does not represent H, and wherein no two or more adjacent substituents R 4 form a ring system.

3. The compound according to claim 1 or 2, wherein o = 1. wherein p is 0, 1, 2, 3 or 4, 4. The compound according to one or more of the preceding claims, wherein L 1 and L 2 are identical or different and are a single bond or an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms which can in each case be substituted by one or more R 4 radicals.

5. The compound according to one or more of the preceding claims, wherein W = NAr 2 , O, S or (CR 2 )2, and wherein Ar 2 and R 2 have the definitions given in claim 1.

6. The compound according to claim 5, wherein W = O, S or (CR 2 )2, and R 2 are identical or different and are selected from linear alkyl groups having 1-20 carbon atoms, branched alkyl chains having 3 to 10 carbon atoms, wherein one or more hydrogen atoms in these alkyl chains can be replaced by D or F, aromatic ring systems having 5 to 25 ring atoms and which can be substituted by one or more R 7 groups, or two R 2 groups form an aromatic or heteroaromatic ring system of the formula (III) or (IV), and the other symbols and signs have the definitions given in claim 1.

8. A mixture comprising at least one compound according to one or more of claims 1 to 7, and at least one further compound selected from a matrix material, a phosphorescent emitter, a fluorescent emitter and / or an emitter showing TADF (thermally activated delayed fluorescence), and / or a solvent.

9. An organic electronic device comprising an anode, a cathode and at least one organic layer, which organic layer comprises at least one compound according to one or more of claims 1 to 7.

7. The compound according to one or more of claims 1 to 6, wherein Ar and Ar 1 are identical or different and are selected from phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, mesityl, dibenzofuran, dibenzothiophene or carbazole, each of these groups can be substituted by one or more substituents R 3 substituted.

10. The organic electronic device according to claim 9, wherein the device is an organic electroluminescent device.

11. The organic electronic device according to claim 9 or 10, wherein the organic layer comprises at least one light-emitting layer, which light-emitting layer contains a compound according to one or more of claims 1 to 7 as matrix material.

12. The organic electronic device according to claim 11, wherein the light-emitting layer contains at least one further matrix material.

13. The organic electronic device according to claim 12, wherein the at least one further matrix material comprises a compound of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) as further matrix material: Formula (HH-1), Formula (HH-2), wherein the symbols and signs used are as follows: A is in each case independently a radical of formula (HH-4-1) or (HH-4-2), Formula (HH-3), Formula (HH-4), Formula (HH-5), Formula (HH-6), c, c1, c2 are in each case independently of each other 0 or 1, wherein the sum of the indices c + c1 + c2 = 1 in each case; A 1 is C(R 9 )2, NR 9 , O or S; L is a bond, O, S, C(R 9 )2 or NR 9 ; d, d1, d2 are in each case independently of each other 0 or 1, wherein the sum of the indices d + d1 + d2 = 1 in each case; Equation (HH-4-1), Equation (HH-4-2); X2is the same or different at each occurrence and is CH, CR 6 or N, wherein no more than 2 symbols X2may be N; indicates the bonding site to formula (HH-4); U 1 , U 2 In the case of their occurrence is a bond, O, S, C(R 9 )2or NR 9 ; R 8 identical or different in each case and are D; F; CN; a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl groups can in each case be substituted by one or more R 7 groups and in which one or more non-adjacent CH2groups can be replaced by Si(R 9 )2, C=0, NR 9 , O, S or CONR 9 ; or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which can in each case be substituted by one or more R 9 groups; here, two R 6 groups can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar5is identical or different in each case and is independently an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which can be substituted by one or more R 9 groups; n is 0, 1, 2, 3, 4 or 5; and each R1is independently selected from the group consisting of H, F, CI, Br, I, CN, N02, CF3, CH2F, CHF2 R 9 identical or different in each case and are D; F; CI; Br; I; N(R 8 )2; CN; N02; OR 10 ; SR 10 ; Si(R 10 )3; B(OR 10 )2; C(=0)R 10 ; P(=0)(R 10 )2; S(=0)R 10 ; S(=0)2R 10 ; OSO2R 10 ; a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl groups can in each case be substituted by one or more radicals R 10 , where one or more non-adjacent CH2groups can be replaced by Si(R 10 )2, C=0, NR 10 , O, S or CONR 10 ; or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which can in each case be substituted by one or more radicals R 10 ; and two or more radicals R 9 may together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; preferably, the radicals R 9 do not form any such ring system; R 10 in each case identical or different and are H, D, F, or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in particular a hydrocarbyl radical, wherein one or more hydrogen atoms can also be replaced by F; q, q1, q2 are in each case independently 0, 1, 2, 3 or 4; s is identical or different in each case and is 0, 1, 2, 3 or 4; t is identical or different in each case and is 0, 1, 2 or 3; u is identical or different in each case and is 0, 1 or 2; u1, u2 are in each case independently of each other 0 or 1, wherein the sum u1 + u2 = 1; and v is 0, 1, 2 or 3. ​ ​ 14. Organic electronic device according to claim 9 or 10, wherein the organic layer contains at least one electron-transporting or electron-injecting or hole-blocking layer comprising a compound according to any of claims 1 to 7.

15. Organic electronic device according to claim 9, which is an electroluminescent device selected from organic light emitting transistors (OLETs), organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic light emitting diodes (OLEDs).

16. Use of a compound according to one or more of claims 1 to 7 or of a mixture according to claim 8 in an organic electroluminescent device.

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