Materials for organic electroluminescent devices

Abstract

The present invention relates to materials for organic electroluminescent devices. In particular, the present invention relates to amines having dibenzofuran, dibenzothiophene and fluorene groups for use as triplet matrix materials, in particular in organic electroluminescent devices. The invention also relates to a method for producing the compounds according to the invention and to electronic devices comprising said compounds.

Description

[0001] This invention patent application is a divisional application of the invention patent application with international application number PCT / EP2017 / 000154, international application date of February 6, 2017, application number 201780014250.2 which entered the Chinese national phase, and the invention title "Materials for Organic Electroluminescent Devices". Technical Field

[0002] This invention relates to materials for use in organic electroluminescent devices. Specifically, the invention describes amines having dibenzofuran, dibenzothiophene, and fluorene groups, particularly used as triplet matrix materials in organic electroluminescent devices. The invention also relates to methods for preparing the compounds of the invention and to electronic devices comprising these compounds. Background Technology

[0003] The structures of organic light-emitting diodes (OLEDs) using organic semiconductors as functional materials are described in, for example, US 4539507, US 5151629, EP 0676461, and WO 98 / 27136. The luminescent materials used are typically phosphorescent organometallic complexes. For quantum mechanical reasons, using organometallic compounds as phosphorescent emitters can achieve up to four times the energy efficiency and power efficiency. In general, there remains a need for improvements in OLEDs, particularly phosphorescent OLEDs, in areas such as efficiency, operating voltage, and lifetime.

[0004] The performance of phosphorescent OLEDs is not solely determined by the triplet emitter used. More specifically, other materials employed, such as the matrix material, are also crucial. Therefore, improvements in these materials lead to significant improvements in OLED performance.

[0005] According to the prior art, amines having fluorene and dibenzofuran groups are known from US 2014 / 0284578. Compounds having carbazole are also known from EP 2421064. US 2013 / 0234118 discloses amines having fused aromatic groups such as pyrene.

[0006] In summary, there remains a need for improvements, particularly in lifetime and oxidation sensitivity, as well as in device efficiency and operating voltage, when using these materials as matrix materials. Summary of the Invention

[0007] The object of this invention is to provide compounds suitable for use in phosphorescent or fluorescent OLEDs, particularly as matrix materials. More specifically, the object of this invention is to provide matrix materials suitable for use in OLEDs emitting red, yellow, and green phosphorescence, and also suitable for use in OLEDs emitting blue phosphorescence, resulting in long lifetime, good efficiency, and low operating voltage. In particular, the properties of the matrix materials also have a significant impact on the lifetime and efficiency of organic electroluminescent devices.

[0008] Surprisingly, it has been found that electroluminescent devices containing compounds of the following formula (1) have improvements over the prior art, especially when used as a matrix material for phosphorescent dopant.

[0009] Therefore, the present invention provides a compound of the following formula (1):

[0010] Equation (1)

[0011] The symbols used are as follows: X is O or S; Y is O, S, or CR2; Ar may be the same or different in each case, and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms that may be substituted by one or more R groups, wherein Ar contains only aryl or heteroaromatic groups having at most 15 aromatic ring atoms, and does not contain carbazolyl as a heteroaromatic group, and does not contain 9,9'-spirobisfluorenel. R may be the same or different in each case, and is selected from H, D, F, Cl, Br, I, CN, NO2, N (Ar) 1 )2,N(R 4 )2,C(=O)Ar 1 C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of which may be derived from one or more R groups. 4 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 4 C=CR 4 C=O, C=S, C=NR 4 P(=O)(R) 4 SO, SO2, NR 4 O, S or CONR 4(where one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2), having 5 to 40 aromatic ring atoms and in each case, being replaced by one or more R atoms. 4 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 1 A group-substituted aryloxy or heteroaryloxy group, or having 5 to 40 aromatic ring atoms and being capable of being substituted by one or more R groups. 4 The alkyl or heteroaryl groups are substituted with a group; additionally, optionally, two R substituents bonded to the same or adjacent carbon atoms can form a group that can be substituted by one or more R groups. 4 Monocyclic or polycyclic aliphatic ring systems with substituted groups; R 1 The same or different in each case, and selected from H, D, F, Cl, Br, I, CN, NO2, N (Ar) 1 )2,N(R 4 )2,C(=O)Ar 1 C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of which may be derived from one or more R groups. 4 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 4 C=CR 4 C=O, C=S, C=NR 4 P(=O)(R) 4 SO, SO2, NR 4 O, S or CONR 4 (where one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2), having 5 to 40 aromatic ring atoms and in each case, being replaced by one or more R atoms. 4 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 4 A group-substituted aryloxy or heteroaryloxy group, or having 5 to 40 aromatic ring atoms and being capable of being substituted by one or more R groups. 4 The alkyl or heteroaryl group is substituted with a group; and optionally, two R groups are bonded to adjacent carbon atoms. 1 Substituents or two Rs 1 and R 3 Substituents can form groups that can be formed by one or more R groups.4 Monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring systems with substituted groups; R 2 The same or different in each case, and selected from H, D, F, Cl, Br, I, CN, NO2, N (Ar) 1 )2,N(R 4 )2,C(=O)Ar 1 C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of which may be derived from one or more R groups. 4 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 4 C=CR 4 C=O, C=S, C=NR 4 P(=O)(R) 4 SO, SO2, NR 4 O, S or CONR 4 (where one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2), having 5 to 40 aromatic ring atoms and in each case, being replaced by one or more R atoms. 4 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 4 A group-substituted aryloxy or heteroaryloxy group, or having 5 to 40 aromatic ring atoms and being capable of being substituted by one or more R groups. 4 The alkyl or heteroaryl group is substituted with a group; and optionally, two R groups are bonded to adjacent carbon atoms. 2 Substituents can form groups that can be formed by one or more R groups. 4 Monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring systems with substituted groups; R 3 The same or different in each case, and selected from H, D, F, Cl, Br, I, CN, NO2, N (Ar) 1 )2,N(R 4 )2,C(=O)Ar 1 C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1)2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of which may be derived from one or more R groups. 4 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 4 C=CR 4 C=O, C=S, C=NR 4 P(=O)(R) 4 SO, SO2, NR 4 O, S or CONR 4 (where one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2), having 5 to 40 aromatic ring atoms and in each case, being replaced by one or more R atoms. 4 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 4 A group-substituted aryloxy or heteroaryloxy group, or having 5 to 40 aromatic ring atoms and being capable of being substituted by one or more R groups. 4 The alkyl or heteroaryl group is substituted with a group; and optionally, two R groups are bonded to adjacent carbon atoms. 3 and R 1 Substituents can form groups that can be formed by one or more R groups. 4 Monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring systems with substituted groups; Ar 1 The same or different in each case, and having 5 to 30 aromatic ring atoms and can be separated by one or more non-aromatic R atoms. 4 Aromatic or heteroaromatic ring systems with substituent groups; simultaneously, two Ar atoms bonded to the same phosphorus or boron atom. 1 Groups can also be formed by single bonds or by means of N(R) 4 ), C(R 4 2. The bridge bases of O and S are connected to each other; R 4 The same or different in each case, and selected from H, D, F, Cl, Br, I, CN, NO2, N(R) 5 )2,C(=O)R 5 A straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms (each of these groups may be generated by one or more R groups). 5 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 5 C=CR 5C=O, C=S, C=NR 5 P(=O)(R) 5 SO, SO2, NR 5 O, S or CONR 5 (where one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2), having 5 to 40 aromatic ring atoms and in each case, being replaced by one or more R atoms. 5 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 5 A group-substituted aryloxy or heteroaryloxy group, or having 5 to 40 aromatic ring atoms and being capable of being substituted by one or more R groups. 5 Group-substituted aralkyl or heteroaralkyl groups; simultaneously, optionally, two R groups bonded to the same or adjacent carbon atoms. 4 Substituents can form groups that can be formed by one or more R groups. 5 Monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring systems with substituted groups; R 5 In each case, the same or different, and selected from H, D, F, CN, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms can be replaced by D, F, Cl, Br, I or CN, and said aromatic or heteroaromatic ring system can be replaced by one or more alkyl groups each having 1 to 4 carbon atoms; simultaneously, two or more adjacent R 5 Substituents can work together to form monocyclic or polycyclic aliphatic ring systems; In one case, the nitrogen atom is bonded to the corresponding carbon atom in place of R. 1 Or R 3 In R 3 In this case, Y is not CR2.

[0012] In the case of this invention, adjacent carbon atoms are carbon atoms that are directly bonded to each other.

[0013] In the context of this invention, the term "two or more groups that can form a ring together" should specifically mean that the two groups are linked to each other by chemical bonds, wherein two hydrogen atoms are formally eliminated. This is illustrated by the following scheme:

[0014] However, the above terminology should also mean that if one of the two groups is hydrogen, the second group binds to the position where the hydrogen atom is bonded, forming a ring. This will be illustrated by the following scheme:

[0015] In the context of this invention, a fused aryl group is a group in which two or more aromatic groups are fused together along a common edge, i.e., ring-enhanced, as in naphthalene, for example. Conversely, in the context of this invention, fluorene is not a fused aryl group because the two aromatic groups in fluorene do not have a common edge.

[0016] In the present invention, the aryl group contains 6 to 40 carbon atoms; in the present invention, the heteroaryl group contains 2 to 40 carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. Here, aryl or heteroaryl means a simple aromatic ring, i.e., benzene or a simple heteroaromatic ring such as pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

[0017] In the context of this invention, the aromatic ring system contains 6 to 40 carbon atoms. In the context of this invention, the heteroaromatic ring system contains 1 to 40 carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. In the context of this invention, an aromatic or heteroaromatic ring system should not necessarily refer to a system containing only aryl or heteroaryl groups, but rather a system in which two or more aryl or heteroaryl groups can also be interrupted by non-aromatic units (preferably less than 10% of non-H atoms), such as carbon, nitrogen, or oxygen atoms, or carbonyl groups. Therefore, systems such as 9,9'-spirodifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, stilbene, etc., should also be considered as aromatic ring systems in the context of this invention, and systems in which two or more aryl groups are interrupted by, for example, straight-chain or cyclic alkyl groups or by silyl groups are also considered as aromatic ring systems in the context of this invention. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to each other, such as biphenyl, terphenyl, tetraphenyl, or bipyridine, should also be considered as aromatic or heteroaromatic ring systems.

[0018] In the context of this invention, cyclic alkyl, alkoxy, or thioalkoxy means monocyclic, bicyclic, or polycyclic groups.

[0019] In the case of this invention, each hydrogen atom or CH2 group may also be replaced by the C1- to C2- groups described above. 20-alkyl, meaning such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl 1-Methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl- 1,1-octyl-1-yl, 1,1-dimethyl-n-decane-1-yl, 1,1-dimethyl-n-dodecane-1-yl, 1,1-dimethyl-n-tetradecane-1-yl, 1,1-dimethyl-n-hexadecane-1-yl, 1,1-dimethyl-n-octadecane-1-yl, 1,1-diethyl-n-hexane-1-yl, 1,1-diethyl-n-heptane-1-yl, 1,1-diethyl-n-octyl-1-yl, 1,1-diethyl-n-decane -1-yl, 1,1-diethyl-n-dodecane-1-yl, 1,1-diethyl-n-tetradecane-1-yl, 1,1-diethyl-n-hexadecane-1-yl, 1,1-diethyl-n-octadecane-1-yl, 1-(n-propyl)cyclohexyl-1-yl, 1-(n-butyl)cyclohexyl-1-yl, 1-(n-hexyl)cyclohexyl-1-yl, 1-(n-octyl)cyclohexyl-1-yl and 1-(n-decyl)cyclohexyl-1-yl groups. Alkenyl means, for example, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. Alkynyl means, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptenyl or octynyl. C1- to C1- 40 -alkoxy means, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, or 2-methylbutoxy.

[0020] An aromatic or heteroaromatic ring system having 5-40 aromatic ring atoms, and in each case potentially substituted by the aforementioned groups and linked at any desired position, meaning, for example, derived from groups such as: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, etc. Perylene, fluoranthene, benzo[a]fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, biphenyl ethylene, terphenyl, terphenyl ethylene, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorene, cis or trans monobenzo[a]fluorene, cis or trans dibenzo[a]fluorene, trimer indene, isotrimer indene, spirotrimer indene, spiroisotrimer indene, furan Benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indole-carbazole, indole-carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenanthrene Azides, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthiazoles, phenanthreneimidazoles, pyridinium imidazoles, pyrazinium imidazoles, quinoxaline imidazoles azole, benzo[ azole, naphtho azole, anthraquinone azole, phenanthrene azole, isotonic Azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenazine Azides, phenothiazines, fluorescent rings, naphthidine, azacarbazole, benzo[a]carbline, phenanthroline, 1,2,3-triazoles, 1,2,4-triazoles, benzo[a]triazoles, 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, indazine, and benzothiadiazole.

[0021] Preferably, for equation (1), when Y is CR2, the nitrogen atom is bonded to the corresponding carbon atom in place of R. 1 Furthermore, when Y is O or S, the nitrogen atom bonds to the corresponding carbon atom in place of R. 1 Or R 3 .

[0022] In a preferred embodiment, X is O.

[0023] In other preferred embodiments, Y is CR2.

[0024] In other preferred embodiments, X is O and Y is CR2.

[0025] In other preferred embodiments of the invention, when the compound of formula (1) has R which is optionally substituted carbazole... 1 Or R 2 When substituents are present, the carbazole does not bind at its 2-position.

[0026] In other embodiments of the invention, the compound is selected from compounds of formula (1-1) or formula (1-2).

[0027] Equation (1-1)

[0028] Equation (1-2)

[0029] The symbols correspond to the symbols in equation (1).

[0030] In other preferred embodiments of the invention, Ar may be the same or different in each case, and is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, and more preferably an aromatic ring system having 6 to 12 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 aromatic ring atoms. Each of the groups may be substituted by one or more R groups, but preferably unsubstituted, wherein Ar contains only aryl or heteroaromatic groups having up to 15 aromatic ring atoms, and does not contain carbazolyl or 9,9'-spirodifluorene. Examples of suitable Ar groups are selected from phenyl, ortho, meta, or para biphenyl, terphenyl, especially branched terphenyl, tetraphenyl, especially branched tetraphenyl, 1-, 2-, 3-, or 4-fluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3-, or 4-dibenzofuranyl and 1-, 2-, 3-, or 4-dibenzothiopheneyl, each of which may be substituted with one or more R groups, but is preferably unsubstituted.

[0031] In a preferred embodiment of the present invention, Ar is selected from structures of formulas (Ar-1) to (Ar-16).

[0032] Where the symbol corresponds to the symbol in equation (1), and furthermore, Q is the same or different in every case and is CR 4 Or N, where no more than 3 Q symbols in each ring are N; E is the same or different in every case, and is C(R) 4 2. O, S, or C=O, where two R's 4It does not form aromatic or hybrid aromatic ring systems; G is NR in every case 4 C(R) 4 )2, O, S, or C=O; and This represents a bond attached to a nitrogen atom.

[0033] Preferably, there is no Q, which is N.

[0034] In other preferred embodiments, the Ar group is selected in each case from groups having structures of formulas (Ar-1) to (Ar-16), wherein the general formula is replaced by each of the particularly preferred embodiments of formulas (Ar-1-1) to (Ar-16-6) below (e.g., formula (Ar-1) is replaced by one of formulas (Ar-1-1) to (Ar-1-9):

[0035]

[0036]

[0037]

[0038] The symbols correspond to those in equations (Ar-1) to (Ar-16). The equations can be represented by R in their free positions. 4 replace.

[0039] In other embodiments of the present invention, R 2 Whether the cases are the same or different, and in the case of aromatic or heteroaromatic ring systems, the structures selected from formulas (Ar-1) to (Ar-16) or their preferred embodiments, as well as the structures of formulas (Ar-17) and (Ar-18):

[0040] The symbols correspond to those in equation (1). Furthermore, for equations (Ar-17) and (Ar-18): Q is the same or different in every case and is CR 4 Or N, where no more than 3 Q symbols in each ring are N; E is the same or different in every case and is NR 4 C(R) 4 2. O, S, or C=O, where two R's 4 It does not form aromatic or hybrid aromatic ring systems; G is NR in every case 4 C(R) 4 )2, O, S, or C=O; and This represents a bond that connects to an aromatic ring system.

[0041] Preferably, there is no Q, which is N.

[0042] In other preferred embodiments, R 2 In each case, in the case of an aromatic or heteroaromatic ring system, the group is selected from groups having a structure of formula (Ar-1) to (Ar-18), wherein the general formula is replaced by each of the following particularly preferred embodiments of formulas (Ar-1-1) to (Ar-16-6) (for example, formula (Ar-1) is replaced by one of formulas (Ar-1-1) to (Ar-1-9), and the following formulas are preferred:

[0043] The symbols correspond to the symbols in equation (1).

[0044] In one embodiment of the present invention, the compound has the structure of formula (2) or formula (3):

[0045] Equation (2)

[0046] Equation (3)

[0047] The symbol corresponds to the symbol in equation (1), where an R bonded to a carbon atom 2 And an R 4 Replaced by a single bond, and in R 2 In the case of R, preferably one of the six-membered rings not bonded to the nitrogen atom in equation (2) is used. 2 It has been replaced by a single key.

[0048] In a preferred embodiment of the invention, carbazole is not bonded at its 2-position.

[0049] In other preferred embodiments of the invention, the compound is a compound with one of the structures of formulas (2-1) and (2-2):

[0050] Equation (2-1)

[0051] Equation (2-2)

[0052] The symbol corresponds to the symbol in equation (2), where one R in equation (2-1) 2 And the R bonded to the carbon atom in formula (2-2) 4Replaced by a single bond, and in the case of equation (2-2), an R not bonded to the six-membered ring of the nitrogen atom. 2 It has been replaced by a single key.

[0053] In other preferred embodiments of the invention, the compound is a compound of formula (2-3):

[0054] Equation (2-3)

[0055] The symbols correspond to the symbols in equation (2).

[0056] In other preferred embodiments of the invention, the compound is a compound with one of the structures of formulas (3-1) and (3-2):

[0057] Equation (3-1)

[0058] Equation (3-2)

[0059] The symbol corresponds to the symbol in equation (3), where one R in equation (3-1) 2 And the R bonded to the carbon atom in formula (3-2) 4 Replaced by a single bond, and in the case of equation (3-2), an R bonded to the six-membered ring of the nitrogen atom. 2 It has been replaced by a single key.

[0060] In other preferred embodiments of the invention, the compound is a compound of formula (3-3):

[0061] Equation (3-3)

[0062] The symbols correspond to those in equation (3).

[0063] In other embodiments of the invention, the compound is a compound of formula (2-1a), (2-1b), (2-2a), (2-2b):

[0064] Equation (2-1a)

[0065] Equation (2-1b)

[0066] Equation (2-2a)

[0067] Equation (2-2b)

[0068] The symbols correspond to the symbols in equation (2).

[0069] In other embodiments of the invention, the compound is a compound of formula (3-1a), (3-1b), (3-2a), or (3-2b):

[0070] Equation (3-1a)

[0071] Equation (3-1b)

[0072] Equation (3-2a)

[0073] Equation (3-2b)

[0074] The symbols correspond to those in equation (3).

[0075] In other preferred embodiments of the invention, the compound is a compound of formula (2-3a) or (2-3b):

[0076] Equation (2-3a)

[0077] Equation (2-3b)

[0078] The symbols correspond to those in equation (2-3).

[0079] In other preferred embodiments of the invention, the compound is a compound of formula (3-3a) or (3-3b):

[0080] Equation (3-3a)

[0081] Equation (3-3b)

[0082] The symbols correspond to those in equation (3-3).

[0083] In other embodiments of the present invention, R 1 and R 3In each case, the same or different, and in the case of aromatic or heteroaromatic ring systems, selected from one of formulas (Ar-1) to (Ar-16), where the definition of the symbol corresponds to the symbol defined for Ar, and It is a bond that connects to the aromatic ring system.

[0084] Preferably, the R substituents bonded to Ar are selected from H, D, F, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms; or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3, 4, 5 or 6 carbon atoms; or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms, wherein the alkyl or alkenyl group in each case may be one or more R 4 The groups are substituted (but preferably unsubstituted), or are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more R groups. 4 The groups are substituted, but preferably unsubstituted; alternatively, the two R substituents bonded to adjacent carbon atoms can form a monocyclic or polycyclic aliphatic ring system, which can be substituted by one or more R substituents. 4 The groups may be substituted, but preferably unsubstituted.

[0085] When Y is CR2, preferably, the R group bonded to this carbon atom may be the same or different in each case, and is a straight-chain alkyl group having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms; or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3, 4, 5 or 6 carbon atoms; or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms (wherein each alkyl or alkenyl group may be bonded to one or more R groups). 4 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by O, and one or more hydrogen atoms can be replaced by D or F), or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, each of said groups can be replaced by one or more R groups. 4 Group substitution; alternatively, the two R substituents can form a group that can be substituted by one or more R groups. 4 Monocyclic or polycyclic aliphatic ring systems with substituent groups. Cyclonation between two R substituents forms a spirocyclic system.

[0086] Preferably, the R 1 Substituents are selected from H, D, F, CN, N (Ar) 1)2, a straight-chain alkyl group having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms; or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3, 4, 5 or 6 carbon atoms; or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms, wherein the alkyl or alkenyl group in each case may be one or more R 4 The groups are substituted (but preferably unsubstituted), or are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more R groups. 4 The groups are substituted, but preferably unsubstituted; and optionally, two R groups bonded to the same or adjacent carbon atoms are... 1 Substituents or two Rs 1 and R 3 Substituents can form monocyclic or polycyclic aliphatic ring systems, which can be formed by one or more R groups. 4 The groups may be substituted, but preferably unsubstituted.

[0087] Preferably, the R 2 Substituents are selected from H, D, F, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms; or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3, 4, 5 or 6 carbon atoms; or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms, wherein the alkyl or alkenyl group in each case may be one or more R 4 The groups are substituted (but preferably unsubstituted), or are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more R groups. 4 The groups are substituted, but preferably unsubstituted; and optionally, two R groups bonded to the same or adjacent carbon atoms are... 2 Substituents can form monocyclic or polycyclic aliphatic ring systems, which can be formed by one or more R groups. 4 The groups may be substituted, but preferably unsubstituted.

[0088] Preferably, the R 3 Substituents are selected from H, D, F, CN, N (Ar) 1)2, a straight-chain alkyl group having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms; or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3, 4, 5 or 6 carbon atoms; or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms, wherein the alkyl or alkenyl group in each case may be one or more R 4 The groups are substituted (but preferably unsubstituted), or are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more R groups. 4 The groups are substituted, but preferably unsubstituted; and optionally, two R groups bonded to the same or adjacent carbon atoms are... 3 and R 1 Substituents can form monocyclic or polycyclic aliphatic ring systems, which can be formed by one or more R groups. 4 The groups may be substituted, but preferably unsubstituted.

[0089] Preferably, the R 4 Substituents are selected from H, D, F, CN, N (Ar) 1 )2,N(R 5 )2, a straight-chain alkyl group having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms; or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3, 4, 5 or 6 carbon atoms; or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms (wherein the alkyl or alkenyl group can be one or more R in each case). 5 The groups are substituted (but preferably unsubstituted), or are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic R groups. 5 The groups are substituted, but preferably unsubstituted; and optionally, two R groups bonded to the same or adjacent carbon atoms are... 4 Substituents can form monocyclic or polycyclic aliphatic ring systems, which can be formed by one or more R groups. 5 The groups may be substituted, but preferably unsubstituted.

[0090] When E or G is NR 4 Preferably, R bonded to the nitrogen atom 4 The groups may be the same or different in each case, and are aromatic rings with 5 to 24 atoms, and in each case can be one or more R groups. 5 Aromatic or heteroaromatic ring systems with substituted groups, more preferably having 6 to 18 aromatic ring atoms and capable of being substituted by one or more R groups.5 Aromatic or heteroaromatic ring systems with substituted groups. Suitable R 4 Examples of substituents are selected from phenyl, ortho, meta, or para-biphenyl, terphenyl, especially branched terphenyl, tetraphenyl, especially branched tetraphenyl, 1-, 2-, 3-, or 4-fluorenyl, 1-, 2-, 3-, or 4-spirodifluorenyl, pyridyl, pyrimidinyl, 1,3,5-triazinyl, 4,6-diphenyl-1,3,5-triazinyl, 1-, 2-, 3-, or 4-dibenzofuranyl, 1-, 2-, 3-, or 4-dibenzothiopheneyl, and 1-, 2-, 3-, or 4-carbazoleyl, wherein the carbazoleyl group is replaced by an R other than H or D on the nitrogen atom. 5 These groups can each be substituted with one or more R groups. 5 The groups may be substituted, but preferably unsubstituted.

[0091] In other embodiments of the invention, the compound does not contain any other unbridged amines besides the central nitrogen atom. This means, for example, that no group is N(Ar). 1 )2 or N(R 4 )2.

[0092] In other embodiments of the present invention, at least one R, R in formula (1) 1 R 2 Or R 3 It is a heteroaryl group.

[0093] In other embodiments of the invention, Ar is not a group of formula (Ar-10-2), such as 2-fluorenyl.

[0094] The preferred scenarios mentioned above can occur individually or together. Preferably, the preferred scenarios mentioned above occur together.

[0095] Examples of suitable compounds of the present invention are those shown below.

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] The compounds of the present invention can be prepared by synthetic steps known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc. Suitable synthetic methods are generally shown in Scheme 1 below: Option 1

[0109] The compound of formula (2) can be obtained according to the following scheme (2): Option 2

[0110] In this scheme, R is R, R according to equation (1) or (2). 1 R 2 Or R 3 In addition to fluorene derivatives, dibenzofuran derivatives or dibenzothiophene derivatives can also be used accordingly.

[0111] To process the compounds of the present invention from the liquid phase by methods such as 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, the use of a mixture of two or more solvents is preferred. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-, or p-xylene, methyl benzoate, mesitylene, naphthol, veratrine ether, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, etc. Alkane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenazine, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, naphthane, dodecylbenzene, Ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenethyl ether, 1,4-diisopropylbenzene, diphenylmethyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindane, or mixtures of these solvents.

[0112] Therefore, the present invention also provides formulations comprising the compounds of the present invention and at least one other compound. The other compound may be, for example, a solvent, particularly one of the solvents mentioned above or a mixture of these solvents. The other compound may optionally be at least one other organic or inorganic compound also used in electronic devices, such as a luminescent compound, particularly a phosphorescent dopant, and / or other matrix material. Suitable luminescent compounds and other matrix materials are listed below in the section relating to organic electroluminescent devices. Such other compounds may also be polymeric.

[0113] The compounds and mixtures of the present invention are suitable for use in electronic devices. An electronic device is defined as a device containing at least one layer comprising at least one organic compound. The assembly may also comprise layers of inorganic materials or layers formed entirely of inorganic materials.

[0114] Therefore, the present invention also provides the use of the compounds or mixtures of the present invention in electronic devices, particularly organic electroluminescent devices.

[0115] The present invention also provides electronic devices comprising at least one of the compounds or mixtures of the present invention detailed above. In this case, the preferred embodiments described in detail above for the compounds also apply to the electronic devices.

[0116] The electronic device is preferably selected from organic electroluminescent devices (OLED, PLED), organic integrated circuits (O-IC), organic field-effect transistors (O-FET), organic thin-film transistors (O-TFT), organic light-emitting transistors (O-LET), organic solar cells (O-SC), organic dye-sensitized solar cells, organic photosensors, organic photosensors, organic field quenching devices (O-FQD), light-emitting electrochemical cells (LEC), organic laser diodes (O-laser), and organic plasma emitting devices, and is more preferably organic electroluminescent devices (OLED, PLED), especially phosphorescent OLEDs.

[0117] The organic electroluminescent device comprises a cathode, an anode, and at least one emitting layer. In addition to these layers, it may also comprise 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, and / or charge generation layers in each case. Similarly, an intermediate layer, for example, having exciton blocking functionality, may be introduced between two emitting layers. However, it should be noted that each of these layers is not necessarily required. In this case, the organic electroluminescent device may contain one emitting layer, or it may contain multiple emitting layers. If multiple emitting layers are present, they preferably have a total of multiple emission peaks between 380 nm and 750 nm, such that the overall result is white light emission; in other words, various different luminescent compounds capable of emitting fluorescence or phosphorescence are used in the emitting layers. One embodiment of the invention relates to a system having three emitting layers, wherein the three layers exhibit blue, green, and orange or red light emission. These layers may be fluorescent or phosphorescent emitting layers or a hybrid system in which fluorescent and phosphorescent emitting layers are combined with each other. Another embodiment of the invention relates to a tandem OLED. Electroluminescent devices that emit white light can be used in applications such as lighting, and can also be combined with color filters for full-color displays.

[0118] Depending on the specific structure, the compounds of the present invention according to the embodiments detailed above can be used in different layers. Depending on the specific substitutions, preferred organic electroluminescent devices comprise the compound of formula (1) or according to the preferred embodiments as a matrix material, used for fluorescent or phosphorescent emitters or for emitters exhibiting TADF (thermally activated delayed fluorescence), particularly for phosphorescent emitters, and / or for use in electron transport layers and / or electron blocking or exciton blocking layers and / or hole transport layers and / or hole injection layers. In this case, the preferred embodiments detailed above also apply to the use of said materials in organic electronic devices.

[0119] In a preferred embodiment of the invention, formula (1) or the compound according to the preferred embodiment is used as a matrix material for a fluorescent or phosphorescent compound in the light-emitting layer, particularly for a phosphorescent compound. In this case, the organic electroluminescent device may contain one light-emitting layer, or it may contain multiple light-emitting layers, wherein at least one light-emitting layer contains at least one compound of the present invention as a matrix material.

[0120] When the compound of formula (1) or according to the preferred embodiment is used as a matrix material in the luminescent compound of the luminescent layer, it is preferably used in combination with one or more phosphorescent materials (triple-state luminescent materials). In the case of this invention, phosphorescence refers to luminescence from an excited state with a spin multiplicity >1, particularly from an excited triplet state. In the case of this application, all luminescent transition metal complexes and luminescent lanthanide metal complexes, particularly all iridium, platinum, and copper complexes, should be considered as phosphorescent compounds.

[0121] The mixture of formula (1) or the compound according to the preferred embodiment with the luminescent compound, based on the total mixture of the luminescent material and the matrix material, contains between 99 vol% and 1 vol%, preferably between 98 vol% and 10 vol%, more preferably between 97 vol% and 60 vol%, and particularly between 95 vol% and 80 vol% of the compound of formula (1) or the compound according to the preferred embodiment. Accordingly, the mixture, based on the total mixture of the luminescent material and the matrix material, contains between 1 vol% and 99 vol%, preferably between 2 vol% and 90 vol%, more preferably between 3 vol% and 40 vol%, and particularly between 5 vol% and 20 vol% of the luminescent material. If the compound is processed from solution, it is preferable to use the corresponding amount in weight % rather than the amount in volume % as specified above.

[0122] In particular, suitable phosphorescent compounds (= triplet luminescent substances) are those that emit light when properly excited, preferably in the visible light region, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially metal atoms having such atomic numbers. Preferred phosphorescent substances used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, especially compounds containing iridium or platinum. In the case of this invention, all luminescent compounds containing the above-mentioned metals are considered phosphorescent compounds.

[0123] Examples of the aforementioned luminescent materials can be found in applications WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO The following are listed: WO2011 / 032626, WO2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 023377, WO2014 / 094961, WO 2014 / 094960, WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO2016 / 015815, and WO 2016 / 124304. In general, all phosphorescent complexes known to those skilled in the art for use in phosphorescent OLEDs according to existing technology in the field of organic electroluminescence are suitable, and those skilled in the art can use other phosphorescent complexes without inventive effort.

[0124] Another preferred embodiment of the invention is the use of the compound of formula (1) or according to the preferred embodiment, which is combined as a matrix material with other matrix materials for use in a phosphorescent emitter. In a preferred embodiment of the invention, the other matrix material is a hole transport compound. In another preferred embodiment of the invention, the other matrix material is an electron transport compound. In yet another preferred embodiment, the other matrix material is a compound with a large band gap, which, even if it participates in hole and electron transport, does not significantly participate in hole and electron transport in the layer.

[0125] Suitable matrix materials that can be used in combination with the compounds of formula (1) or according to preferred embodiments are aromatic ketones, aromatic phosphine oxides, or aromatic sulfoxides or sulfones, for example according to WO 2004 / 013080, WO 2004 / 093207, WO2006 / 005627 or WO 2010 / 006680; triarylamines, especially monoamines, for example according to WO 2014 / 015935; carbazole derivatives, such as CBP (N,N-biscarbazole biphenyl) or carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851; indolecarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 056746; indobenzocarbazole derivatives, for example according to WO 2010 / 136109 and WO2011 / 000455; azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160; bipolar matrix materials, for example according to WO 2007 / 137725; silanes, for example according to WO 2005 / 111172; azaborane cyclopentadiene or borate esters, for example according to WO 2006 / 117052; triazine derivatives, for example according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746; zinc complexes, for example according to EP 652273 or WO 2009 / 062578; diazasiloxane or tetraazasiloxane derivatives, for example according to WO 2010 / 054729; diazaphosphanecyclopentadiene derivatives, for example according to WO 2010 / 054730; bridged carbazole derivatives, for example according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107, WO 2011 / 088877 or WO 2012 / 143080; benzo[a]phenanthrene derivatives, for example according to WO 2012 / 048781; lactams, for example according to WO 2011 / 116865, WO 2011 / 137951 or WO 2013 / 064206; or 4-spirocarbazole derivatives, for example according to WO 2014 / 094963 or WO 2015 / 192939. Similarly, other phosphorescent emitters that emit light at shorter wavelengths than the actual emitter can also exist as co-substrate in the mixture.

[0126] Preferred co-host materials are triarylamine derivatives, especially monoamines, indocarbazole derivatives, 4-spirocarbazole derivatives, lactams, and carbazole derivatives.

[0127] In another embodiment of the invention, the organic electroluminescent device of the present invention does not contain any separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, meaning that the light-emitting layer is directly adjacent to the hole injection layer or anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode, as described, for example, in WO 2005 / 053051. Furthermore, a metal complex consistent with or similar to the metal complex in the light-emitting layer can be used as the hole transport or hole injection material directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0128] Furthermore, the compounds of the present invention can be used in hole transport or electron blocking layers.

[0129] 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 can use any material known for use in organic electroluminescent devices in combination with formula (1) of the present invention or the compound according to the preferred embodiment without any inventive effort.

[0130] Furthermore, a preferred organic electroluminescent device is one in which one or more layers are coated by sublimation. In this case, the material is sublimated in a vacuum sublimation system at a temperature below 10°C. -5 mbar, preferably below 10 -6 An initial pressure of mbar is applied via vapor deposition. This initial pressure can also be even lower or higher, for example, below 10 mbar. -7 mbar.

[0131] Similarly, preferred organic electroluminescent devices are characterized by one or more layers being coated by an OVPD (organic vapor deposition) method or with the aid of carrier gas sublimation. In this case, the material is in 10 -5 The material is applied at pressures between mbar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and thus structured (e.g., MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0132] Furthermore, a preferred organic electroluminescent device is characterized by one or more layers being produced from a solution, for example by spin coating or by any printing method such as inkjet printing, LITI (photoinduced thermal imaging, thermal transfer printing), screen printing, flexographic printing, offset printing, or nozzle printing. For this purpose, a soluble compound is required, which is obtained, for example, through suitable substitution.

[0133] The compounds of the present invention exhibit improved oxidative stability, particularly in solution, especially compared to commonly used diamines. This is particularly important for printing processes. Another characteristic of the compounds of the present invention is their high thermal stability, allowing them to be evaporated under high vacuum without decomposition. Thermal stability also improves the operating life of the compounds.

[0134] Furthermore, hybrid methods are feasible, in which, for example, one or more layers are applied from a solution, and another one or more layers are applied via vapor deposition. For example, a luminescent layer can be applied from a solution and an electron transport layer can be applied via vapor deposition.

[0135] In summary, these methods are known to those skilled in the art and can be applied by those skilled in the art to organic electroluminescent devices containing the compounds of the present invention without inventive effort.

[0136] The compounds of the present invention generally exhibit very good performance when used in organic electroluminescent devices. In particular, the lifetime of the compounds of the present invention is significantly better compared to similar compounds according to the prior art in the application of organic electroluminescent devices. At the same time, other properties of the organic electroluminescent devices, especially efficiency and voltage, are also better or at least comparable.

[0137] The invention will now be illustrated in detail by way of the following embodiments, which are not intended to limit the invention in any way.

[0138] Example

[0139] The following synthesis, unless otherwise stated, was carried out under a protective gas atmosphere in anhydrous solvents. Solvents and reagents can be purchased, for example, from Sigma-Aldrich or ABCR. For compounds known from the literature, the corresponding CAS numbers are also reported in each case.

[0140] Synthesis example

[0141] a) 4-Bromo-9-methyl-9-phenyl-9H-fluorene

[0142] 30 g (94 mmol) of 2,2'-dibromobiphenyl was dissolved in 200 mL of anhydrous THF in a baked flask. The reaction mixture was cooled to -78 °C. At this temperature, 37.7 mL of a 2.5 M solution (94 mmol) of n-butyllithium in hexane was slowly added dropwise (over approximately 1 h). The mixture was stirred at -70 °C for 1 h. Subsequently, 11.1 mL of acetophenone (94 mmol) was dissolved in 100 mL of THF and added dropwise at -70 °C. After the addition was complete, the reaction mixture was gradually heated to room temperature, quenched with NH4Cl, and then concentrated using a rotary evaporator. 300 mL of acetic acid was carefully added to the concentrated solution, followed by 50 mL of fuming HCl. The mixture was heated to 75 °C for 6 h. During this time, a white solid precipitated. The mixture was cooled to room temperature, the precipitated solid was filtered off by suction and washed with methanol. The residue was dried under reduced pressure at 40 °C. The yield was 25.3 g (75 mmol) (80% of the theoretical value).

[0143] b) 4-Bromo-9,9-diphenyl-9H-fluorene

[0144] 37 g (152 mmol) of 2,2'-dibromobiphenyl was dissolved in 300 mL of anhydrous THF in a baked flask. The reaction mixture was cooled to -78 °C. At this temperature, 75 mL of a 15% solution (119 mmol) of n-butyllithium in hexane was slowly added dropwise (over approximately 1 h). The mixture was stirred at -70 °C for 1 h. Subsequently, 21.8 g of benzophenone (119 mmol) was dissolved in 100 mL of THF and added dropwise at -70 °C. After the addition was complete, the reaction mixture was gradually heated to room temperature, quenched with NH4Cl, and then concentrated using a rotary evaporator. 510 mL of acetic acid was carefully added to the concentrated solution, followed by 100 mL of fuming HCl. The mixture was heated to 75 °C for 4 h. During this time, a white solid precipitated. The mixture was cooled to room temperature, the precipitated solid was filtered off by suction and washed with methanol. The residue was dried under reduced pressure at 40 °C. The yield was 33.2 g (83 mmol) (70% of the theoretical value).

[0145] The following brominated compounds were prepared in a similar manner:

[0146] c) 6-Bromo-2-fluoro-2'-methoxybiphenyl

[0147] 200 g (664 mmol) of 1-bromo-3-fluoro-2-iodobenzene, 101 g (664 mmol) of 2-methoxyphenylboronic acid, and 137.5 g (997 mmol) of sodium tetraborate were dissolved in 1000 mL of THF and 600 mL of water and degassed. 9.3 g (13.3 mmol) of bis(triphenylphosphine)palladium(II) chloride and 1 g (20 mmol) of hydrazine hydroxide were added. The reaction mixture was then stirred at 70 °C for 48 h under a protective atmosphere. Toluene was added to the cooled solution, which was repeatedly washed with water, dried, and concentrated. The product was purified by column chromatography on silica gel using toluene / heptane (1:2). Yield: 155 g (553 mmol), 83% of the theoretical value.

[0148] The following compounds were prepared in a similar manner:

[0149] d) 6'-Bromo-2'-fluorobiphenyl-2-ol

[0150] 112 g (418 mmol) of 6-bromo-2-fluoro-2'-methoxybiphenyl was dissolved in 2 L of dichloromethane and cooled to 5 °C. 41.0 mL (431 mmol) of boron tribromide was added dropwise to the solution over 90 min, and the mixture was stirred overnight. The mixture was then gradually mixed with water, the organic phase was washed three times with water, dried over Na₂SO₄, concentrated by rotary evaporation, and purified by chromatography. Yield: 104 g (397 mmol), 98% of theoretical value.

[0151] The following compounds were prepared in a similar manner:

[0152] e) 1-Bromodibenzofuran

[0153] 111 g (416 mmol) of 6'-bromo-2'-fluorobiphenyl-2-ol was dissolved in 2 L of DMF (maximum 0.003% H2O) SeccoSolv® and cooled to 5°C. 20 g (449 mmol) of sodium hydride (60% suspension in paraffin oil) was added aliquots to the solution. Once the addition was complete, the mixture was stirred for 20 min and then heated to 100°C for 45 min. After cooling, 500 mL of ethanol was gradually added to the mixture, which was then concentrated by rotary evaporation and purified by chromatography. Yield: 90 g (367 mmol), 88.5% of theoretical value.

[0154] The following compounds were prepared in a similar manner:

[0155] f) Biphenyl-4-yldibenzofuran-1-ylamine

[0156] First, 30.0 g (177 mmol, 1.0 eq) of 4-aminobiphenyl was loaded together with 43.7 g (177 mmol, 1.0 eq) of 1-bromodibenzofuran and 2.4 g (212 mmol, 1.20 eq) of sodium tert-amyl alcohol [14593-46-5] in 600 mL of anhydrous toluene and degassed for 30 min. Then, 398 mg (1.77 mmol, 0.01 eq) of palladium(II) acetate [3375-31-3] and 1.46 g (3.56 mmol, 0.02 eq) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl SPHOS [657408-07-6] were added, and the mixture was heated under reflux overnight. After the reaction was complete, the mixture was cooled to room temperature and extracted with 500 mL of water. The aqueous phase was then washed three times with toluene, the combined organic phases were dried over sodium sulfate, and the solvent was removed by rotary evaporation. The brown residue was transferred to approximately 200 ml of toluene and filtered through silica gel. For further purification, recrystallization from toluene / heptane was performed. Yield: 44 g (133 mmol), 76% of theoretical value.

[0157] The following compounds were prepared in a similar manner:

[0158]

[0159]

[0160] g) Dibenzofuran-1-yl-(4-dibenzofuran-4-ylphenyl)-(9,9-dimethyl-9H-fluoren-4-yl)amine

[0161] A mixture of 13.6 g (50 mmol) 4-bromo-9,9-dimethyl-9H-fluorene, 25.5 g (60 mmol) dibenzofuran-1-yl-(4-dibenzofuran-4-ylphenyl)amine, 7.7 g (80 mmol) sodium tert-butoxide, 1.4 g (5 mmol) tricyclohexylamine, 561 mg (2.5 mmol) palladium(II) acetate, and 300 ml mesitylene was heated under reflux for 24 h. After cooling, 200 ml of water was added, and the mixture was stirred for another 30 min. The organic phase was removed, and the mixture was filtered through a short diatomaceous earth bed. The solvent was then removed under reduced pressure. The residue was recrystallized from DMF five times and finally fractionated twice (p = approximately 10). -6 mbar (T = 340-350℃). Yield: 23 g (37 mmol), 75% of theoretical value; purity obtained by HPLC was 99.9%.

[0162] The following compounds were obtained in a similar manner:

[0163]

[0164]

[0165]

[0166] h)1-Bromo-8-iododibenzofuran

[0167] 20 g (80 mmol) of dibenzofuran-1-boric acid, 2.06 g (40.1 mmol) of iodine, 3.13 g (17.8 mmol) of iodic acid, 80 ml of acetic acid, 5 ml of sulfuric acid, 5 ml of water, and 2 ml of chloroform were stirred at 65 °C for 3 h. After cooling, the mixture was mixed with water, and the precipitated solid was filtered off by suction filtration and washed three times with water. The residue was recrystallized from toluene and from dichloromethane / heptane. The yield was 25.6 g (68 mmol), corresponding to 85% of the theoretical value.

[0168] The following compounds were prepared in a similar manner:

[0169] i)3-(9-bromodibenzofuran-2-yl)-9-phenyl-9H-carbazole

[0170] 58 g (156 mmol) of 1-bromo-8-iododibenzofuran, 50 g (172 mmol) of N-phenylcarbazole-3-boric acid, and 36 g (340 mmol) of sodium carbonate were suspended in 1000 ml of ethylene glycol dimethyl ether and 280 ml of water. 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)palladium(O) was added to the suspension, and the reaction mixture was heated under reflux for 16 h. After cooling, the organic phase was removed, filtered through silica gel, washed three times with 200 ml of water, and then concentrated to dryness. The yield was 48 g (89 mmol), corresponding to 64% of the theoretical value.

[0171] The following compounds were prepared in a similar manner:

[0172]

[0173]

[0174] j) Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl)-[8-(9-phenyl-9H-carbazol-3-yl)dibenzofuran-1-yl]amine

[0175] A mixture of 9.3 g (26 mmol) biphenyl-4-yl-(9,9-dimethyl-9H-fluorene-4-yl)amine, 12 g (26 mmol) 3-(9-bromodibenzofuran-2-yl)-9-phenyl-9H-carbazole, 7.7 g (80 mmol) sodium tert-butoxide, 2.6 ml (78 mmol) tritert-butylphosphine (1M, toluene), 224 mg (2.6 mmol) palladium(II) acetate, and 300 ml mesitylene was heated under reflux for 24 h. After cooling, 200 ml of water was added, and the mixture was stirred for another 30 min. The organic phase was removed and filtered through a short diatomaceous earth bed, followed by solvent removal under reduced pressure. The residue was recrystallized from DMF five times and then fractionally sublimed twice (p = approximately 10). -6 mbar (T = 340-350℃). Yield: 13 g (17 mmol), 68% of theoretical value; purity obtained by HPLC was 99.9%.

[0176] The following compounds were prepared in a similar manner:

[0177]

[0178]

[0179]

[0180]

[0181] OLED production

[0182] Data for various OLEDs are presented in the following examples C1 to I9 (see Tables 1 and 2).

[0183] Pretreatment for Examples C1-I9: To improve processing, a glass plate coated with a 50 nm thick structured ITO (indium tin oxide) was coated with a 20 nm layer of PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate), purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH, Germany, spin-coated from an aqueous solution). These coated glass plates form the substrate for applying the OLED.

[0184] The OLED generally has the following layer structure: substrate / hole transport layer (HTL) / optional intermediate layer (IL) / electron blocking layer (EBL) / emitting layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally a cathode. The cathode is formed of an aluminum layer with a thickness of 100 nm. The specific structure of the OLED can be found in Table 1. The materials used to produce the OLED are shown in Table 3.

[0185] All materials are applied in a vacuum chamber via thermal vapor deposition. In this case, the luminescent layer always consists of at least one matrix material (host material) and a luminescent dopant (emitting agent), which is added to the matrix material by co-evaporation in a specific volume ratio. Details given, for example, in the form of IC5:IC3:TEG1 (45%:45%:10%) 30 nm, mean that materials IC5, IC3, and TEG1 are present in the layer at a volume ratio of 45%, 45%, and 10%, respectively. Similarly, the electron transport layer can also be composed of a mixture of the two materials.

[0186] The OLED was characterized in a standard manner. For this purpose, the electroluminescence spectrum, voltage, external quantum efficiency (EQE, measured as a percentage), and lifetime were determined. Voltage and EQE as functions of luminance were calculated from the current / voltage / luminance characteristic line (IUL characteristic line) under the assumption of Lambertian luminescence characteristics. The electroluminescence spectrum was measured at 1000 cd / m². 2The brightness is determined at a given level. Here, parameter U1000 in Table 2 refers to 1000 cd / m². 2 The voltage required for brightness. EQE1000 refers to the voltage required at 1000 cd / m². 2 The external quantum efficiency at the operating luminance. Lifetime LT is defined as the time it takes for the luminance to decrease from its initial value to a certain percentage L1 during operation with a constant current. The figures L0;j0 = 4000 cd / m² and L1 = 70% in Table 2 mean that the lifetime reported in the LT column corresponds to the time it takes for the initial luminance to decrease from 4000 cd / m² to 2800 cd / m². Similarly, L0;j0 = 20 mA / cm² and L1 = 80% mean that during operation at 20 mA / cm², the luminance decreases to 80% of its initial value after time LT.

[0187] Data for various OLEDs are summarized in Table 2. Examples C1 to C8 are comparative examples based on the prior art; Examples I1-I9 illustrate data for the OLEDs of the present invention.

[0188] To illustrate the advantages of the OLED of the present invention, certain embodiments are described in detail below.

[0189] Use of the mixture of the present invention in the light-emitting layer of a phosphorescent OLED

[0190] When used in the emissive layer (EML) and electron blocking layer (EBL) of phosphorescent OLEDs, the materials of the present invention offer significant improvements over the prior art, particularly in terms of the lifetime of OLED components. By using the compounds INV-1 to INV-3 of the present invention in combination with IC5 and the green dopant TEG1, a lifetime increase of over 40% compared to the prior art VG-1 to VG-4 can be observed (comparison of Examples C1-C4 with I1-I3). By using the compounds INV-1 to INV-3 of the present invention in the EBL, a lifetime increase of over 25% compared to the prior art VG-1 to VG-4 can be observed (comparison of Examples C5-C8 with I4-I6).

[0191]

[0192]

[0193]

[0194]

Claims

1. A compound of formula (1) for use in an electron blocking and / or exciton blocking layer and / or hole transport layer and / or hole injection layer of an organic electroluminescent device, Equation (1) The symbols used are as follows: X is O or S; Y is O, S, or CR2; Ar is selected from structures of formulas (Ar-2) to (Ar-4), (Ar-8), (Ar-9), (Ar-11), and (Ar-13) to (Ar-16), wherein Ar contains only aryl or heteroaryl groups having at most 15 aromatic ring atoms, and does not contain carbazolyl groups as heteroaryl groups, nor 9,9'-spirodifluorene groups. in Q is the same or different in every case and is CR 4 Or N, where no more than 3 Q symbols in each ring are N; E is the same or different in every case, and is C(R) 4 2. O, S, or C=O, where two R's 4 It does not form aromatic or hybrid aromatic ring systems; G is the same or different in every case, and is NR 4 C(R) 4 )2, O, S, or C=O; and This represents a bond attached to a nitrogen atom; R may be the same or different in each case, and is selected from H, D, F, Cl, I, CN, NO2, N (Ar) 1 )2,N(R 4 )2,C(=O)Ar 1 C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of said groups being capable of being generated by one or more R 4 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 4 C=CR 4 C=O, C=S, C=NR 4 P(=O)(R) 4 SO, SO2, NR 4 O, S or CONR 4 The atoms are replaced, and one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2, having 5 to 40 aromatic ring atoms and in each case, being replaced by one or more R atoms. 4 Aromatic ring systems with substituted groups, having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 1 A group-substituted aryloxy or heteroaryloxy group, or having 5 to 40 aromatic ring atoms and being capable of being substituted by one or more R groups. 4 The alkyl or heteroaryl groups are substituted with a group; additionally, optionally, two R substituents bonded to the same or adjacent carbon atoms can form a group that can be substituted by one or more R groups. 4 Monocyclic or polycyclic aliphatic ring systems with substituted groups; R 1 The same or different in each case, and selected from H, D, F, Cl, I, CN, NO2, N (Ar) 1 )2,N(R 4 )2,C(=O)Ar 1 C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of said groups being capable of being generated by one or more R 4 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 4 C=CR 4 C=O, C=S, C=NR 4 P(=O)(R) 4 SO, SO2, NR 4 O, S or CONR 4 The atoms can be replaced by D, F, Cl, Br, I, CN, or NO2, and the rings have 5 to 40 aromatic ring atoms and can be replaced by one or more R atoms. 4 A group-substituted aryloxy or heteroaryloxy group, or having 5 to 40 aromatic ring atoms and being capable of being substituted by one or more R groups. 4 The alkyl or heteroaryl group is substituted with a group; and optionally, two R groups are bonded to adjacent carbon atoms. 1 Substituents or two Rs 1 and R 3 Substituents can form groups that can be formed by one or more R groups. 4 Monocyclic or polycyclic aliphatic ring systems with substituted groups; R 2 The same or different in each case, and selected from H, D, F, Cl, Br, I, CN, NO2, N (Ar) 1 )2,N(R 4 )2,C(=O)Ar 1 C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of said groups being capable of being generated by one or more R 4 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 4 C=CR 4 C=O, C=S, C=NR 4 P(=O)(R) 4 SO, SO2, NR 4 O, S or CONR 4 The atoms are replaced, and one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2, having 5 to 40 aromatic ring atoms and in each case, being replaced by one or more R atoms. 4 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 4 A group-substituted aryloxy or heteroaryloxy group, or having 5 to 40 aromatic ring atoms and being capable of being substituted by one or more R groups. 4 The alkyl or heteroaryl group is substituted with a group; and optionally, two R groups are bonded to adjacent carbon atoms. 2 Substituents can form groups that can be formed by one or more R groups. 4 Monocyclic or polycyclic aliphatic ring systems with substituted groups; R 3 The same or different in each case, and selected from H, D, F, Cl, Br, I, CN, NO2, N (Ar) 1 )2,N(R 4 )2,C(=O)Ar 1 C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of said groups being capable of being generated by one or more R 4 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 4 C=CR 4 C=O, C=S, C=NR 4 P(=O)(R) 4 SO, SO2, NR 4 O, S or CONR 4 The atoms are replaced, and one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2, having 5 to 40 aromatic ring atoms and in each case, being replaced by one or more R atoms. 4 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 4 A group-substituted aryloxy or heteroaryloxy group, or having 5 to 40 aromatic ring atoms and being capable of being substituted by one or more R groups. 4 The alkyl or heteroaryl group is substituted with a group; and optionally, two R groups are bonded to adjacent carbon atoms. 1 and R 3 Substituents can form groups that can be formed by one or more R groups. 4 Monocyclic or polycyclic aliphatic ring systems with substituted groups; Ar 1 The same or different in each case, and having 5 to 30 aromatic ring atoms and can be separated by one or more non-aromatic R atoms. 4 Aromatic or heteroaromatic ring systems with substituent groups; simultaneously, two Ar atoms bonded to the same phosphorus or boron atom. 1 Groups can also be formed by single bonds or by means of N(R) 4 ), C(R 4 2. The bridge bases of O and S are connected to each other; R 4 The same or different in each case, and selected from H, D, F, Cl, Br, I, CN, NO2, N(R) 5 )2,C(=O)R 5 The groups are straight-chain alkyl, alkoxy, or thioalkyl groups having 1 to 20 carbon atoms, or branched or cyclic alkyl, alkoxy, or thioalkyl groups having 3 to 20 carbon atoms, or alkenyl groups having 2 to 20 carbon atoms, each of which may be derived from one or more R groups. 5 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 5 C=CR 5 C=O, C=S, C=NR 5 P(=O)(R) 5 SO, SO2, NR 5 O, S or CONR 5 The atoms are replaced, and one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2, having 5 to 40 aromatic ring atoms and in each case, being replaced by one or more R atoms. 5 Aromatic ring systems with substituted groups, having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 5 A group-substituted aryloxy or heteroaryloxy group, or having 5 to 40 aromatic ring atoms and being capable of being substituted by one or more R groups. 5 Group-substituted aralkyl or heteroaralkyl groups; simultaneously, optionally, two R groups bonded to the same or adjacent carbon atoms. 4 Substituents can form groups that can be formed by one or more R groups. 5 Monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring systems with substituted groups; R 5 In each case, the same or different, and selected from H, D, F, CN, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms can be replaced by D, F, Cl, Br, I or CN, and said aromatic or heteroaromatic ring system can be replaced by one or more alkyl groups each having 1 to 4 carbon atoms; simultaneously, two or more adjacent R 5 Substituents can work together to form monocyclic or polycyclic aliphatic ring systems; in, In one case, the nitrogen atom is bonded to the corresponding carbon atom in place of R. 1 Or R 3 In R 3 In this case, Y cannot be CR2; in Exclude the following compounds: 。 2. The compound according to claim 1, characterized in that... X is O.

3. The compound according to one or more of claims 1 and 2, characterized in that... Y is either O or S.

4. The compound according to one or more of claims 1 to 3, characterized in that... The compound is a compound of formula (1-1) or formula (1-2). Equation (1-1) Equation (1-2) The symbols have the definitions given in claim 1.

5. The compound according to one or more of claims 1 to 4, characterized in that... The compound is a compound of formula (2). Equation (2) The symbol has the definition given in claim 1, and wherein an R bonded to a carbon atom 2 And an R 4 It has been replaced by a single key.

6. The compound according to one or more of claims 1 to 5, characterized in that... The compound is a compound of formulas (2-1) and (2-2). Equation (2-1) Equation (2-2) The symbols have the definition given in claim 1, and one of the R symbols in equation (2-2) has the definition given in claim 1. 2 And the R bonded to the carbon atom in formula (2-1) 4 It has been replaced by a single key.

7. The compound according to claim 6, characterized in that... In equation (2-2), R is replaced by a single bond. 2 It is not arranged on the 6-membered ring bonded to the nitrogen atom.

8. The compound according to one or more of claims 1 to 7, characterized in that... Ar is selected from groups of formula (Ar-2-1) to (Ar-16-6): The symbols correspond to those in equations (Ar-2) to (Ar-16), and the above equations can be represented by R in their free positions. 4 replace.

9. The compound according to one or more of claims 1 to 8, characterized in that... Ar is a group of formula (Ar-14), where G is the same or different in each case and is NR. 4 C(R) 4 )2 or O.

10. The compound according to claim 9, characterized in that... G is the same or different in every case and is C(R) 4 )2 or O.

11. The compound according to one or more of claims 1 to 10, characterized in that: Applicable to the symbols used: X, Y, and Ar have the definitions in claim 1; R may be the same or different in each case, and is selected from H, D, straight-chain alkyl groups having 1 to 8 carbon atoms or branched or cyclic alkyl groups having 3 to 8 carbon atoms, each of which may be represented by one or more R groups. 4 Group substitution, wherein one or more hydrogen atoms can be replaced by D, or having 6 to 18 aromatic ring atoms and in each case being replaced by one or more R groups. 4 Aromatic ring systems with substituted groups; R 1 The same or different in each case, and selected from H, D, F, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 8 carbon atoms or a branched or cyclic alkyl group having 3 to 8 carbon atoms, each of said groups may be generated by one or more R 4 Group substitution, in which one or more hydrogen atoms can be replaced by D; R 2 The same or different in each case, and selected from H, D, F, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 8 carbon atoms or a branched or cyclic alkyl group having 3 to 8 carbon atoms, each of said groups may be generated by one or more R 4 Group substitution, wherein one or more hydrogen atoms can be replaced by D, or having 6 to 18 aromatic ring atoms and in each case being replaced by one or more R groups. 4 Aromatic or heteroaromatic ring systems with substituted groups; R 3 The same or different in each case, and selected from H, D, F, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 8 carbon atoms or a branched or cyclic alkyl group having 3 to 8 carbon atoms, each of said groups may be generated by one or more R 4 Group substitution, wherein one or more hydrogen atoms can be replaced by D, or having 6 to 18 aromatic ring atoms and in each case being replaced by one or more R groups. 4 Aromatic or heteroaromatic ring systems with substituted groups; Ar 1 The same or different in each case, and having 5 to 30 aromatic ring atoms and can be separated by one or more non-aromatic R atoms. 4 Aromatic or heteroaromatic ring systems with substituted groups; R 4 In each case, the same or different, and selected from H, D, F, CN, a straight-chain alkyl group having 1 to 8 carbon atoms or a branched or cyclic alkyl group having 3 to 8 carbon atoms, wherein one or more hydrogen atoms may be replaced by D, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms; and optionally, two R atoms bonded to the same carbon atom 4 Substituents can form monocyclic or polycyclic aliphatic or aromatic ring systems; In one case, the nitrogen atom is bonded to the corresponding carbon atom in place of R. 1 Or R 3 .

12. The compound according to one or more of claims 1 to 11, characterized in that: Applicable to the symbols used: X is O; Y is O; Ar has the definition in claim 1; R 1 The same or different in each case, and selected from H, D, N (Ar) 1 )2, a straight-chain alkyl group having 1, 2, 3 or 4 carbon atoms or a branched or cyclic alkyl group having 3, 4, 5 or 6 carbon atoms, wherein one or more hydrogen atoms may be replaced by D; R 2 The same or different in each case, and selected from H, D, N (Ar) 1 )2, a straight-chain alkyl group having 1, 2, 3, or 4 carbon atoms, or a branched or cyclic alkyl group having 3, 4, 5, or 6 carbon atoms, wherein one or more hydrogen atoms may be replaced by D, or having 6 to 13 aromatic ring atoms and in each case may be replaced by one or more R atoms. 4 Aromatic ring systems with substituted groups; R 3 In each case, the same or different, and selected from H, D, a straight-chain alkyl group having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3, 4, 5 or 6 carbon atoms, wherein one or more hydrogen atoms may be replaced by D, or having 6 to 13 aromatic ring atoms and in each case may be replaced by one or more R atoms. 4 Aromatic ring systems with substituted groups; Ar 1 The same or different in each case, and having 5 to 30 aromatic ring atoms and can be separated by one or more non-aromatic R atoms. 4 Aromatic ring systems with substituted groups; R 4 In each case, the same or different, and selected from H, D, a straight-chain alkyl group having 1, 2, 3, or 4 carbon atoms, or a branched or cyclic alkyl group having 3, 4, 5, or 6 carbon atoms, wherein one or more hydrogen atoms may be replaced by D, or an aromatic ring system having 6 to 13 aromatic ring atoms; and optionally, two R atoms bonded to the same carbon atom 4 Substituents can form monocyclic or polycyclic aliphatic or aromatic ring systems; In one case, the nitrogen atom is bonded to the corresponding carbon atom in place of R. 1 Or R 3 .

13. The compound according to one or more of claims 1 to 12, characterized in that: Applicable to the symbols used: X is O; Y is O; Ar has the definition in claim 1; R 1 The same or different in each case, and selected from H, D or N (Ar) 1 )2; R 2 The same or different in each case, and selected from H or D; R 3 The same or different in each case, and selected from H or D; Ar 1 The same or different in each case, and is an aromatic ring system with 5 to 30 aromatic ring atoms; R 4 In each case, they may be the same or different, and are selected from H, D, or an aromatic ring system having 6 to 13 aromatic ring atoms; meanwhile, optionally, two R atoms bonded to the same carbon atom 4 Substituents can form monocyclic or polycyclic aliphatic or aromatic ring systems; In one case, the nitrogen atom is bonded to the corresponding carbon atom in place of R. 1 Or R 3 .

14. The compound according to one or more of claims 1 to 13, characterized in that: Applicable to the symbols used: X is O; Y is O; Ar is a group of formula (Ar-14), where G is the same or different in each case and is C(R). 4 )2 or O; R 1 The same or different in each case, and selected from H, D or N (Ar) 1 )2; R 2 The same or different in each case, and selected from H or D; R 3 The same or different in each case, and selected from H or D; R 4 In each case, they may be the same or different, and are selected from H, D, or an aromatic ring system having 6 aromatic ring atoms; meanwhile, optionally, the two R atoms bonded to the same carbon atom 4 Substituents can form monocyclic or polycyclic aliphatic or aromatic ring systems; In one case, the nitrogen atom is bonded to the corresponding carbon atom in place of R. 1 Or R 3 .

15. A mixture comprising at least one compound according to one or more of claims 1 to 14 and at least one other compound and / or at least one solvent.

16. Use of the compound according to one or more of claims 1 to 14 or the mixture according to claim 15 in an electronic device.

17. An electronic device comprising at least one compound according to one or more of claims 1 to 14 or a mixture according to claim 15.

18. The electronic device according to claim 17, characterized in that... It is an organic electroluminescent device.

19. The electronic device according to claim 18, characterized in that... The compound according to one or more of claims 1 to 14 or the mixture according to claim 15 is used in the light-emitting layer, or in the hole transport layer or the electron blocking layer.

20. The electronic device according to claim 18 or 19, characterized in that... The compound according to one or more of claims 1 to 14 is used in a hole transport layer or an electron blocking layer.

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