Materials for organic light emitting devices

Abstract

The present invention relates to OLED materials for use in electronic devices, in particular in organic light emitting devices, and to electronic devices, in particular organic light emitting devices, containing these OLED materials.

Description

[0001] The present application relates to OLED materials for use in electronic devices, in particular for use in organic light emitting devices, and to electronic devices, in particular organic light emitting devices, comprising these OLED materials.

[0002] Electronic devices containing organic semiconductors and / or organometallic semiconductors are used in many commercial products, for example in organic light emitting diodes (OLEDs). In this case, there is an urgent need to improve the performance data, in particular the lifetime, the efficiency and the operating voltage. This is particularly true for blue phosphorescent OLEDs or hyperphosphorescent OLEDs.

[0003] It was an object of the present application to provide compounds suitable for use in electronic devices, in particular in OLEDs, in particular electron blocking materials and / or host materials, wherein they lead to good performance. WO 2010 / 054729 discloses diazasilane derivatives and tetraazasilane derivatives for use as electron blocking materials and / or as matrix materials for green or blue phosphorescent compounds. Although good results have already been achieved with these compounds, further improvements are still desired here, in particular further improvements in efficiency, voltage and / or lifetime.

[0004] Surprisingly, it has been found that this object is achieved by specific asymmetric tetraazasilane derivatives for use in electronic devices, in particular OLEDs, which are described in more detail below. In particular, the OLEDs have an improved lifetime, a higher efficiency and / or a lower operating voltage compared to OLEDs containing symmetric tetraazasilane derivatives. The present application therefore provides these compounds and electronic devices, in particular organic electroluminescent devices, comprising these compounds.

[0005] The present application provides a compound of formula (1)

[0006]

[0007] Formula (1)

[0008] The symbols used are as follows:

[0009] X is identical or different in each case and is CR or N, with the proviso that not more than two X per ring are N;

[0010] Ar 1 , Ar 2 , Ar 3 , Ar 4 in each case identical or different and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and can be substituted by one or more R groups;

[0011] R is the same or different in each case and is H, D, F, Cl, Br, I, OR 1 SR 1 B(OR) 1 )2, CHO, C(=O)R 1 CR 1 =C(R 1 )2, CN, C(=O)OR 1 C(=O)NR 1 ,Si(R 1 )3,Ge(R) 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 OR 1 N(R) 1 )2,S(=O)R 1 S(=O)2R 1 SR 1 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 1 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by -R 1 C=CR 1 -、-C≡C-、Si(R 1 2. CONR 1 ,C=O,C=S,-C(=O)O-,P(=O)(R 1 It can be replaced by -O-, -S-, SO or SO2, or have 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case can be replaced by one or more R 1 Aromatic or heteroaromatic ring systems with substituted R groups; at the same time, two or more R groups together can form a ring system;

[0012] R 1 The same or different in each case and for H, D, F, Cl, Br, I, B (OR) 2 )2, CHO, C(=O)R 2 CR 2 =C(R 2 )2, CN, C(=O)OR 2 ,Si(R 2 )3,Ge(R) 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 SR 2 S(=O)R2 S(=0)2R 2 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 group can in each case be substituted by one or more R 2 groups and where one or more CH2 groups in the above groups can be replaced by -R 2 C=CR 2 -, -C≡C-, Si(R 2 )2, C=0, C=S, -C(=0)0-, CONR 2 , P(=0)(R 2 ), -S-, SO or SO2 and where one or more hydrogen atoms in the above groups can be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which can in each case be substituted by one or more R 2 groups, where two or more R 1 groups together can form a ring system;

[0013] R 2 are identical or different in each case and are H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, where one or more hydrogen atoms can also be replaced by D or F; it is also possible for two or more substituents R 2 to be linked to one another and form a ring;

[0014] characterized in that not all of the groups Ar 1 , Ar 2 , Ar 3 and Ar 4 are identical and / or in that the two rings containing X are different and / or the two rings containing X are substituted differently;

[0015] The present application excludes the following compounds:

[0016] .

[0017] The condition that not all of the groups Ar 1 , Ar 2 , Ar 3 and Ar 4 are identical can also mean that Ar 1 , Ar 2 , Ar 3 and Ar 4 represent the same aromatic or heteroaromatic ring system, but these ring systems are substituted differently.

[0018] An aryl group in the context of the present application contains 6 to 40 carbon atoms; a heteroaryl group in the context of the present application contains 5 to 40 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and / or S. Here, an aryl group or a heteroaryl group means: a simple aromatic ring, i.e. benzene; or a simple heteroaromatic ring such as pyridine, pyrimidine, thiophene, etc.; or a fused (annelated) aryl or heteroaryl group such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatic compounds which are connected to each other by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0019] An aromatic ring system in the context of the present application contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, in the ring system. A heteroaromatic ring system in the context of the present application contains 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and at least one heteroatom in the ring system, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and / or S. In the context of the present application, an aromatic or heteroaromatic ring system shall mean a system which does not necessarily contain only aryl or heteroaryl groups, but in which two or more aryl or heteroaryl groups can also be connected by non-aromatic units, preferably less than 10% of the non-H atoms, such as carbon, nitrogen or oxygen atoms, or carbonyl groups. These shall also mean systems in which two or more aryl or heteroaryl groups are connected directly to each other, such as biphenyl, terphenyl, bipyridine or phenylpyridine. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-dialkylfluorene, triarylamine, diaryl ether, stilbene, etc. shall also be regarded as aromatic ring systems in the context of the present application, as are systems in which two or more aryl groups are connected, for example, by straight-chain or cyclic alkyl groups or by silyl groups. Preferred aromatic or heteroaromatic ring systems are: simple aryl or heteroaryl groups; and groups in which two or more aryl or heteroaryl groups are connected directly to each other, such as biphenyl, terphenyl, quaterphenyl or bipyridine, and also fluorene or spirobifluorene.

[0020] An electron-rich heteroaromatic ring system is characterized in that it is a heteroaromatic ring system which does not contain an electron-deficient heteroaryl group. An electron-deficient heteroaryl group is a six-membered heteroaryl group having at least one nitrogen atom; or a five-membered heteroaryl group having at least two heteroatoms, one of which is a nitrogen atom and the other of which is an oxygen, sulfur or substituted nitrogen atom, wherein in each case further aryl or heteroaryl groups can also be fused to these groups. In contrast, an electron-rich heteroaryl group is a five-membered heteroaryl group having exactly one heteroatom selected from oxygen, sulfur or substituted nitrogen, to which further aryl groups and / or further electron-rich five-membered heteroaryl groups can be fused. As a result, examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene or indeno-carbazole. An electron-rich heteroaryl group is also referred to as an electron-rich heteroaromatic group.

[0021] An electron-deficient heteroaromatic ring system is characterized in that it contains at least one electron-deficient heteroaryl group, particularly preferably no electron-rich heteroaryl groups.

[0022] In the context of the present application, the term "alkyl group" is used as a collective term for straight-chain and branched alkyl groups and also cyclic alkyl groups. Similarly, the terms "alkenyl group" and "alkynyl group" are used as a collective term for straight-chain or branched alkenyl or alkynyl groups and also cyclic alkenyl or alkynyl groups. In the context of the present application, cyclic alkyl, alkoxy or thioalkoxy groups mean monocyclic, bicyclic or polycyclic groups.

[0023] In the context of the present application, aliphatic hydrocarbon-based radicals or alkyl radicals or alkenyl or alkynyl radicals which can contain from 1 to 40 carbon atoms and in which individual hydrogen atoms or CH2groups can also be replaced by the above-mentioned radicals are preferably intended to mean the following radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1 -methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1 -methylcyclohexyl, n-octyl, cyclooctyl, 2-ethylhexyl, 1 -bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1 -dimethyl-n-hex-1 -yl, 1,1 -dimethyl-n-hept-1 -yl, 1,1 -dimethyl-n-oct-1 -yl, 1,1 -dimethyl-n-dec-1 -yl, 1,1 -dimethyl-n-dodec-1 -yl, 1,1 -dimethyl-n-tetradec-1 -yl, 1,1 -dimethyl-n-hexadec-1 -yl, 1,1 -dimethyl-n-octadec-1 -yl, 1,1 -diethyl-n-hex-1 -yl, 1,1 -diethyl-n-hept-1 -yl, 1,1 -diethyl-n-oct-1 -yl, 1,1 -diethyl-n-dec-1 -yl, 1,1 -diethyl-n-dodec-1 -yl, 1,1 -diethyl-n-tetradec-1 -yl, 1,1 -diethyl-n-hexadec-1 -yl, 1,1 -diethyl-n-octadec-1 -yl, 1 -(n-propyl)-cyclohex-1 -yl, 1 -(n-butyl)-cyclohex-1 -yl, 1 -(n-hexyl)-cyclohex-1 -yl, 1 -(n-octyl)-cyclohex-1 -yl and 1 -(n-decyl)-cyclohex-1 -yl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, cyclooctadienyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. Alkoxy radicals OR 1 Preferably mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. Thioalkyl radicals SR 1In particular, it refers to thiols, ethylthiols, n-propylthiols, isopropylthiols, n-butylthiols, isobutylthiols, sec-butylthiols, tert-butylthiols, n-pentylthiols, sec-pentylthiols, n-hexylthiols, cyclohexylthiols, n-heptylthiols, cycloheptylthiols, n-octylthiols, cyclooctylthiols, 2-ethylhexylthiols, trifluoromethylthiols, pentafluoroethylthiols, 2,2,2-trifluoroethylthiols, ethylenethiols, propylenethiols, butenethiols, pentenethiols, cyclopentenethiols, hexenethiols, cyclohexenethiols, heptenthiols, cycloheptenethiols, octenethiols, cyclooctenethiols, ethynylthiols, propynylthiols, butynylthiols, pentynylthiols, hexynylthiols, heptenylthiols, or octynylthiols. Typically, the alkyl, alkoxy, or thioalkyl groups according to the present invention can be straight-chain, branched, or cyclic, wherein one or more non-adjacent CH2 groups can be replaced by the aforementioned groups; furthermore, one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2, preferably by D, F, Cl, or CN, and more preferably by D, F, or CN.

[0024] An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case potentially substituted by the aforementioned groups or hydrocarbon groups, and which can be attached to the aromatic or heteroaromatic system via any desired position, particularly refers to groups derived from or combinations thereof of the following substances: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, pyrene, celestene, perylene, fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, diphenylenexide, terphenyl, terphenylenexide, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indeno[a]fluorene, cis or trans Indocarbazole, cis or trans-indocarbazole, cis or trans monobenzoindofluorene, cis or trans dibenzoindofluorene, trimer indene, isotrimer indene, spirotrimer indene, spiroisotrimer indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenothiazine, pyrazole, indazole, imidazole, benzimidazole, naphthiamidazole, phenanthridine Pyridine-imidazolium, pyrazinibimidazolium, quinoxaline-imidazolium, pyrazine, benzo[a]azole, naphtho[a]azole, anthra[a]azole, phenanthreneibimidazolium, iso[a]azole, 1,2-thiazole, 1,3-thiazole, benzo[a]thiazole, pyridazine, hexaazatribenzide, benzo[a]pyridazine, pyrimidine, benzo[a]pyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenothiazine, fluorescein ring, naphthidine, azacarbazole, benzene Benzoline, phenanthrene, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-diazole, 1,2,4-diazole, 1,2,5-diazole, 1,3,4-diazole, 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. These groups can also be deuterated.

[0025] In the context of this specification, the phrase "two or more groups together can form a ring system" should specifically refer to the condition that two groups are linked together by chemical bonds, provided that two hydrogen atoms are formally eliminated. This is illustrated by the following scheme:

[0026] .

[0027] However, the above wording should also refer to the fact that if one of the two groups is hydrogen, the second group bonds to the site where a hydrogen atom is bonded, thereby forming a ring. This will be illustrated by the following scheme:

[0028] .

[0029] In a preferred embodiment of the invention, all X groups are CR; or two X groups in each of the two rings are N, thereby forming a pyrazine; or two X groups in one of the two rings are N, thereby forming a pyrazine, and all X groups in the other ring are CR. Therefore, compounds of formulas (2), (3), and (4) are preferred, with compound (2) being particularly preferred.

[0030]

[0031] The symbols used have the definitions given above.

[0032] According to the present invention, these structures are asymmetrical. They are characterized in that not all four Ar... 1 Ar 2 Ar 3 and Ar 4 The groups are all the same, and / or characterized by two different rings containing the X group, as in the case of, for example, the compound containing the X group (4). Compounds in which the two rings containing the X group are different also include the case where, for example, as in the case of, all X are CR, but the R groups on the two rings are chosen differently and / or bonded at different positions.

[0033] If the substituents combine with the two benzene rings in the structure of formula (2), the preferred structures are compounds of formulas (2a) to (2f).

[0034]

[0035]

[0036] These structures can also be partially or completely deuterated, and Ar 1 To Ar 4 R has the definitions given above. Here, the structures of (2a), (2b) and (2d) are preferred.

[0037] When Ar 1 To Ar 4Similarly, the substituents R on the two phenylene rings are different and / or bonded at different positions. Examples of such compounds are compounds of formula (2d) or (2e), where one R is H or D and the other R is phenyl; o-phenyl, meta-phenyl, or para-phenyl; N-carbazolyl; 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl, or 4-dibenzofuranyl; or N-benzimidazolylbenzimidazole.

[0038] In a preferred embodiment of the invention, not all four Ar groups 1 Ar 2 Ar 3 and Ar 4 They are all the same. For this purpose, multiple implementation schemes are appropriate:

[0039] (1) Ar 1 =Ar 2 And Ar 3 =Ar 4 But Ar 1 ≠Ar 3

[0040] (2) Ar 1 =Ar 3 And Ar 2 =Ar 4 But Ar 1 ≠Ar 2

[0041] (3) Ar 1 =Ar 2 =Ar 3 And Ar 4 ≠Ar 1

[0042] (4) Ar 1 =Ar 2 And Ar 3 ≠Ar 4 ≠Ar 1

[0043] (5) Ar 1 =Ar 3 And Ar 2 ≠Ar 4 ≠Ar 1

[0044] (6) Ar 1 ≠Ar 2 ≠Ar 3 ≠Ar 4 .

[0045] Here, implementation schemes (1), (2), and (6) are particularly preferred. Different Ar... 1 To Ar 4 The groups can be different aromatic or heteroaromatic ring systems and / or the same aromatic or heteroaromatic ring system, but substituted differently.

[0046] The following describes Ar 1 To Ar 4 A preferred embodiment of the invention. In a preferred embodiment of the invention, Ar 1 To Ar 4 In each case, the same or different, and selected from aromatic or heteroaromatic ring systems having 6 to 30 aromatic ring atoms, more preferably 6 to 24 aromatic ring atoms, and most preferably 6 to 18 aromatic ring atoms, each of which may be substituted with one or more R groups.

[0047] In a preferred embodiment of the invention, Ar 1 To Ar 4 At least one of the groups contains at least 12 aromatic ring atoms. More preferably, Ar 1 To Ar 4 At least two of the groups each contain at least 12 aromatic ring atoms.

[0048] When Ar 1 To Ar 4 When each group contains only 6 aromatic ring atoms, the compound preferably has at least one aromatic or heteroaromatic substituent R containing at least 12 aromatic ring atoms and / or the compound has at least two aromatic or heteroaromatic substituents R.

[0049] Suitable aromatic or hybrid aromatic ring systems Ar 1 To Ar 4 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; fluorene that may be linked at positions 1, 2, 3, or 4; spirodifluorene that may be linked at positions 1, 2, 3, or 4; naphthalene that may be linked at positions 1 or 2; indole; benzofuran; benzothiophene that may be linked at positions 1, 2, 3, or 4; and fluorene that may be linked via positions 1, 2, 3, or 4. Dibenzofuran linked at positions 1, 2, 3, or 4; carbazole linked at positions 1, 2, 3, or 4; dibenzothiophene linked at positions 1, 2, 3, or 4; indobenzocarbazole; indolecarbazole; pyridine; pyrimidine; pyrazine; pyridazine; triazine; quinoline; quinazoline; benzimidazole; benzimidazole-benzimidazole; phenanthrene; triphenylide; or combinations of two or three of these groups, each of which may be substituted with one or more R groups, preferably non-aromatic R groups. When Ar 1When the group is a heteroaryl group, especially a triazine, pyrimidine, quinazoline or carbazole, an aromatic or heteroaryl R group on the heteroaryl group is preferred.

[0050] Preferred Ar 1 To Ar 4 The functional groups may be the same or different in each case and are selected from the functional groups of the following formulas (Ar-1) to (Ar-144).

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[0096] Where R has the definition given above, the dashed bond represents the bond connected to the nitrogen atom in equation (1), and in addition:

[0097] Ar # In each case they may be the same or different and are divalent aromatic or heteroaromatic ring systems having 6 to 18 aromatic ring atoms and in each case they may be substituted by one or more R groups;

[0098] A 1 In each case, they may be the same or different and are BR, C(R)2, C=O, NR, O, or S;

[0099] p is either 0 or 1, where p=0 means Ar # The functional group is absent, and the corresponding aromatic or heteroaromatic functional group is directly bonded to the nitrogen atom;

[0100] r can be 0 or 1, where r=0 means there is no A. 1 The group is bonded at this position, and the R group is bonded to the corresponding carbon atom at that position.

[0101] In a preferred embodiment, Ar 1 To Ar 4 It contains no fused aryl groups. In contrast, fused heteroaryl groups in which there are no six-membered rings directly fused to each other can be suitable, such as carbazole, dibenzofuran, or dibenzothiophene.

[0102] Specially selected Ar 1 To Ar 4 The functional groups may be the same or different in each case and are selected from the following structures: Ar-a to Ar-l.

[0103]

[0104] The dashed bonds represent bonds connected to nitrogen atoms, and these structures can be partially or completely deuterated.

[0105] Ar 1 Ar 2 Ar 3 and Ar 4 Examples of particularly preferred combinations are those listed in the table below:

[0106]

[0107] The preferred substituents R, R are described below. 1 and R 2 In a particularly preferred embodiment of the invention, R, R are referred to below. 1 and R 2The specified preferred options occur simultaneously and apply to the structure of Equation (1) and all preferred implementations.

[0108] with Ar 1 To Ar 4 The preferred substituent R in each case may be the same or different and is selected from H, D, F, CN, Si(R) 1 )3,Ge(R) 1 3, a straight-chain alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group in each case may be one or more R 1 The groups are substituted, but preferably unsubstituted, and one or more non-adjacent CH2 groups can be replaced by O; simultaneously, two adjacent R groups can form a cyclic system with each other. More preferably, with Ar 1 To Ar 4 The R in each case may be the same or different and is selected from H, D, F, CN, Si(R) 1 )3, having 1 to 6 carbon atoms, especially a straight-chain alkyl group having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein in each case the alkyl group may be one or more R 1 The group is substituted, but preferably unsubstituted; simultaneously, two adjacent Rs can form a ring system with each other. Most preferably, it is with Ar. 1 To Ar 4 The R in each case may be the same or different and is selected from H, D, F, CN, Si(C6H5)3, wherein the phenyl group may optionally be deuterated and / or replaced by one or more optionally deuterated methyl groups, or optionally deuterated methyl groups.

[0109] When X=CR, the preferred substituent R that bonds to the carbon atom is the same or different in each case and is selected from H, D, F, CN, OR. 1 N(R) 1 )2,Si(R 1 )3,Ge(R) 1 3, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein in each case the alkyl group may be one or more R 1 The group is substituted, but preferably unsubstituted, or has 6 to 30 aromatic ring atoms and in each case can be substituted by one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups. More preferably, when X=CR, the R bonded to the carbon atom is the same or different in each case and is selected from H, D, F, CN, Si(R) 1)3, having 1 to 6 carbon atoms, especially a straight-chain alkyl group having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein in each case the alkyl group may be one or more R 1 The group is substituted, but preferably unsubstituted, and has 6 to 24 aromatic ring atoms and may optionally be deuterated and in each case be one or more R groups. 1 Groups, preferably non-aromatic R 1 A group-substituted aromatic or heteroaromatic ring system. Most preferably, when X=CR, the R bonded to the carbon atom is the same or different in each case and is selected from H, D, F, CN, Si(C6H5)3, wherein the phenyl group may optionally be deuterated and / or may be substituted by one or more optionally deuterated methyl groups, or an optionally deuterated aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, more preferably having 6 to 18 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may in each case be substituted by one or more R groups. 1 Groups, preferably non-aromatic R 1 Group substitution.

[0110] Suitable aromatic or heteroaromatic ring systems R are 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; fluorene that can be linked at positions 1, 2, 3, or 4; spirodifluorene that can be linked at positions 1, 2, 3, or 4; naphthalene that can be linked at positions 1 or 2; indole; benzofuran; and fluorene that can be linked at positions 1 or 2. Benzothiophene linked at positions 1, 2, 3, or 4; dibenzofuran linked at positions 1, 2, 3, or 4; carbazole linked at positions 1, 2, 3, or 4; dibenzothiophene linked at positions 1, 2, 3, or 4; indobenzocarbazole; indolocarbazole; pyridine; pyrimidine; pyrazine; pyridazine; triazine; quinoline; quinazoline; benzimidazole; phenanthrene; biphenylide; or combinations of two or three of these groups, each of which can be mediated by one or more R 1 Group substitution. When R is a heteroaryl group, especially a triazine, pyrimidine, or quinazoline, it is also preferable to use an aromatic or heteroaromatic R on the heteroaryl group. 1 Group.

[0111] When the R group here is an aromatic or heteroaromatic ring system, it is preferably selected from groups of the following formulas R-1 to R-144.

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[0157] Where R 1 With the definitions given above, a dashed bond represents a bond connected to the stated group, and furthermore:

[0158] Ar # In each case, they may be the same or different, and they have 6 to 18 aromatic ring atoms and in each case can be one or more R 1 Divalent aromatic or heteroaromatic ring systems with substituted groups;

[0159] A 1 Same or different in each case and for BR 1 C(R) 1 2. C=O, NR 1 , O or S;

[0160] p is either 0 or 1, where p=0 means Ar# The functional group is absent, and the corresponding aromatic or heteroaromatic functional group is directly bonded to the corresponding carbon atom;

[0161] r can be 0 or 1, where r=0 means there is no A. 1 The group is bonded at this position, but it is R. 1 The functional group is bonded to the corresponding carbon atom.

[0162] When the aforementioned Ar-1 to Ar-144 groups relating to Ar or R-1 to R-144 groups relating to R have two or more A's 1 When considering functional groups, feasible choices for these functional groups include A. 1 All combinations defined. In this case, the preferred embodiment is: when the group in question is an Ar group, one of the A groups... 1 The group is C(R)2, NR, O or S, and the other A 1 The group is C(R)2, NR, O, or S; or when the group under discussion is an R group, one of the A groups is... 1 The group is C(R) 1 2. NR 1 , O or S, and another A 1 The group is C(R) 1 2. NR 1 、O or S.

[0163] When A 1 For NR or NR 1 When the substituent R or R bonded to the nitrogen atom 1 Preferably, it has 5 to 24 aromatic ring atoms and can also be divided by one or more R 1 Or R 2 Aromatic or heteroaromatic ring systems substituted with a substituent group. In a particularly preferred embodiment, the substituent R or R 1 In each case, they may be the same or different and have 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms, and in each case may also be one or more R 1 Or R 2 Aromatic or heteroaromatic ring systems with substituted groups. Particularly preferred are phenyl, biphenyl, terphenyl, and tetraphenyl rings having the bonding patterns listed above for Ar-1 to Ar-35 or R-1 to R-35, wherein these structures can be substituted with one or more R or R 1 Group substitution is preferred, but unsubstituted groups are preferred.

[0164] When A 1 C(R)2 or C(R) 1 When )2, the substituent R or R that is bonded to the carbon atom 1Preferably, in each case, the same or different, and is a straight-chain alkyl group containing 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or has 5 to 24 aromatic ring atoms and may also be composed of one or more R 1 Or R 2 Aromatic or heteroaromatic ring systems substituted with groups. More preferably, R or R 1 It is a methyl group or a phenyl group. In this case, R or R 1 The groups together can also form a ring system, resulting in a spirocyclic system.

[0165] In one embodiment, the compound of the present invention contains at least one representative that can be respectively R or R in each case. 1 Substituted electron-rich heteroaryl groups or substituents of benzimidazole and benzimidazole Ar 1 To Ar 4 And / or R, and / or when adjacent X=CR, two R groups bonded to X together with the carbon atoms bonded to them form a group that can be R 1 Substituted electron-rich heteroaryl groups. In another embodiment of the compounds of the present invention, the substituent Ar... 1 To Ar 4 R does not represent an electron-rich heteroaryl group or benzimidazole, and when adjacent X=CR, the two R groups bonded to X do not form an electron-rich heteroaryl group together with the carbon atom bonded to them.

[0166] In another preferred embodiment of the invention, R 1 The same or different in each case and selected from H, D, F, CN, Si(R) 2 )3,Ge(R) 2 3, a straight-chain alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group in each case may be one or more R 2 Group substitution, or having 6 to 30 aromatic ring atoms and in each case being substituted with one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 1 The groups together can form an aliphatic ring system. In a particularly preferred embodiment of the invention, R 1 In each case, the same or different and selected from H, D, Si(C6H5)3, wherein the phenyl group may be substituted with one or more methyl groups in each case, having 1 to 6 carbon atoms, especially a straight-chain alkyl group having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl group may be substituted with one or more R2 The group is substituted, but preferably unsubstituted; or has 6 to 24 aromatic ring atoms and in each case can be substituted by one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups.

[0167] In another preferred embodiment of the invention, R 2 In each case, the same or different groups are H, D, CN, F, alkyl groups having 1 to 4 carbon atoms or aryl groups having 6 to 10 carbon atoms, wherein the aryl groups may be substituted with alkyl groups having 1 to 4 carbon atoms, but are preferably not substituted.

[0168] In another preferred embodiment of the invention, all R 1 The groups, if they are aromatic or heteroaromatic ring systems, are selected from R-1 to R-144 groups, except that each of these groups is respectively marked with R 2 Replaced rather than by R 1 replace.

[0169] In a preferred embodiment, the compound is at least 30%, particularly at least 50%, more preferably at least 70%, even more preferably at least 90%, and especially preferably at least 98% deuterated. This means that in such a compound, the corresponding proportion of hydrogen atoms present in the undeuterated compound has been exchanged for D. The undeuterated compound is the corresponding compound containing hydrogen in a naturally occurring isotopic distribution. In the fully deuterated compound, all H atoms have been exchanged for D.

[0170] In another embodiment of the invention, the compounds of the invention are undeuterated, i.e., they contain hydrogen in a naturally occurring isotopic distribution.

[0171] Meanwhile, in the compounds of the present invention processed by vacuum evaporation, the alkyl group preferably has no more than five carbon atoms, more preferably no more than four carbon atoms, and most preferably no more than one carbon atom.

[0172] The compounds of the present invention can be used in the form of a racemic mixture or a pure enantiomer. For example, when Ar in the compounds of the present invention 1 Ar 2 Ar 3 and Ar 4 When all the functional groups are different, enantiomers can be formed.

[0173] The above-described preferred embodiments can be combined with each other as needed within the limitations defined in claim 1. In a particularly preferred embodiment of the invention, the above-described preferences occur simultaneously.

[0174] Examples of preferred compounds according to the embodiments detailed above are the compounds detailed in the table below. In this case, the deuterated compound may be a fully deuterated compound or a partially deuterated compound, or it may be a mixture of compounds deuterated at different positions and / or with different degrees of deuteration.

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198] The compound (5) of the present invention can be synthesized by a method including that according to Scheme 1. Starting from a 1,2-diamino-substituted aromatic compound or heteroaromatic compound (1), a 1,2-bis(aryl / heteroarylamino) aromatic compound or heteroaromatic compound (2) is obtained by two consecutive mono-N-arylations. Coupling can be carried out by methods known to those skilled in the art, for example, in the presence of a base (e.g., alkyllithium such as n-BuLi or n-Hex-Li, alkali metal alkoxide such as NaO-t-Bu or KO-t-Bu, inorganic base such as alkali metal phosphate or carbonate), a palladium source (e.g., Pd2dba3, Pd(OAc)2, etc.), preferably in combination with an electron-rich phosphine (e.g., DPPF, BiNap, P(t-Bu)3, S-Phos, X-Phos, AmPhos, etc.) or a copper source (e.g., Cu, CuCl, CuI, CuOTf, etc.), in combination with an amine (e.g., pyridine, bipyridine, phenanthroline, glycine, DACH, etc.), starting from Ar-Hal, where Hal = Cl, Br, I, in an anhydrous solvent (e.g., toluene, xylene, THF, dialkylene, DMF, DMAC, NMP, DMSO, etc.), in a Buchwald-Hartwig or Ullmann coupling reaction. Furthermore, coupling can proceed in the presence of a base (e.g., alkyllithium such as n-BuLi or n-Hex-Li, alkali metal alkoxides such as NaO-t-Bu or KO-t-Bu, inorganic bases such as alkali metal phosphates or carbonates) in a dipolar aprotic solvent (DMF, DMAC, NMP, DMSO, sulfolane, etc.) via an SN2Ar reaction with Ar-Hal, where Hal = F, Cl. If the Ar to be introduced... 1 and Ar 2 If the functional groups are identical, coupling can be performed in one step using the method described above. In the second step, the secondary diamine (2) is dilithiated in a solvent (e.g., diethyl ether, di-n-butyl ether, methyl tert-butyl ether, tetrahydrofuran (THF), dialkyl, toluene, etc.) using a base (alkyllithium or aryllithium compounds, such as n-BuLi, t-BuLi, PhLi, etc., or aminolithium, such as diisopropylaminolithium (LDA), 2,2',6,6'-tetramethylpiperidinelithium (LiHMP), hexamethyldisilaminolithium (LiHMDS), etc.), and then converted to intermediate (3) using silicon halide, preferably silicon tetrachloride SiCl4. This reaction is carried out selectively at a reactant stoichiometric ratio of (2) to SiCl4 of 1:1, thereby generating intermediate (3) because the reactivity of the latter is greatly reduced relative to the formation of (5) by further reaction. In the third step, intermediate (3) reacts with the dilithiated diamine (4) to generate the product of the present invention (5). If the diamine (2) to be introduced is the same, i.e., the Ar group is the same 1 =Ar 3And Ar 2 =Ar 4 The coupling can be carried out in one step by the above method, wherein the stoichiometric ratio of (2) to SiCl4 is 2:1.

[0199] Option 1:

[0200]

[0201] Therefore, the present invention also provides a method for preparing the compound of the invention, characterized by the following steps:

[0202] (A) Provided by -NHAr 1 and -NHAr 2 A benzene derivative or a corresponding heteroaromatic derivative in which groups are substituted in the ortho position with each other, and optionally provided with -NHAr 3 and -NHAr 4 Benzene derivatives or corresponding heteroaromatic derivatives in which groups are substituted for each other at the ortho position; and

[0203] (B) To react SiHal4, especially SiCl4, with -NHAr 1 Groups and -NHAr 2 A benzene derivative or corresponding heteroaromatic derivative in which groups are substituted at the ortho position with each other, optionally followed by a reaction with -NHAr 3 Groups and -NHAr 4 Reactions of benzene derivatives or corresponding heteroaromatic derivatives in which groups are substituted for each other at the ortho position.

[0204] The present invention also provides an oligomer, polymer, or dendritic macromolecule comprising one or more compounds of formula (1), wherein there are thus bonds connected to the polymer chain in place of one or more R groups.

[0205] For processing 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 are required. These formulations can be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents are preferably used. Suitable solvents are known to those skilled in the art. The manufacture of such solutions is known to those skilled in the art and is described, for example, in WO 2002 / 072714, WO 2003 / 019694, and the documents cited therein.

[0206] Therefore, the present invention also provides a formulation, particularly a solution, dispersion, or emulsion, comprising at least one compound of the present invention and at least one other compound. Other compounds may be, for example, solvents and / or other organic or inorganic compounds also used in electronic devices, such as luminescent compounds and / or matrix materials.

[0207] The compounds of the present invention are suitable for use in electronic devices, particularly organic light-emitting diodes (OLEDs). Depending on the substitution, the compounds can be used in different functions and layers. Therefore, the present invention also provides for the use of the compounds of the present invention in electronic devices.

[0208] The present invention further provides an electronic device comprising at least one compound of the present invention.

[0209] In the context of this invention, an electronic device is a device comprising at least one layer containing at least one organic compound. The assembly may also comprise other layers of inorganic materials or materials entirely composed of inorganic materials.

[0210] The electronic devices are preferably selected from: organic light-emitting devices (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), dye-sensitized organic solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic photodiodes (OPDs), organic field quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic plasma light-emitting devices.

[0211] The device is more preferably an organic light-emitting device (OLED), which includes a cathode, an anode, and at least one light-emitting layer, wherein the at least one layer contains at least one compound of the present invention. In addition to these layers, the organic light-emitting device may further include other layers, such as one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers, and / or organic or inorganic p / n junctions in each case. Introducing an intermediate layer with, for example, exciton blocking functionality between two light-emitting layers is also feasible. However, it should be noted that each of these layers is not necessarily present. The organic light-emitting device may contain one or more light-emitting layers. If multiple light-emitting layers are present, it is preferable that these light-emitting layers collectively have multiple emission peaks between 380 nm and 750 nm, resulting in white emission; in other words, a variety of fluorescent or phosphorescent light-emitting compounds are used in the light-emitting layers. A system with three light-emitting layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. The organic electroluminescent device of the present invention can also be a series OLED, especially a white OLED.

[0212] The compounds of formula (1) are preferably used in organic electroluminescent devices containing one or more phosphorescent emitters, wherein the compounds of the present invention can be used in different layers depending on the exact structure.

[0213] In a preferred embodiment of the invention, the compound of formula (1) is used as a hole transport material. In this case, the compound of the invention is preferably present in a hole transport layer, an exciton blocking layer, or a hole conduction host material.

[0214] In the context of this application, a hole transport layer is a layer with hole transport functionality between the anode and the light-emitting layer. In the context of this application, an exciton blocking layer is a layer directly adjacent to the light-emitting layer on the anode side. In a particular embodiment, this layer is a hole transport layer.

[0215] If the compound of formula (1) is used as a hole transport material in a hole transport layer or an exciton blocking layer, the compound can be used in the layer as a pure material, i.e., in a 100% proportion, or it can be used in combination with one or more other compounds.

[0216] In another preferred embodiment of the invention, the compound of the invention is used as a matrix material in the luminescent layer, wherein the luminescent layer may be phosphorescent, superphosphorescent, or fluorescent.

[0217] The superphosphorescent emissive layer is a layer that typically contains one or more matrix materials, one or more phosphorescent compounds used as sensitizers and whose luminescence is not observed to a significant degree, and one or more phosphorescent emitters responsible for OLED luminescence.

[0218] The term "phosphorescent compound" (= triplet luminescent) generally refers to a compound that emits light through spin-forbidden transitions, such as transitions from an excited triplet state or a state with a higher spin quantum number, such as a quintet state. Preferred phosphorescent compounds are luminescent complexes containing transition metals or lanthanides, especially when they contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, particularly compounds containing iridium, platinum, or copper. In the context of this invention, all luminescent iridium, platinum, or copper complexes are considered phosphorescent compounds. Iridium or platinum complexes are particularly preferred.

[0219] Examples of phosphorescent emitters can be found in the following applications: WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626、WO 2011 / 066898、WO 2011 / 157339、WO 2012 / 007086、WO 2014 / 008982、WO 2014 / 023377、WO 2014 / 094961、WO 2014 / 094960、WO 2015 / 036074、WO 2015 / 104045、WO 2015 / 117718、WO 2016 / 015815、WO 2016 / 124304、WO 2017 / 032439、WO 2018 / 011186、WO 2018 / 041769、WO 2019 / 020538、WO 2018 / 178001, WO 2019 / 115423 and WO 2019 / 158453. Generally, all phosphorescent complexes known to those skilled in the art and in the field of organic electroluminescence for use in phosphorescent OLEDs are suitable, and other phosphorescent complexes can be used by those skilled in the art without inventive effort. Other phosphorescent complexes can be combined with compounds of formula (1) in organic electroluminescent devices without inventive effort. Since the compounds of the present invention can also have high triplet energy depending on the substitution, they can also be used in particular as matrix materials for blue phosphorescent emitters.

[0220] Suitable phosphorescent metal complexes that can be used as sensitizers in phosphorescent OLEDs or superphosphorescent OLEDs are also disclosed, including those from: Sungho Nam et al., Adv. Sci. 2021, 2100586; Eungdo Kin et al., Sci. Adv. 2022, 8, 1641. Other compounds suitable as sensitizers are disclosed in the following documents: EP 3435438 A2, particularly compounds 2 and 3 on page 21; CN 109111487, particularly compounds on pages 76 and 77; US 2020 / 0140471, particularly compounds on pages 166 to 175; KR 2020108705, particularly compounds on pages 8 to 14; US2019 / 0119312, particularly compounds on pages 114 to 121; and US 2020 / 0411775, particularly compounds on pages 123 to 128. Other suitable phosphorescent metal complexes are disclosed in US 2022 / 0115607, US 2022 / 0298193, US2016 / 0072082 and US 2022 / 0271236.

[0221] In this case, the proportion of matrix material in the light-emitting layer is between 50.0 vol% and 99.9 vol% for the fluorescent light-emitting layer, preferably between 80.0 vol% and 99.5 vol%, more preferably between 92.0 vol% and 99.5 vol%, and between 85.0 vol% and 97.0 vol% for the phosphorescent light-emitting layer.

[0222] Accordingly, the proportion of luminescent compounds is between 0.1 vol% and 50.0 vol% for the fluorescent luminescent layer, preferably between 0.5 vol% and 20.0 vol%, more preferably between 0.5 vol% and 8.0 vol%, and between 3.0 vol% and 15.0 vol% for the phosphorescent luminescent layer.

[0223] The luminescent layer may also comprise a system containing multiple matrix materials (a mixed matrix system) and / or multiple luminescent compounds. In this case, typically, the luminescent compound is a smaller proportion of the compound in the system, and the matrix material is a larger proportion of the compound in the system. However, in individual cases, the proportion of a single matrix material in the system may be less than the proportion of a single luminescent compound.

[0224] The compound of formula (1) is preferably used as a component of the mixed matrix system. The mixed matrix system is preferably composed of two or three different matrix materials, more preferably two different matrix materials. One of the two materials is preferably a material with hole transport properties, and the other material is a material with electron transport properties. The compound of formula (1) is preferably a matrix material with hole transport properties. Other mixed matrix components may also perform other functions. The two different matrix materials may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, and most preferably 1:4 to 1:1. The mixed matrix system is preferably used in phosphorescent or superphosphorescent organic electroluminescent devices. Particularly suitable matrix materials that can be combined with the compounds of the present invention as matrix components of the mixed matrix system are described in more detail below.

[0225] Examples of phosphorescent compounds are listed below.

[0226]

[0227]

[0228]

[0229]

[0230] In a preferred embodiment of the invention, the organic electroluminescent device of the present invention contains at least one blue phosphorescent metal complex, particularly at least one blue phosphorescent platinum complex. The at least one blue phosphorescent metal complex preferably has a LUMO of -1.8 eV to -2.2 eV and a HOMO of -5.0 eV to -5.6 eV as defined by quantum mechanical calculations. The lowest triplet energy T1 of the at least one blue phosphorescent metal complex, as defined by quantum mechanical calculations, is preferably >2.55 eV, more preferably >2.65 eV, and most preferably >2.75 eV.

[0231] Energy levels of molecular orbitals (highest occupied molecular orbital HOMO, lowest unoccupied molecular orbital LUMO, lowest triplet T1, lowest excited singlet S1) were determined via quantum mechanical calculations. The Gaussian16 (version B.01) software package was used in all quantum chemical calculations. The neutral singlet ground state was optimized at the B3LYP / 6-31G(d) level. HOMO and LUMO values ​​for the ground state energies optimized for B3LYP / 6-31G(d) were determined at the B3LYP / 6-31G(d) level. TD-DFT singlet and triplet excited states (vertical excitations) were then calculated using the same method (B3LYP / 6-31G(d)) and optimized ground state geometry. Standard settings for SCF and gradient convergence were used. HOMO and LUMO values ​​(in eV) from the quantum chemical calculations were adjusted using the following factors:

[0232] HOMO_corr = 0.90603 × HOMO (in eV) - 0.84836

[0233] LUMO_corr = 0.99687 × LUMO (in eV) - 0.72445

[0234] In the context of this application, these values ​​should be regarded as the HOMO and LUMO energy levels of the material.

[0235] The lowest triplet state T1 is defined as the energy of the triplet state having the lowest energy shown by the quantum chemical calculations. The lowest excited singlet state S1 is defined as the energy of the excited singlet state having the lowest energy shown by the quantum chemical calculations.

[0236] Suitable platinum complexes, appropriate as blue phosphorescent emitters or as sensitizers for superphosphorescent OLEDs, are disclosed in US 2022 / 0140471, US 2020 / 0216481, US 2021 / 0284672, US 2020 / 0271236, US 2022 / 0399517, US 2023 / 0157041, US 2023 / 0147748 and US 2023 / 0065887.

[0237] The most suitable blue phosphorescent metal complexes are compounds of the formula (Pt-1) defined below:

[0238]

[0239] Equation (Pt-1)

[0240] in:

[0241] Y 1 Y 2 Y3 Y 4 Y 5 The same or different in each case and for CR Y Or N group; or Y group 1 -Y 2 and / or Y 3 -Y 4 Or Y 4 -Y 5 It can form fused aryl or heteroaryl rings having 5 to 18 aromatic ring atoms and which can be substituted by one or more R groups;

[0242] E 50 The same or different in each case and for C(R) C0 2. NR N0 , O or S;

[0243] Ar 50 In each case, they may be the same or different and are aromatic or heteroaromatic ring systems having 5 to 40 aromatic ring atoms and in each case, they may also be substituted by one or more R groups;

[0244] Ar 51 Ar 52 Ar 53 The same or different and being fused aryl or heteroaryl rings having 5 to 18 aromatic ring atoms and in each case also being substituted by one or more R groups;

[0245] R Y In each case, the same or different groups are selected from the following: H, D, F, Cl, Br, I, CHO, CN, C(=O)R, P(=O)(R)2, S(=O)R, S(=O)2Ar, N(R)2, NO2, Si(R)3, B(OR)2, OSO2R, straight-chain alkyl, alkoxy, or thioalkyl groups having 1 to 40 carbon atoms, or branched or cyclic alkyl, alkoxy, or thioalkyl groups having 3 to 40 carbon atoms, each of which may be substituted by one or more R groups, wherein one or more non-adjacent CH groups The two groups can be replaced by RC=CR, C≡C, Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, P(=O)(R), SO, SO2, O, S, or CONR in each case, and one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2; an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and being substituted by one or more R groups in each case; and an aryloxy group having 5 to 40 aromatic ring atoms and being substituted by one or more R groups, wherein two R groups are substituted by one or more R groups. YThe groups together can form aliphatic, aromatic, or heteroaromatic ring systems that can be substituted by one or more R' groups;

[0246] R C0 In each case, the same or different groups are selected from: H, D, straight-chain alkyl groups having 1 to 40 carbon atoms and which may be substituted by one or more R groups, aryl or heteroaryl groups having 6 to 18 aromatic ring atoms and which may also be substituted by one or more R groups in each case, wherein two R groups are... C The groups together can form aliphatic, aromatic, or heteroaromatic ring systems substituted with one or more R groups;

[0247] R N0 In each case, the same or different groups are selected from the following: H, D, F, straight-chain alkyl groups having 1 to 40 carbon atoms or branched or cyclic alkyl groups having 3 to 40 carbon atoms, each of which is substituted by one or more R groups, and wherein one or more hydrogen atoms may be replaced by D, F or CN, and aromatic or heteroaromatic ring systems having 5 to 40 aromatic ring atoms and in each case may also be substituted by one or more R groups;

[0248] And R has the same meaning as above.

[0249] Preferably, Ar 50 In each case, they may be the same or different and are aromatic or heteroaromatic ring systems having 5 to 30, more preferably 6 to 24, most preferably 6 to 18 aromatic ring atoms and in each case may also be substituted by one or more R groups.

[0250] Preferably, Ar 51 Ar 52 Ar 53 The same or different fused aryl or heteroaryl rings having 6 aromatic ring atoms and, in each case, being substituted by one or more R groups.

[0251] Preferably, R Y In each case, the same or different and of the form H, D, F, having 1 to 40, preferably 1 to 20, even more preferably 1 to 10 carbon atoms, straight-chain alkyl, alkoxy, or thioalkyl groups, or having 3 to 40, preferably 3 to 20, even more preferably 3 to 10 carbon atoms, branched or cyclic alkyl, alkoxy, or thioalkyl groups, each of which may be substituted by one or more R groups, wherein one or more non-adjacent CH2 groups may be substituted by RC=CR, C≡C, O, or S in each case, and wherein one or more hydrogen atoms may be substituted by D or F, having 5 to 30, more preferably 5 to 18 aromatic ring atoms, and in each case may also be substituted by one or more R groups, an aromatic or heteroaromatic ring system having 5 to 30, more preferably 5 to 18 aromatic ring atoms, and in each case may also be substituted by one or more R groups.

[0252] Preferably, R C0 In each case, the same or different groups are selected from: H, D, straight-chain alkyl groups having 1 to 10, preferably 1 to 6, even more preferably 1 to 3 carbon atoms and which may be substituted by one or more R groups, aryl or heteroaryl groups having 6 to 18, preferably 6 to 12 aromatic ring atoms and which may also be substituted by one or more R groups in each case, wherein two R groups are... C0 The groups together can form an aliphatic, aromatic, or heteroaromatic ring system substituted with one or more R groups.

[0253] Preferably, R N0 In each case, the same or different groups are selected from the following: aromatic or heteroaromatic ring systems having 5 to 40, more preferably 5 to 30, or even more preferably 5 to 18 aromatic ring atoms and in each case being substituted by one or more R groups.

[0254] Examples of particularly suitable blue phosphorescent metal complexes are described below:

[0255]

[0256]

[0257]

[0258]

[0259] Other suitable blue phosphorescent compounds that can be used as sensitizers are listed in the table below:

[0260]

[0261] Preferred matrix materials for phosphorescent compounds that can also be used in combination with the compounds of the present invention are aromatic ketones, aromatic phosphine oxides, or aromatic sulfoxides or sulfones, such as those according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680; triarylamines; carbazole derivatives, such as CBP (N,N-dicarbazolyl biphenyl) or WO2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO2013 / 041176; indolocarbazole derivatives, such as those according to WO 2007 / 063754 or WO 2008 / 056746; indobenzocarbazole derivatives, such as those according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azacarbazole derivatives, such as those according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160; bipolar matrix materials, such as those according to WO 2007 / 137725; silanes, such as those according to WO 2005 / 111172; borazolacine or borate esters, such as those according to WO 2006 / 117052; triazine derivatives, such as those according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO WO 2011 / 060859 or WO 2011 / 060877; zinc complexes, for example according to EP 652273 or WO 2009 / 062578; silylated diazacyclopentane or silylated tetrazacyclopentane derivatives, for example according to WO 2010 / 054729; phosphorus diazacyclopentane derivatives, for example according to WO 2010 / 054730; bridged carbazole derivatives, for example according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080; triphenylide derivatives, for example according to WO 2012 / 048781; lactams, for example according to WO 2011 / 116865 or WO 2011 / 137951; or dibenzofuran derivatives, such as those according to WO 2015 / 169412, WO2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565.The mixture may also contain other phosphorescent emitters with shorter emission wavelengths than the actual emitter as a co-host, or compounds that participate in charge transport but not to a significant extent, such as those described in WO 2010 / 108579.

[0262] Since the compound of formula (1) or the preferred embodiment has hole transport properties, when the compound is used in a mixed matrix system, the compound is preferably used in combination with a compound having electron transport properties.

[0263] Therefore, it is also preferred that the composition of the present invention contains at least one electron transport matrix material in addition to the hole transport matrix material of formula (1).

[0264] Particularly suitable matrix materials that can be advantageously combined with the compounds of the present invention in a mixed matrix system may be selected from compounds of formula (eTMM1), (eTMM2), (eTMM3), (eTMM4) or (eTMM5) as described later.

[0265] Therefore, the present invention also provides a mixture comprising at least one compound of the present invention and at least one compound of formula (eTMM1), (eTMM2), (eTMM3), (eTMM4) and / or (eTMM5).

[0266] Formula (eTMM1)

[0267] Formula (eTMM2)

[0268] Formula (eTMM3)

[0269] Formula (eTMM4)

[0270] Formula (eTMM5),

[0271] The symbols and markings used are as follows:

[0272] L 2 In each case, they may be the same or different and are either single bonds or have 5 to 24 ring atoms and in each case can be one or more R 7 Aromatic or heteroaromatic ring systems with substituted groups;

[0273] R# may be the same or different in each case and is D, F, CN, or has 6 to 24 ring atoms and can be one or more R 6 Aromatic ring systems with substituted groups;

[0274] Y is the same or different in each case and is N or CR. 7 This eliminates the possibility that two Y values ​​side-by-side are both N;

[0275] V 2 For O or S;

[0276] R 6 The same or different in each case and for H, D, F, CN, Si(R) 7 )3,Ge(R) 7 3, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group in each case may be one or more R 7 The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 7 2. C=O, NR 7 O, S or CONR 7 Replacement, or having 5 to 60 ring atoms and in each case being replaceable by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two R groups... 6 The groups together can also form aromatic, heteroaromatic, aliphatic or heteroaliphatic ring systems;

[0277] Ar 5 In each case, they may be the same or different and have 5 to 40 ring atoms and can be one or more R 7 Aromatic or heteroaromatic ring systems with substituted groups;

[0278] R 7 The same or different in each case and for H, D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 )3,Ge(R) 8 )3, B(OR 8 )2,C(=O)R 8 , P(=O)(R 8 )2,S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 8The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Replacement, or having 5 to 40 ring atoms and in each case being replaceable by one or more R atoms. 8 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 7 The groups together can form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems;

[0279] R 8 In each case, the same or different and are H, D, F, or aliphatic, aromatic or heteroaromatic organic groups having 1 to 20 carbon atoms, especially hydrocarbon groups, in which one or more hydrogen atoms may be replaced by F;

[0280] b1 is 0, 1, 2, 3 or 4;

[0281] b2 can be 0, 1, 2, or 3.

[0282] 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 present invention and a mixture thereof comprising at least one compound of the formula (eTMM1), (eTMM2), (eTMM3), (eTMM4) and / or (eTMM5).

[0283] Preferred compounds of formula (eTMM1) are those of formulas (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), and (eTMM1e).

[0284] Formula (eTMM1a)

[0285] Formula (eTMM1b)

[0286] Formula (eTMM1c)

[0287] Formula (eTMM1d)

[0288] Formula (eTMM1e),

[0289] The symbols and notations for these expressions are defined as follows:

[0290] W, W 1 The same or different in each case and for O, S, C(R)W )2 or N-Ar 5 ;

[0291] R W In each case, the same or different, and is a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more hydrogen atoms may be replaced by D, F, or CN; or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and being replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more hydrogen atoms in the alkyl group of the aromatic or heteroaromatic ring system may be replaced by D, F, or CN; simultaneously, two R atoms bonded to the same carbon atom W Groups can also form ring systems together;

[0292] A is the same or different in every case and is CR. 7 Or N, wherein each ring has no more than two A groups that are N and wherein when L 2 When bonded to this position, A becomes C;

[0293] a3 may be the same or different in each case and can be 0, 1, 2, 3 or 4;

[0294] b3 is the same or different in each case and is 0, 1, 2 or 3;

[0295] Ring B Derived from aryl groups having 6 to 20 ring atoms and being substituted by one or more substituents R#;

[0296] Ring C for or ;

[0297] L3 is an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms, wherein the ring system can be composed of one or more R atoms. 7 Group substitution;

[0298] L 2 X, Ar5, R 7 R# has the definitions given above.

[0299] A particularly preferred matrix material for blue phosphorescent OLEDs or superphosphorescent OLEDs is the following formula (eTMM1c) ) compounds,

[0300] Formula (eTMM1c) )

[0301] The symbols and markings used have the definitions given above, and the compounds may be partially or completely deuterated. Particularly preferred Ar... 5 The functional groups may be the same or different in each case and are selected from phenyl, metaphenyl, or N-carbazole groups, each of which may also be converted by one or more R groups. 7 Group substitution. More preferably, with an N-carbazole group or with an Ar group. 5 At least one of the substituents, and particularly preferably exactly one, is a triphenylsilyl group. More preferably, formula (eTMM1c) The compound has an Ar group representing a phenyl group substituted at the meta position by a triphenylsilyl group. 5 Group.

[0302] The preferred compound of formula (eTMM3) is the compound of formula (eTMM3a).

[0303] Formula (eTMM3a)

[0304] The symbols and notations of this formula (eTMM3a) are defined as follows:

[0305] W 1 The same or different in each case and for O, S, C(R) W )2 or N-Ar 5 ;

[0306] #X represents CR or NAR 5 NAR is preferred 5 ;

[0307] R W In each case, the same or different are a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more hydrogen atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and being replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more hydrogen atoms in the alkyl group of the aromatic or heteroaromatic ring system may be replaced by D, F or CN;

[0308] a3 may be the same or different in each case and can be 0, 1, 2, 3 or 4;

[0309] Ring B Derived from aryl groups having 6 to 20 ring atoms and being substituted by one or more substituents R##;

[0310] Ring C for or ;

[0311] Where L 2 Ar 5 R# has the definitions given above.

[0312] In compounds of formula (eTMM1a), W is preferably O or N-Ar. 5 .

[0313] In compounds of formula (eTMM1a), A is preferably the same or different in each case and is CR. 7 , where L 2 When bonded to this position, A becomes C.

[0314] In compounds of formula (eTMM1d) or (eTMM3a), W 1 Preferably O, C(R) W )2 or N-Ar 5 More preferably N-Ar 5 .

[0315] In compounds of formula (eTMM1e), L 3 Preferably, it has 9 to 30 ring atoms and can be converted by one or more R atoms. 7 Heteroaromatic ring systems with substituted groups.

[0316] In a preferred embodiment of the compounds of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4), and (eTMM5), R 7 The same or different in each case and selected from H, D, F, CN, Si(R) 8 3, 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 8 Group substitution, or having 5 to 60 ring atoms, preferably 5 to 40 ring atoms, and in each case being substituted with one or more R groups. 8 Aromatic or heteroaromatic ring systems with substituted groups.

[0317] In a particularly preferred embodiment of the compounds of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4), and (eTMM5), R 7In each case, they may be the same or different and selected from H, D, or have 6 to 30 ring atoms and can be derived from one or more R atoms. 8 Aromatic or heteroaromatic ring systems with substituted groups.

[0318] The preparation of compounds of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4), and (eTMM5) is generally known, and some of these compounds are commercially available.

[0319] Combined formula (eTMM1) compounds are intellectual, examples, and knowledge Publications: WO 2007 / 077810A1, WO 2008 / 056746 A1, WO 2010 / 136109 A1, WO 2011 / 057706 A2, WO 2011 / 160757 A1, WO2012 / 023947 A1, WO 2012 / 048781 A1, WO 2013 / 077352 A1, WO 2013147205 A1, WO 2013 / 083216 A1, WO 2014 / 094963 A1, WO 2014 / 007564 A1, WO 2014 / 015931 A1, WO 2015 / 090504 A2, WO 2015 / 105251 A1, WO 2015 / 169412 A1, WO 2016 / 015810 A1, WO 2016 / 013875 A1, WO 2016 / 010402 A1, WO 2016 / 033167 A1, WO 2017 / 178311 A1, WO 2017 / 076485 A1, WO 2017 / 186760 A1, WO 2018 / 004096 A1, WO 2018 / 016742 A1, WO 2018 / 123783 A1, WO 2018 / 159964 A1, WO 2018 / 174678 A1, WO 2018 / 174679 A1, WO 2018 / 174681 A1, WO 2018 / 174682 A1, WO 2019 / 177407 A1, WO 2019 / 245164 A1, WO 2019 / 240473 A1, WO 2019 / 017730 A1, WO 2019 / 017731 A1, WO 2019 / 017734 A1, WO 2019 / 145316 A1, WO 2019 / 121458 A1, WO 2020 / 130381 A1, WO 2020 / 130509 A1, WO 2020 / 169241 A1, WO 2020 / 141949 A1, WO 2021 / 066623 A1, WO 2021 / 101220 A1, WO 2021 / 037401 A1, WO 2021 / 180614 A1, WO 2021 / 239772 A1, WO 2022 / 015084 A1, WO 2022 / 025714 A1, WO 2022 / 055169 A1, EP 3575296 A1, EP 3591728 A1, US 2014 / 0361254A1, US2014 / 0361268 A1, KR 20210036304 A, KR 20210036857 A, KR 2021147993 A, JP 2011 / 160367 A2 and JP 2017 / 107992 A2.

[0320] Compounds of suitable formula (eTMM2) are known, for example, in the following publications: WO 2015 / 182872A1, WO 2015 / 105316 A1, WO 2017 / 109637 A1, WO 2018 / 060307 A1, WO 2018 / 151479 A2, WO2018 / 088665 A2, WO 2018 / 060218 A1, WO 2018 / 234932 A1, WO 2019 / 058200 A1, WO 2019 / 017730 A1, WO 2019 / 017731 A1, WO 2019 / 066282 A1, WO 2019 / 059577 A1, WO 2020 / 141949 A1, WO 2020 / 067657 A1, WO 2022063744 A1, WO 2022 / 090108 A1, WO 2022 / 207678A1, KR 2019035308 A, KR 2021147993 A, CN 110437241 A, US 2016 / 072078 A1.

[0321] Compounds of the suitable formula (eTMM3) are known, for example, in the following publications: WO 2017 / 160089A1, WO 2019 / 017730 A1, WO 2019 / 017731 A1, WO 2020 / 032424 A1.

[0322] Compounds of the suitable formula (eTMM5) are known, for example, in the following publications: WO 2015 / 093878A1, WO 2016 / 033167 A1, WO 2017 / 183859 A1, WO 2017 / 188655 A1, WO 2018 / 159964 A1.

[0323] For combinations with compounds of the present invention as described above or as preferably described, suitable compounds are in particular those of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), and / or (eTMM2), as described above or as preferably described, or the corresponding compounds covered by these formulas in the table below. Compounds of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), and / or (eTMM1e) are particularly preferred herein.

[0324] As described above, other examples of suitable host materials for formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4), and (eTMM5) that can be combined with the compounds detailed above according to the present invention are the structures shown in Tables A and B below.

[0325] Table A:

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335] As described above, the compounds of the formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM1f) and / or (eTMM2) that are particularly suitable for combination with the compounds detailed above according to the invention and for use in the electroluminescent devices or mixtures of the invention are compounds E1 to E40 in Table B.

[0336] Table B:

[0337]

[0338]

[0339]

[0340]

[0341] The main materials of the present invention mentioned above, as well as the preferred embodiments thereof described herein, together with the matrix materials / main materials mentioned above, matrix materials / main materials of formula (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), and the preferred embodiments thereof described herein or the compounds E1 to E45 from Table 2, may be combined in any desired manner in the device of the present invention.

[0342] If the matrix material is a deuterated compound, then the matrix material can be a mixture of deuterated compounds with the same basic chemical structure but different levels of deuteration.

[0343] In a preferred embodiment of the matrix material, the latter is a deuterated compound of the present invention or a mixture of compounds of the formula (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5) as described above, wherein the deuteration level of these compounds is at least 50% to 90%, preferably 70% to 100%.

[0344] As described above, or preferably in the mixtures of the present invention or in the light-emitting layer of the device of the present invention, the total concentration of all the main materials of the present invention is generally in the range of 5 vol% to 90 vol%, preferably in the range of 10 vol% to 85 vol%, more preferably in the range of 20 vol% to 85 vol%, even more preferably in the range of 30 vol% to 80 vol%, very particularly preferably in the range of 20 vol% to 60 vol%, and most preferably in the range of 30 vol% to 50 vol%.

[0345] The total concentration of all the main materials of the formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4), or (eTMM5) as preferably described above, in the mixture of the present invention, or in the light-emitting layer of the device of the present invention, is generally in the range of 5 vol% to 90 vol%, preferably in the range of 10 vol% to 85 vol%, more preferably in the range of 20 vol% to 85 vol%, even more preferably in the range of 30 vol% to 80 vol%, very particularly preferably in the range of 20 vol% to 60 vol%, and most preferably in the range of 30 vol% to 50 vol%.

[0346] The present invention also relates to a mixture comprising, in addition to the main materials of the present invention mentioned above and at least one main material of formula (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) and (eTMM5) as described above or preferably, at least one phosphorescent emitter.

[0347] Examples of particularly suitable matrix materials for blue phosphorescent metal complexes are described below:

[0348]

[0349]

[0350]

[0351]

[0352] Preferably, at least one phosphor in the composition has a peak emission wavelength between 420 nm and 550 nm, more preferably between 420 nm and 470 nm.

[0353] Preferred fluorescent compounds for use in superphosphorescent OLEDs are selected from arylamines. In the context of this invention, arylamines or aromatic amines refer to compounds comprising three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyreneamines, aromatic pyrene diamines, aromatic pyrimethamines, or aromatic pyrimethamines. An aromatic anthraceneamine is a compound in which one of the diaryl amino groups 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 aromatic pyreneamines, pyrene diamines, pyrimethamines, and pyrimethamines are similarly defined, wherein the diaryl amino groups are preferably bonded to pyrene at the 1-position or at the 1- and 6-positions. Other preferred luminescent compounds are: indofluoreneamine or fluorene diamine, for example according to WO 2006 / 108497 or WO 2006 / 122630; benzo[a]indofluoreneamine or benzo[a]indofluorene diamine, for example according to WO 2008 / 006449; and dibenzo[a]indofluoreneamine or dibenzo[a]indofluorene diamine, for example according to WO 2007 / 140847; and indofluorene derivatives having fused aryl groups disclosed in WO 2010 / 012328. Also preferred are pyrene arylamines disclosed in WO 2012 / 048780 and WO 2013 / 185871. Also preferably are benzo[a]indofluoreneamine disclosed in WO2014 / 037077, benzo[a]fluoreneamine disclosed in WO 2014 / 106522, extended benzo[a]indofluorene disclosed in WO 2014 / 111269 and WO 2017 / 036574, phenazine disclosed in WO 2017 / 028940 and WO 2017 / 028941, and fluorene derivatives bonded to furan or thiophene units disclosed in WO 2016 / 150544. Additionally, methods according to WO 2020 / 208051, WO 2015 / 102118, WO 2016 / 152418, WO 2018 / 095397, WO 2019 / 004248, WO 2019 / 132040, US 2020 / 0161552 and WO may be used. 2021 / 089450, WO 2015 / 102118, KR 2018046851, WO 2019 / 009052, WO 2020 / 101001, US 2020 / 0207787, WO 2020 / 138874, KR 2020081978, JP 2020-147563、US Boron compounds of 2020 / 0335705 or KR 2022041028.

[0354] Preferably, at least one phosphor has a half-width at half maximum (FWHM) of ≤50 nm, more preferably FWHM ≤ 40 nm, and more preferably FWHM ≤ 30 nm.

[0355] Preferably, at least one fluorescent emitter has a LUMO defined by quantum chemical calculations of -2.1 eV to -2.5 eV, more preferably -2.2 eV to -2.4 eV. Preferably, at least one fluorescent emitter has a HOMO defined by quantum chemical calculations of -4.8 eV to -5.2 eV, more preferably -4.9 eV to -5.1 eV.

[0356] Preferably, the lowest singlet energy S1 of the fluorescent emitter, as defined by quantum mechanical calculations, is 2.65 eV to 2.9 eV, more preferably 2.7 eV to 2.8 eV, and even more preferably 2.7 eV to 2.75 eV.

[0357] In a preferred embodiment of the present invention, the fluorescent emitter is selected from the structure of formula (F-1).

[0358] Equation (F-1)

[0359] Where R has the definition given above and the following symbols and notations are used in addition:

[0360] Ar 30 Ar 31 Ar 32 In each case, they may be the same or different and are substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms;

[0361] Y 30 It can be B or N;

[0362] Y 31 Y 32 Y 33 The same or different in each case and for O, S, C(R) 0 2, C=O, C=S, C=NR 0 C=C(R) 0 )2,Si(R 0 )2, BR 0 NR 0 PR 0 SO2, SeO2, or chemical bonds, provided that when Y 30 When it is B, Y 31 Y 32 Y 33 At least one of the groups is NR 0 And when Y 30 When Y is N,31 Y 32 Y 33 At least one of the groups is BR 0 ;

[0363] R 0 In each case, the same or different and of the form H, D, F, having 1 to 20 straight-chain alkyl groups, preferably having 1 to 10 carbon atoms, or having 3 to 20, preferably 3 to 10 carbon atoms, and in each case, branched or cyclic alkyl groups that may be substituted by one or more substituents R, wherein one or more non-adjacent CH2 groups may be substituted by O or S in each case, and wherein one or more hydrogen atoms may be substituted by D or F, or having 5 to 40, preferably 5 to 30, more preferably 6 to 18 aromatic ring atoms, and in each case, substituted by one or more substituents R; while two adjacent substituents R 0 Together they can form aliphatic or aromatic ring systems that can be substituted by one or more substituents R;

[0364] q is 0 or 1.

[0365] The following compounds are particularly preferred here, wherein:

[0366] - q=0; Y 30 =B; and Y 31 Y 32 =NR 0 ;or

[0367] - q=0; Y 30 =B; and Y 31 Y 32 =NR 0 ;or

[0368] - q=1; Y 30 =N; and Y 31 Y 32 =BR 0 ;Y 33 =Chemical bond.

[0369] Examples of suitable fluorescent emitters are described in the table below:

[0370]

[0371]

[0372]

[0373]

[0374]

[0375]

[0376] Suitable charge transport materials that can be used in the hole injection layer, hole transport layer, electron / exciton blocking layer, or electron transport layer of the electronic components of the present invention, in addition to the compounds of formula (1), include, for example, compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials used in these layers according to the prior art.

[0377] The material used for the hole transport layer can be any material that is used as a hole transport material in a hole transport layer according to existing technology. Aromatic amine compounds can be used. Other compounds preferably used in the hole transport layer of the OLED of the present invention include, in particular: indene-fluoreneamine derivatives (e.g., according to WO 2006 / 122630 or WO 2006 / 100896), amine derivatives disclosed in EP1661888, hexaazatriphenylide derivatives (e.g., according to WO 01 / 049806), amine derivatives having fused aromatics (e.g., according to US 5,061,569), amine derivatives disclosed in WO 95 / 09147, monobenzo[a]indenefluoreneamine (e.g., according to WO 08 / 006449), dibenzo[a]indenefluoreneamine (e.g., according to WO 07 / 140847), spirodifluoreneamine (e.g., according to WO 2012 / 034627 and WO 2013 / 120577), fluoreneamine (e.g., according to WO 2012 / 034627 and WO 2013 / 120577), and fluoreneamine (e.g., according to WO 2012 / 034627 and WO 2013 / 120577). WO 2004 / 015937, WO 2014 / 015938, WO 2014 / 015935 and WO 2015 / 082056), spirodibenzopyranamine (e.g. according to WO 2013 / 083216), dihydroacridine derivatives (e.g. according to WO 2012 / 150001), spirodibenzofuran and spirodibenzothiophene (e.g. according to WO 2015 / 022051, WO 2016 / 102048 and WO 2016 / 131521), phenanthrenediarylamine (e.g. according to WO 2015 / 131976), spirotribenzocycloheptatrienolone (e.g. according to WO 2016 / 087017), spirodifluorene having a m-phenylenediamine group (e.g. according to WO 2004 / 015937, WO 2014 / 015938, WO 2014 / 015935 and WO 2015 / 082056), 2016 / 078738), spirobacidine (e.g., according to WO 2015 / 158411), xanthondiarylamine (e.g., according to WO 2014 / 072017) and 9,10-dihydroanthracene spiro compounds having a diarylamino group according to WO 2015 / 086108.

[0378] Spirodifluorene with a diarylamino group substituted at the 4-position is particularly preferred as a hole-transporting compound, especially those compounds disclosed in WO 2013 / 120577, and spirodifluorene with a diarylamino group substituted at the 2-position is preferred as a hole-transporting compound, especially those compounds disclosed in WO 2012 / 034627.

[0379] The OLED of the present invention preferably comprises two or more different electron transport layers. The compounds in these layers can be any material used as an electron transport material in the electron transport layer according to the prior art. Particularly suitable are aluminum complexes such as Alq3, zirconium complexes such as Zrq4, lithium complexes such as Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, diazole derivatives, aromatic ketones, lactams, boranes, phosphonodiazepine derivatives, and phosphine oxide derivatives. Other suitable materials are derivatives of the above compounds, as disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975, and WO 2010 / 072300.

[0380] The device is appropriately structured (depending on the application), connected to the contact points, and finally sealed to eliminate the harmful effects of water and air.

[0381] In the other layers of the organic electroluminescent device of the present invention, any material commonly used in the prior art can be used. Therefore, those skilled in the art will be able to combine any known material for organic electroluminescent devices with the compounds of the present invention of formula (1) or the preferred embodiments described above without inventive effort.

[0382] Another preferred organic electroluminescent device is characterized by coating one or more layers via a sublimation method. In this case, by using a vacuum sublimation system at a temperature of less than 10... -5 millibars, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of millibars. However, the initial pressure can be even lower, for example, less than 10. -7 millibar.

[0383] Also preferred is an organic electroluminescent device, characterized by coating one or more layers by OVPD (organic vapor deposition) 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 OVJP (organic vapor phase inkjet printing), in which the material is applied directly through a nozzle and thus structured.

[0384] Another preferred organic electroluminescent device is characterized by producing one or more layers from a solution, for example, by spin coating, or by any printing method such as screen printing, flexographic printing, offset printing, LITI (photoinduced thermal imaging, thermal transfer), inkjet printing, or nozzle printing. For this purpose, a soluble compound, for example, obtained through suitable substitution, is required.

[0385] Furthermore, a hybrid approach is feasible, for example, in which one or more layers are applied from a solution and one or more other layers are applied by vapor deposition.

[0386] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices containing the compounds of the present invention without any inventive effort.

[0387] The compounds of this invention and the organic electroluminescent devices of this invention are known for one or more of the following properties:

[0388] 1. Compared with symmetrical compounds according to the prior art, the compounds of the present invention provide improved lifespan.

[0389] 2. Compared with symmetrical compounds according to the prior art, the compounds of the present invention bring about improvements in power efficiency.

[0390] 3. Compared with symmetrical compounds according to the prior art, the compounds of the present invention result in a reduction in operating voltage.

[0391] The invention is illustrated in more detail by way of the following examples, but is not intended to limit the invention. Those skilled in the art will be able to use the information given to practice the invention throughout the entire scope of the disclosure, prepare other compounds of the invention and use them in electronic devices, or employ the methods of the invention without inventive effort.

[0392] Example

[0393] Unless otherwise specified, the following synthesis shall be carried out in a dry solvent under a protective gas atmosphere. Solvents and reagents are available from ALDRICH or ABCR.

[0394] 1) Synthesis of the compounds of the present invention:

[0395] Example B1:

[0396]

[0397] Within 20 minutes, 67.3 g (200 mmol) of N was administered. 1 -[1,1'-biphenyl]-3-yl-N 237.3 ml (400 mmol) of n-butyllithium (in n-hexane, 10.6 M) was added dropwise to a well-stirred mixture of 1200 ml diethyl ether cooled to 0 °C. The mixture was then stirred for another 10 min. 11.5 ml (100 mmol) of silicon tetrachloride [10026-04-7] was added dropwise over 30 min, and the mixture was then heated to room temperature while stirring. After 16 hours, all volatile components were removed under reduced pressure. The residue was dissolved in 1200 ml dichloromethane (DCM), filtered as a DCM slurry through a silica gel column (15 cm diameter), and washed with 300 ml of DCM. The eluent was concentrated to dryness under reduced pressure. The crude product was dissolved in 200 ml DCM and the solution was slowly added dropwise to 600 ml ethanol at room temperature with thorough stirring. The mixture was stirred for another 5 hours, the crystalline solid was filtered off, and dried under reduced pressure. Crystallization with ethanol was repeated twice, followed by crystallization with 600 ml of acetonitrile, repeated three times. Finally, the product was subjected to two fractional sublimations under high vacuum (p approx. 10). -5 mbar, T approx. 260°C to 280°C. Yield: 31.5 g (45 mmol), 45%; purity by HPLC: >99.9%.

[0398] The following compounds can be prepared similarly:

[0399]

[0400] Example B100:

[0401]

[0402] Within 20 minutes, 26.0 g (100 mmol) of N was administered. 1 N 2 18.7 ml (200 mmol) of n-butyllithium (in n-hexane, 10.6 M) was added dropwise to a well-stirred mixture of diphenyl-o-phenylenediamine [28394-83-4] cooled to 0 °C in 500 ml of toluene. The reaction mixture was heated to room temperature and stirred for another 1 hour. Subsequently, 11.5 ml (100 mmol) of silicon tetrachloride [10026-04-7] was added to the well-stirred reaction mixture, and the mixture was heated under reflux for 3 hours. After cooling, the mixture was filtered through a diatomaceous earth bed as a toluene slurry, and the filtrate was concentrated to dryness under reduced pressure (final temperature about 100 °C, final pressure about 0.1 mbar). The resulting dichlorosilane was dissolved in 500 ml of THF; this dichlorosilane solution was used for the next reaction.

[0403] Within 20 minutes, 41.3 g (100 mmol) of N was administered. 1 N 2 18.7 mL (200 mmol) of n-butyllithium (in n-hexane, 10.6 M) was added dropwise to a well-stirred mixture of bis([1,1'-biphenyl]-3-yl)-1,2-phenylenediamine [1225231-02-6] cooled to 0 °C in 500 mL tetrahydrofuran (THF). The reaction mixture was then heated to room temperature and stirred for another 1 hour.

[0404] Then, a dichlorosilane solution was added and stirred thoroughly, followed by stirring for another 16 hours. All volatile components were removed under reduced pressure. The residue was dissolved in 1200 ml of dichloromethane (DCM), filtered as a DCM slurry through a silica gel column (15 cm diameter), and washed with 300 ml of DCM. The eluent was concentrated to dryness under reduced pressure. The crude product was dissolved in 200 ml of DCM and slowly added dropwise to 600 ml of ethanol at room temperature with thorough stirring. The mixture was stirred for another 5 hours, the crystalline solid was filtered off, and dried under reduced pressure. Crystallization with ethanol was repeated twice, followed by crystallization with 600 ml of acetonitrile, repeated three times. Finally, the product was subjected to two fractional sublimations under high vacuum (p approximately 10). -5 mbar, T approx. 260°C to 280°C. Yield: 30.2 g (43 mmol), 43%; purity by HPLC: >99.9%.

[0405] The following compounds can be prepared similarly:

[0406]

[0407] Comparison of glass transition temperatures

[0408] The table below lists the glass transition temperatures (Tg) of the materials according to the prior art (WO 2010 / 054729) and the compounds of the present invention. Because Ar is present... 1 To Ar 4 The compound SdT, representing the phenyl group, has a Tg of only 64°C, which is too low for the commercial manufacturing of OLEDs. Therefore, in subsequent OLED examples, the compound of the present invention is compared with material H-2 according to the prior art.

[0409]

[0410] OLED Examples

[0411] The manufacture of OLEDs has been described multiple times in the literature, for example in WO 2004 / 058911. The method is adapted to the conditions described below, namely variations in layer thickness, layer sequence, and materials. Examples of OLED components according to preferred embodiments of the present invention are described below.

[0412] All exemplary OLED components are characterized by the following layer structure:

[0413] - Glass plate (hereinafter also referred to as glass substrate or base),

[0414] - Indium tin oxide (hereinafter referred to as ITO) is used as the anode.

[0415] - Hole injection layer (hereinafter referred to as HIL),

[0416] - Hole transport layer (hereinafter referred to as HTL),

[0417] - Electron blocking layer (hereinafter referred to as EBL),

[0418] - Emissive layer (hereinafter referred to as EML),

[0419] - Hole blocking layer (hereinafter referred to as HBL),

[0420] - Electron transport layer (hereinafter referred to as ETL),

[0421] - Electron-injected layer (hereinafter referred to as EIL),

[0422] - Aluminum (hereinafter referred to as cathode).

[0423] A glass substrate with a 50 nm thick structured ITO was pretreated with oxygen plasma, followed by argon plasma. Then, materials for HIL, HTL, EBL, EML, HBL, ETL, and EIL were applied to the pretreated glass substrate via thermal evaporation in a vacuum chamber. Table 1 covers detailed information on HIL, HTL, EBL, EML, HBL, ETL, and EIL for OLED components. The materials used in these examples are listed in Table 2. The cathode consisted of a 100 nm thick aluminum layer.

[0424] In one embodiment of the invention, the EML comprises a hole-transporting host material, an electron-transporting host material, and a phosphorescent metal complex. All materials of the EML are deposited in parallel at a specific deposition rate, i.e., by co-evaporation deposition, thereby forming a homogeneous amorphous mixture. The deposition rate of each material can be selected such that each material is present in the mixture at a specific volume percentage (volume %). For example, the composition of an EML having 40 vol% hole-transporting host material (HH), 40 vol% electron-transporting host material (EH), and 10 vol% phosphorescent metal complex (D) is represented in Table 1 as HH:EH:D (45%:45%:10%). This representation is similarly suitable for describing the composition of EMLs containing two or four different materials, and is also suitable for layers if the HIL, HTL, EBL, HBL, ETL, and EIL of an OLED assembly each contain more than one material.

[0425] The performance of OLED components can be measured using standard methods. For this purpose, the electroluminescence spectrum (EL) can be determined, and the external quantum efficiency (EQE) can be determined from the current / voltage / luminescence density characteristics (IUL characteristics) under assumed Lambertian light emission properties. This can be achieved at 1000 cd / m². 2 The EL spectrum is reported at the luminescence density, and the CIE 1931 x and y coordinates can be calculated from this EL spectrum. The operating voltage U is defined as the current density at 10 mA / cm². 2 Required voltage. Table 1 shows the voltage U as a relative voltage (Rel. U), where the voltage of the reference component (SdT1) in the comparative example has been set to 100% Rel. U. Power efficiency EffP is 1000 cd / m 2 The ratio of radiant luminous flux (optical power) in lumens (lm) to supply power in watts (W) at a given luminous density. Table 1 shows the power efficiency EffP as relative power efficiency (Rel. EffP), where the power efficiency of the reference component (SdT1) in the comparative example has been set to 100% Rel. EffP. Lifetime LT90 is defined as at 5 mA / cm². 2 When operating at a constant current density, the time it takes for the luminous density to drop to 90% of the initial luminous density. Table 1 shows LT90 as a relative lifetime (Rel.LT90), where the lifetime of the reference component (SdT1) in the comparative example has been set to 100% Rel.LT.

[0426] The following working example 1 corresponds to a preferred embodiment of the present invention. SdT1 is an example of an OLED device comprising materials according to the prior art. Table 1 provides detailed information on each HIL, HTL, EBL, EML, HBL, ETL, and EIL. Table 2 provides the molecular structures used. HTM is fluoreneamine.

[0427] Example 1: The EML comprises a hole transport host material H-1, an electron transport host material E-1, and a phosphorescent metal complex D-1. This OLED can be compared with an OLED according to Example SdT1 (Table 1). The difference between the two devices lies in the hole transport host material used in each EML; in the case of SdT1, it is H-2 according to the prior art, while in the case of Example 1, it is H-1. Compared with the OLED according to SdT1, the OLED according to Example 1 has better lifetime (LT90), better power efficiency (EffP), and better operating voltage (U).

[0428] Table 1: Structure and Results of OLED

[0429]

[0430]

[0431]

Claims

1. A compound of formula (1), Equation (1) The symbols used are as follows: X is the same or different in each case and is CR or N, provided that there are no more than two X's in each ring that are N; Ar 1 Ar 2 Ar 3 Ar 4 In each case, they may be the same or different and are aromatic or heteroaromatic ring systems having 5 to 40 aromatic ring atoms that can be substituted by one or more R groups; R is the same or different in each case and is H, D, F, Cl, Br, I, OR 1 SR 1 B(OR) 1 )2, CHO, C(=O)R 1 CR 1 =C(R 1 )2, CN, C(=O)OR 1 C(=O)NR 1 ,Si(R 1 )3,Ge(R) 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 OR 1 N(R) 1 )2,S(=O)R 1 S(=O)2R 1 SR 1 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 1 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by -R 1 C=CR 1 -、-C≡C-、Si(R 1 2. CONR 1 ,C=O,C=S,-C(=O)O-,P(=O)(R 1 It can be replaced by -O-, -S-, SO or SO2, or have 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case can be replaced by one or more R 1 Aromatic or heteroaromatic ring systems with substituted R groups; at the same time, two or more R groups together can form a ring system; R 1 The same or different in each case and for H, D, F, Cl, Br, I, B (OR) 2 )2, CHO, C(=O)R 2 CR 2 =C(R 2 )2, CN, C(=O)OR 2 ,Si(R 2 )3,Ge(R) 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 SR 2 S(=O)R 2 S(=O)2R 2 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 2 Group substitution, wherein one or more CH2 groups of the above groups can be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2. C=O, C=S, -C(=O)O-, CONR 2 P(=O)(R) 2 The group is substituted with -S-, SO, or SO2, and one or more hydrogen atoms in the above groups may be substituted with D, F, Cl, Br, I, CN, or NO2, or it has 5 to 30 aromatic ring atoms and in each case may be substituted with one or more R... 2 Aromatic or heteroaromatic ring systems with substituted groups, wherein two or more R groups are... 1 Groups together can form a ring system; R 2 In each case, the substituents are the same or different and are H, D, F, CN, or an aliphatic, aromatic, or heteroaromatic organic group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be replaced by D or F; and simultaneously, two or more substituents R 2 They can be connected to each other and form a loop; Its features Not all Ar groups 1 Ar 2 Ar 3 and Ar 4 They are all the same, and / or the characteristic is that the two rings containing X are different and / or the two rings containing X are replaced differently; This invention excludes the following compounds: 。 2. The compound according to claim 1, wherein the compound is selected from compounds of formulas (2), (3) and (4). The symbols have the definitions given in claim 1.

3. The compound according to claim 1 or 2, wherein the compound is selected from compounds of formulas (2a) to (2f). These structures can also be partially or completely deuterated, and Ar 1 To Ar 4 R has the definition given in claim 1.

4. The compound according to one or more of claims 1 to 3, characterized in that... Ar 1 To Ar 4 as follows: Ar 1 =Ar 2 And Ar 3 =Ar 4 And Ar 1 ≠Ar 3 ;or Ar 1 =Ar 3 And Ar 2 =Ar 4 And Ar 1 ≠Ar 2 ;or Ar 1 =Ar 2 =Ar 3 And Ar 4 ≠Ar 1 ;or Ar 1 =Ar 2 And Ar 3 ≠Ar 4 ≠Ar 1 ;or Ar 1 =Ar 3 And Ar 2 ≠Ar 4 ≠Ar 1 ;or With 1 ≠With 2 ≠With 3 ≠With 4 ; Among the different Ar 1 To Ar 4 The groups can be different aromatic or heteroaromatic ring systems, or the same aromatic or heteroaromatic ring system but substituted differently.

5. The compound according to one or more of claims 1 to 4, characterized in that... Ar 1 To Ar 4 In each case, they may be the same or different and are selected from aromatic or heteroaromatic ring systems having 6 to 30 aromatic ring atoms, preferably 6 to 24 aromatic ring atoms, more preferably 6 to 18 aromatic ring atoms, and in each case, they may be substituted by one or more R groups.

6. The compound according to one or more of claims 1 to 5, characterized in that... Ar 1 To Ar 4 At least one of the groups contains at least 12 aromatic ring atoms, and / or the compound is characterized by having at least one aromatic or heteroaromatic substituent R containing at least 12 aromatic ring atoms, and / or the compound is characterized by having at least two aromatic or heteroaromatic substituents R.

7. The compound according to one or more of claims 1 to 6, characterized in that... Ar 1 To Ar 4 In each case, the same or different groups are 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; fluorene linked at positions 1, 2, 3, or 4; spirodifluorene linked at positions 1, 2, 3, or 4; naphthalene linked at position 1 or 2; indole; benzofuran; benzothiophene linked at positions 1, 2, 3, or 4; dibenzofuran; carbazole linked at positions 1, 2, 3, or 4; dibenzothiophene linked at positions 1, 2, 3, or 4; indocarbazole; indolecarbazole; pyridine; pyrimidine; pyrazine; pyridazine; triazine; quinoline; quinazoline; benzimidazole; phenanthrene; biphenylide; or combinations of two or three of these groups, each of which may be substituted with one or more R groups.

8. The compound according to one or more of claims 1 to 7, characterized in that... Ar 1 To Ar 4 In each case they may be the same or different and are selected from the following structures Ar-a to Ar-l. The dashed bonds represent bonds connected to nitrogen atoms, and these structures can be partially or completely deuterated.

9. The compound according to one or more of claims 1 to 8, characterized in that... with Ar 1 To Ar 4 The substituent R in each case may be the same or different and is selected from H, D, F, CN, Si(R) 1 )3,Ge(R) 1 3, a straight-chain alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group in each case may be one or more R 1 The groups are substituted, but preferably unsubstituted, and one or more non-adjacent CH2 groups may be replaced by O; at the same time, two adjacent R groups may form a cyclic system with each other; Furthermore, when X=CR, the R bonded to the carbon atom is the same or different in each case and is selected from H, D, F, CN, OR. 1 N(R) 1 )2,Si(R 1 )3,Ge(R) 1 3, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group in each case may be one or more R 1 The group is substituted, but preferably unsubstituted, or has 6 to 30 aromatic ring atoms and in each case can be substituted by one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups.

10. The compound according to one or more of claims 1 to 9, characterized in that... The compound is at least 30% deuterated.

11. A method for preparing a compound according to one or more of claims 1 to 10, Its characteristics include the following steps: (1) Provided by -NHAr 1 and -NHAr 2 A benzene derivative or a corresponding heteroaromatic derivative in which groups are substituted in the ortho position with each other, and optionally provided with -NHAr 3 and -NHAr 4 Benzene derivatives or corresponding heteroaromatic derivatives in which groups are substituted for each other at the ortho position; and (2) Make SiHal4 react with -NHAr 1 Groups and -NHAr 2 A benzene derivative or corresponding heteroaromatic derivative in which groups are substituted at the ortho position with each other, optionally followed by a reaction with -NHAr 3 Groups and -NHAr 4 The reaction of benzene derivatives or corresponding heteroaromatic derivatives in which groups are substituted for each other at the ortho position, where Hal represents a halogen.

12. A mixture comprising at least one compound according to one or more of claims 1 to 10 and at least one other compound.

13. Use of the compound according to one or more of claims 1 to 10 in electronic devices.

14. An electronic device comprising at least one compound according to one or more of claims 1 to 10.

15. The electronic device according to claim 14, wherein the electronic device is an organic electroluminescent device, characterized in that... The compound according to one or more of claims 1 to 10 is used in a hole transport layer and / or an exciton blocking layer and / or as a matrix material in a light-emitting layer.

16. The electronic device according to claim 15, characterized in that... The light-emitting layer is a phosphorescent layer or a superphosphorescent layer.

17. The electronic device according to claim 16, characterized in that... The luminescent layer contains a blue phosphorescent iridium complex or a blue phosphorescent platinum complex as a luminescent compound or as a sensitizer.

18. The electronic device according to one or more of claims 15 to 17, characterized in that... The compound according to one or more of claims 1 to 10 is used as a matrix material in combination with an electron transport matrix material.

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