Materials for electronic devices

Abstract

The present application relates to heterocyclic spirobifluorene compounds and to electronic devices, in particular organic electroluminescent devices, comprising heterocyclic spirobifluorene derivatives.

Description

[0001] The present application relates to heterospirofluorene compounds of formula (I) as defined in detail below. The compounds are preferably used in electronic devices, particularly preferably in organic electroluminescent devices (OLEDs).

[0002] In the context of the present application, electronic devices are to be understood as meaning so-called "organic electronic devices" which contain organic semiconducting materials as functional materials. More particularly, these devices are to be understood as meaning organic electroluminescent (EL) devices, in particular organic light-emitting diodes (OLEDs). The design and general working principle of OLEDs are known to the person skilled in the art.

[0003] In electronic devices, in particular in EL devices such as OLEDs, there is a great interest in improving the performance data, in particular the lifetime, the efficiency and the operating voltage. In these respects, no completely satisfactory solution has yet been found.

[0004] Layers having a hole-transporting function, such as hole-injection layers, hole-transporting layers, electron-blocking layers, and also light-emitting layers, have a great influence on the performance data of electronic devices. In order to be used in these layers, there is a constant search for new materials having hole-transporting properties.

[0005] In the prior art, triarylamine compounds such as spirobifluorene amines and fluorene amines are known as hole-transporting materials and hole-transporting matrix materials for electronic devices. The use of acridine derivatives, more particularly spirobiscridines, in OLEDs has also been disclosed in the prior art, for example in JP 2002-265938, KR 2011-0120075 or WO 2015 / 158411. However, there is still a need for improvement with regard to the performance mentioned above.

[0006] It has now been found that spirobiscridine compounds of formula (I) as defined below are very suitable for use in OLEDs. They are particularly suitable for use in hole-transporting layers, more particularly in electron-blocking layers.

[0007] The compounds found have one or more of the following properties: very good hole-conducting properties, very good electron-blocking properties, high oxidative stability, good solubility and high-temperature stability. When used in OLEDs, they result in OLEDs having one or more of the following advantageous properties: long lifetime, high quantum efficiency and low operating voltage.

[0008] The present application relates to a compound of formula (I)

[0009]

[0010] of formula (I),

[0011] wherein the following applies for the symbols and signs occurring:

[0012] A is C or Si;

[0013] Y is on each occurrence, identically or differently, N or P;

[0014] X is on each occurrence, identically or differently, CR 1 or N;

[0015] Ar 1 , Ar 2 is on each occurrence, identically or differently: an aromatic ring system having 6 to 40 aromatic ring atoms which can be substituted by one or more radicals R 2 or a heteroaromatic ring system having 5 to 40 aromatic ring atoms which can be substituted by one or more radicals R 2 ; whereof at least one of the two radicals Ar 1 and Ar 2 is: an aromatic ring system having 12 to 40 aromatic ring atoms which can be substituted by one or more radicals R 2 or a heteroaromatic ring system having 12 to 40 aromatic ring atoms which can be substituted by one or more radicals R 2 ;

[0016] R 3 , R 4 , R 5 , R 6 is on each occurrence, identically or differently, selected from: D, F, C(=0)R, CF3, OCF3, CN, Si(R)3, N(R)2, P(=0)(R)2, S(=0)R, S(=0)2R, a straight-chain alkyl, alkoxy or thioalkyl radical having 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 20 C atoms, an alkenyl or alkynyl radical having 2 to 20 C atoms, where the alkyl, alkoxy, alkenyl and alkynyl radicals can in each case be substituted by one or more radicals R and where one or more H atoms in the above-mentioned radicals can be replaced by D or F; an aromatic ring system having 6 to 40 aromatic ring atoms which can be substituted by one or more radicals R or a heteroaromatic ring system having 5 to 40 aromatic ring atoms which can be substituted by one or more radicals R;

[0017] R 1 , R 2in each case identically or differently selected from: H, D, F, C(=0)R, CF3, OCF3, CN, Si(R)3, N(R)2, P(=0)(R)2, S(=0)R, S(=0)2R, a straight-chain alkyl, alkoxy or thioalkyl group with 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 C atoms, an alkenyl or alkynyl group with 2 to 20 C atoms, where the alkyl, alkoxy, alkenyl and alkynyl groups can in each case be substituted with one or more radicals R and in which one or more H atoms in the above-mentioned groups can be replaced by D or F; an aromatic ring system with 6 to 40 aromatic ring atoms which can be substituted with one or more radicals R, or a heteroaromatic ring system with 5 to 40 aromatic ring atoms which can be substituted with one or more radicals R; where two or more radicals R 1 or R 2 may be linked to one another and can form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic and heteroaromatic ring systems can each be substituted with one or more radicals R; and in which one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups can be replaced by -R0=CR-, -CºC-, Si(R)2, C=0, C=NR, -C(=0)0-, -C(=0)NR-, NR, P(=0)(R), -0-, -S-, SO or S02;

[0018] R in each case identically or differently is selected from: H, D, F, C(=0)R´, CF3, OCF3, CN, Si(R´)3, N(R´)2, P(=0)(R´)2, S(=0)R´, S(=0)2R´, a straight-chain alkyl, alkoxy or thioalkyl group with 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 C atoms, an alkenyl or alkynyl group with 2 to 20 C atoms, where one or more H atoms in the above-mentioned groups can be replaced by D or F, an aromatic ring system with 6 to 40 aromatic ring atoms and a heteroaromatic ring system with 5 to 40 aromatic ring atoms; where two or more radicals R can be linked to one another and can form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic and heteroaromatic ring systems can each be substituted with one or more radicals R´; and in which one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups can be replaced by -R´C=CR´-, -CºC-, Si(R´)2, C=0, C=NR´, -C(=0)0-, -C(=0)NR´-, NR´, P(=0)(R´), -0-, -S-, SO or S02;

[0019] R' is selected on each occurrence, identically or differently, from the group consisting of: H, D, F, CN, an alkyl group having 1 to 20 C atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where two or more radicals R' can be linked to one another and can form a ring; and where the alkyl group, the aromatic ring system and the heteroaromatic ring system can be substituted by F or CN;

[0020] a, b, c, d are 0, 1, 2, 3 or 4 on each occurrence, identically or differently; where at least one of the signs a, b, c and d is equal to 1 ; and

[0021] at least one group R 3 , R 4 , R 5 or R 6 is present in the compound of the formula (I), which at least one group R 3 , R 4 , R 5 or R 6 represents: F, Si(R)3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where the alkyl, alkoxy or thioalkyl group can in each case be substituted by one or more radicals R and where one or more H atoms in the above-mentioned radicals can be replaced by D or F.

[0022] If the sign a, b, c or d is equal to 0, the corresponding group R 3 , R 4 , R 5 or R 6 is not present.

[0023] If the sign a, b, c or d is equal to 1, the corresponding group R 3 , R 4 , R 5 or R 6 is bonded to one of the groups X of the ring. This group X is then equal to C, the four valency of carbon.

[0024] The following definitions apply to chemical groups used as general definitions. They apply only if no more specific definition is given.

[0025] An aryl group in the sense of the present application contains 6 to 60 aromatic ring atoms which are not heteroatoms. An aryl group in the sense of the present application is to be regarded as meaning a simple aromatic ring, i.e. benzene, or a fused aromatic polycyclic ring system, e.g. naphthalene, phenanthrene or anthracene. A fused aromatic polycyclic ring system in the sense of the present application consists of two or more simple aromatic rings which are fused to one another. The fusion between the rings is to be regarded here as meaning that the rings share at least one edge with one another.

[0026] Heteroaryl groups in the sense of the application contain 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms of the heteroaryl groups are preferably selected from N, O and S. Heteroaryl groups in the sense of the application are to be regarded as meaning simple aromatic rings, i.e. benzene, or simple heteroaromatic rings, for example pyridine, pyrimidine or thiophene, or fused heteroaromatic polycyclic ring systems, for example quinoline or carbazole. Fused heteroaromatic polycyclic ring systems in the sense of the application consist of two or more simple heteroaromatic rings which are fused to one another. The fusion between the rings is to be regarded here as meaning that the rings share at least one edge with one another.

[0027] Aryl or heteroaryl groups which in each case can be substituted by the groups mentioned above and can be attached to the aromatic or heteroaromatic ring system via any desired position are to be regarded as meaning in particular groups which originate from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene, fluoranthene, benzanthracene, benzophenanthrene, benzochole, benzochole, benzopyrene, 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, phenoxazine, pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthylidine, azacarbazole, benzocarbolin, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 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, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0028] An aromatic ring system in the sense of the present application contains 6 to 60 C atoms in the ring system and does not contain heteroatoms as aromatic ring atoms. Thus, an aromatic ring system in the sense of the present application does not contain heteroaryl groups. An aromatic ring system in the sense of the present application is to be understood as meaning a system which does not necessarily contain only aryl groups, but in which a plurality of aryl groups can additionally be connected by single bonds or by non-aromatic units, for example, such as one or more optionally substituted C, Si, N, O or S atoms. The non-aromatic units here contain less than 10% of non-H atoms, based on the total number of non-H atoms in the system. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether and stilbene, and also systems in which two or more aryl groups are connected, for example, by straight-chain or cyclic alkyl, alkenyl or alkynyl groups or by silyl groups, are also to be understood as meaning aromatic ring systems in the sense of the present application. Furthermore, for example, systems in which two or more aryl groups are connected to one another via single bonds, such as systems of biphenyl and terphenyl, are also to be understood as meaning aromatic ring systems in the sense of the present application.

[0029] A heteroaromatic ring system in the sense of the present application contains 5 to 60 aromatic ring atoms, of which at least one is a heteroatom. The heteroatoms of the heteroaromatic ring system are preferably selected from N, O and / or S. The heteroaromatic ring system corresponds to the definition of the aromatic ring system mentioned above, but contains at least one heteroatom as one of the aromatic ring atoms. Thus, in the sense of the definition of the present application, the heteroaromatic ring system is distinguished from the aromatic ring system which, by definition, cannot contain a heteroatom as an aromatic ring atom.

[0030] An aromatic ring system having 6 to 60 aromatic ring atoms or a heteroaromatic ring system having 5 to 60 aromatic ring atoms is to be understood in particular as meaning a group which is derived from the groups mentioned above in the aryl groups and the heteroaryl groups, and from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydropyrene, tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, indenocarbazole, or from combinations of these groups.

[0031] For the purposes of the present application, straight-chain alkyl radicals having 1 to 40 C atoms or branched or cyclic alkyl radicals having 3 to 40 C atoms in which individual H atoms or CH2groups can be substituted by the radicals mentioned above under the definition of the radicals are preferably understood to mean methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl.

[0032] For the purposes of the present application, straight-chain alkyl radicals having 1 to 40 C atoms or branched or cyclic alkyl radicals having 3 to 40 C atoms in which individual H atoms or CH2groups can be substituted by the radicals mentioned above under the definition of the radicals are preferably understood to mean methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, 2-ethylhexyl, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0033] For the purposes of the present application, the expression two or more radicals can form a ring with one another is understood to mean, in particular, that the two radicals are connected to one another by a chemical bond. However, in addition, the expression mentioned above is also understood to mean, in the case where one of the two radicals represents hydrogen, that the second radical is bonded at the position where the hydrogen atom is bonded, thereby forming a ring.

[0034] According to one preferred embodiment, the compounds of the formula (I) do not contain arylamino radicals as substituents. An arylamino radical in the sense of the present application is understood to mean a radical in which one or more aryl or heteroaryl radicals are bonded to a nitrogen atom, preferably three aryl or heteroaryl radicals are bonded to a nitrogen atom.

[0035] According to another preferred embodiment of the invention, the compound of formula (I) does not contain fused aryl groups having more than 10 aromatic ring atoms, and does not contain fused heteroaryl groups having more than 14 aromatic ring atoms.

[0036] According to another preferred embodiment of the present invention, the compound of formula (I) is used as a non-luminescent hole transport material in a layer having hole transport function, such as a hole injection layer, a hole transport layer, or an electron blocking layer.

[0037] According to another preferred embodiment of the present invention, the compound of formula (I) is used as a non-luminescent host material with hole transport properties and combined with the luminescent body in the luminescent layer.

[0038] Preferably, in formula (I), exactly one, two, three, or four of the marks selected from marks a, b, c, and d are equal to 1 or 2.

[0039] Preferably, exactly one, two, or three of the marks selected from marks a, b, c, and d are equal to 1 or 2. Particularly preferred are exactly one or two of the marks selected from marks a, b, c, and d that are equal to 1 or 2.

[0040] According to a preferred embodiment of the present invention, marker a is equal to 1, and markers b, c and d are equal to 0.

[0041] According to an alternative preferred embodiment, labels a and b are equal to 1, and labels c and d are equal to 0.

[0042] According to another preferred embodiment, label a equals 2, and labels b, c, and d equal 0.

[0043] A is preferably a carbon atom.

[0044] Y is preferably a nitrogen atom.

[0045] In the compound of formula (I), each six-membered ring preferably has at most three X groups equal to N, particularly preferably at most two X groups equal to N, and very particularly preferably at most one X group equal to N.

[0046] Preferably, no more than two directly adjacent X groups in the ring are equal to N.

[0047] X is preferred equal to CR 1 , where R 1 Preferably selected from H and D, either the same or different.

[0048] Preferably, Ar 1 and Ar 2 In each case, the same or different selections are made from substances that can be selected by one or more groups R. 2A substituted aromatic ring system having 6 to 24 aromatic ring atoms, or selected from aromatic ring systems that can be substituted by one or more R groups. 2 Substituted heteroaromatic ring systems with 5 to 24 aromatic ring atoms, wherein two Ar groups 1 and Ar 2 At least one of them is: can be converted by one or more groups R 2 Aromatic ring systems with 12 to 24 substituted aromatic ring atoms, or those that can be replaced by one or more R groups 2 Substituted heteroaromatic ring systems having 12 to 24 aromatic ring atoms. More preferably, the Ar group 1 and Ar 2 Both are selected, in each case, either identically or differently, from those that can be selected by one or more groups R. 2 Aromatic ring systems with 12 to 24 substituted aromatic ring atoms, and aromatic ring systems that can be substituted by one or more R groups 2 Substituted heteroaromatic ring systems having 12 to 24 aromatic ring atoms. Even more preferably, the Ar group... 1 and Ar 2 Both are selected, in each case, either identically or differently, from those that can be selected by one or more groups R. 2 Substituted aromatic ring systems with 12 to 18 aromatic ring atoms.

[0049] More preferably, the two Ar groups 1 and Ar 2 At least one of them is: can be converted by one or more groups R 2 Substituted biphenyl, terphenyl, or fluorene groups. Even more preferably, both Ar groups... 1 and Ar 2 Selected, either identically or differently, from: those that can be selected by one or more groups R 2 Substituted biphenyl, terphenyl, and fluorene.

[0050] Preferably, R 3 R 4 R 5 R 6 In each case, the group is selected from the following groups, either identically or differently: F, CF3, OCF3, Si(R)3, straight-chain alkyl, alkoxy, or thioalkyl groups having 1 to 20 C atoms, branched or cyclic alkyl, alkoxy, or thioalkyl groups having 3 to 20 C atoms, wherein the alkyl, alkoxy, and thioalkyl groups may be substituted with one or more groups R in each case and wherein one or more H atoms of the groups mentioned above may be substituted with D or F; aromatic ring systems having 6 to 40 aromatic ring atoms that may be substituted with one or more groups R, or heteroaromatic ring systems having 5 to 40 aromatic ring atoms that may be substituted with one or more groups R.

[0051] According to the present invention, the compound of formula (I) contains at least one group R. 3 R 4 R 5 or R 6 The at least one group R 3 R 4 R 5 or R 6 Representative: F, Si(R)3, 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, wherein the alkyl, alkoxy, or thioalkyl group may in each case be substituted by one or more groups R and wherein one or more H atoms of the groups mentioned above may be substituted by D or F. Preferably, the compound of formula (I) contains at least one group R. 3 R 4 R 5 or R 6 The at least one group R 3 R 4 R 5 or R 6 Representative: a straight-chain alkyl group having 1 to 20 C atoms, more preferably 1 to 10 C atoms, or even more preferably 2 to 10 C atoms; a branched or cyclic alkyl group having 3 to 20 C atoms, more preferably 3 to 10 C atoms, wherein the alkyl group may be substituted by one or more groups R in each case and wherein one or more H atoms of the groups mentioned above may be substituted by D or F.

[0052] The following describes the presence of at least one group R in the compound of formula (I). 3 R 4 R 5 or R 6 An example, the at least one group R 3 R 4 R 5 or R 6 Representatives: F, Si(R)3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, or thioalkyl group may in each case be substituted by one or more groups R and wherein one or more H atoms of the groups mentioned above may be substituted by D or F:

[0053]

[0054] Preferably, the group R 3 R 4 R 5 R6 At least one of the groups selected from formulas R-1 to R-10, more preferably one of the groups R-2 to R-7. Even more preferably, all groups R 3 R 4 R 5 R 6 It may be selected from one of the groups of formula R-1 to R-10, either the same or different, and is particularly preferred to be selected from one of the groups of R-2 to R-7.

[0055] According to a preferred embodiment, all groups R present in the compound of formula (I) 3 R 4 R 5 and R 6 The same or different representations are: F, Si(R)3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, or thioalkyl group may in each case be substituted by one or more groups R and wherein one or more H atoms of the groups mentioned above may be substituted by D or F. Preferably, all groups R present in the compound of formula (I) 3 R 4 R 5 and R 6 The same or different means represent: a straight-chain alkyl group having 1 to 20 C atoms, more preferably 1 to 10 C atoms, even more preferably 2 to 10 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, more preferably 3 to 10 C atoms, wherein the alkyl group may be substituted by one or more groups R in each case and wherein one or more H atoms of the groups mentioned above may be substituted by D or F.

[0056] According to another preferred embodiment, the compound of formula (I) comprises:

[0057] At least one group R 3 R 4 R 5 or R 6 The at least one group R 3 R 4 R 5 or R 6 Representatives: F, Si(R)3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, or thioalkyl group may in each case be substituted by one or more groups R and wherein one or more H atoms of the groups mentioned above may be substituted by D or F, and

[0058] At least one group R 3 R 4 R 5 or R 6 The at least one group R 3 R 4 R 5 or R 6 Representative: Aromatic ring systems having 6 to 40 aromatic ring atoms that can be substituted by one or more groups R, or heteroaromatic ring systems having 5 to 40 aromatic ring atoms that can be substituted by one or more groups R.

[0059] More preferably, the compound of formula (I) comprises:

[0060] At least one group R 3 R 4 R 5 or R 6 The at least one group R 3 R 4 R 5 or R 6 Representative: a straight-chain alkyl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 2 to 10 carbon atoms; a branched or cyclic alkyl group having 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, wherein the alkyl group may in each case be substituted by one or more groups R and wherein one or more H atoms in the groups mentioned above may be substituted by D or F, and

[0061] At least one group R 3 R 4 R 5 or R 6 The at least one group R 3 R 4 R 5 or R 6 Representative: an aromatic ring system having 6 to 30, preferably 6 to 18, aromatic ring atoms that can be substituted by one or more groups R, or a heteroaromatic ring system having 5 to 30, preferably 6 to 18, aromatic ring atoms that can be substituted by one or more groups R.

[0062] Preferably, the compound of formula (I) is selected from one of formulas (I-1) to (I-7).

[0063]

[0064]

[0065] The symbols and markings that appear are as defined above.

[0066] More preferably, the compound of formula (I) is selected from one of formulas (I-1-1) to (I-7-1).

[0067]

[0068]

[0069]

[0070]

[0071] The symbols and markings that appear are as defined above.

[0072] Even more preferably, the compound of formula (I) is selected from the compounds of formulas (I-1-1) to (I-7-1), wherein Ar 1 Ar 2 R 3 R 4 R 5 R 6 Corresponding to the preferred embodiments mentioned above for these groups, and wherein:

[0073] X represents CR 1 , where R 1 Selected from H and D, either the same or different.

[0074] In formulas (I-1-1) to (I-7-1), the preferred formulas are (I-1-1), (I-2-1), (I-3-1), (I-4-1), (I-5-1), (I-6-1), and (I-7-1), the most preferred formulas are (I-2-1), (I-3-1), (I-4-1), and (I-6-1), and the particularly preferred formulas are (I-2-1) and (I-4-1).

[0075] Preferably, in formulas (I-1) to (I-7) and (I-1-1) to (I-7-1):

[0076] - Group R 6 Selected from: F, Si(R)3, straight-chain alkyl, alkoxy, or thioalkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl, alkoxy, or thioalkyl groups having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, or thioalkyl group may in each case be substituted by one or more groups R and wherein one or more H atoms of the groups mentioned above may be substituted by D or F; and

[0077] - Group R 3 R 4 R 5The same or different from: D, F, C(=O)R, CF3, OCF3, CN, Si(R)3, N(R)2, P(=O)(R)2, S(=O)R, S(=O)2R, straight-chain alkyl, alkoxy, or thioalkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl, alkoxy, or thioalkyl groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl, and alkynyl groups are each substituted with one or more groups R in each case and wherein one or more H atoms of the groups mentioned above are substituted with D or F; an aromatic ring system having 6 to 40 aromatic ring atoms that can be substituted with one or more groups R, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms that can be substituted with one or more groups R.

[0078] More preferably, in equations (I-1) to (I-7) and (I-1-1) to (1-7-1):

[0079] - Group R 6 Selected from: F, Si(R)3, straight-chain alkyl, alkoxy, or thioalkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl, alkoxy, or thioalkyl groups having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, or thioalkyl group may in each case be substituted by one or more groups R and wherein one or more H atoms of the groups mentioned above may be substituted by D or F; and

[0080] - Group R 3 R 4 R 5 The same or different are selected from: F, Si(R)3, straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 C atoms, branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, wherein the alkyl, alkoxy or thioalkyl groups are in each case substituted by one or more groups R and wherein one or more H atoms in the groups mentioned above are substituted by D or F; aromatic ring systems having 6 to 30, preferably 6 to 18, aromatic ring atoms that can be substituted by one or more groups R, or heteroaromatic ring systems having 5 to 30, preferably 6 to 18, aromatic ring atoms that can be substituted by one or more groups R.

[0081] Preferably, the compound of formula (I) is a deuterated compound. The term "deuterated compound" here refers to a compound in which deuterium is present at least 100 times more abundant than in nature. Higher degrees of deuteration than in nature can be achieved by using pre-deuterated structural units or by treating the compound with a deuteration method.

[0082] According to the present invention, the degree of deuteration corresponds to the percentage of the number of deuterium atoms in the compound to the total number of deuterium and protium atoms in the compound, as follows:

[0083] Degree of deuteration (%) = (N D 100) / (N P + N D )

[0084] in:

[0085] N D The number of deuterium atoms in the compound

[0086] N P The number of deuterium and protium atoms in the compound

[0087] Unless otherwise stated, the term hydrogen in this invention refers to the protium isotope of hydrogen, which accounts for more than 99.98% of naturally occurring hydrogen in the ocean.

[0088] Preferably, the compound of formula (I) has a deuteration degree of 20%, 40%, 60% or 80%.

[0089] Examples of compounds of formula (I) are described in the table below:

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] Compounds of formula (I) can be prepared using known reactions in organic chemistry, such as bromination, Buchwald coupling, and Suzuki coupling.

[0105] A general method for preparing compounds of formula (I) is illustrated in application WO 2015 / 158411. Specific examples of methods for preparing compounds of formula (I) are also shown in the embodiments.

[0106] The compounds according to the present invention can be used or applied in conjunction with other organic functional materials commonly used in electronic devices according to the prior art. Those skilled in the art of electronic devices know a variety of suitable organic functional materials. Therefore, the present invention also provides a composition comprising: one or more compounds of formula (I), or one or more polymers, oligomers, or dendritic macromolecules containing one or more compounds of formula (I), and at least one other organic functional material selected from: phosphors, phosphorescent materials, host materials, matrix materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, electron blocking materials, hole blocking materials, wide bandgap materials, delayed phosphors, and delayed fluorescence hosts.

[0107] Delayed-fluorescence emitters and delayed-fluorescence hosts are known in the art and disclosed, for example, in Ye Tao et al., Adv. Mater. 2014, 26, 7931-7958, MY Wong et al., Adv. Mater. 2017, 29, 1605444, WO 2011 / 070963, WO 2012 / 133188, WO 2015 / 022974, and WO 2015 / 098975. Typically, delayed-fluorescence materials (emitters and / or hosts) are characterized by exhibiting a relatively small band gap between their singlet energy (S1) and triplet energy (T1). Preferably, ΔE ST The voltage is equal to or less than 0.5 eV, very preferably equal to or less than 0.3 eV, particularly preferably equal to or less than 0.2 eV, and most preferably equal to or less than 0.1 eV, wherein ΔE ST This represents the difference between the singlet energy (S1) and the triplet energy (T1).

[0108] In this invention, wide bandgap materials should be understood to refer to the materials disclosed in US 7,294,849, characterized by a bandgap of at least 3 eV, preferably at least 3.5 eV, and very preferably at least 4.0 eV, wherein the term "bandgap" refers to the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Such systems exhibit particularly advantageous performance characteristics in electroluminescent devices.

[0109] For processing the compounds and compositions of the present invention from a liquid state, for example by spin coating or printing, formulations of the compounds and compositions of the present invention are required. These formulations may be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents are preferred. Suitable and preferred solvents are, for example: toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, naphthylene, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenone, 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, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or mixtures of these solvents.

[0110] Therefore, the present invention also provides a formulation, particularly a solution, dispersion, or emulsion, comprising: at least one compound of formula (I), or an oligomer, polymer, or dendritic macromolecule containing one or more compounds of formula (I), or at least one composition comprising one or more compounds of formula (I) and at least one other organic functional material as described above, and at least one solvent, preferably an organic solvent. Methods for preparing such solutions are known to those skilled in the art and are described, for example, in WO 2002 / 072714, WO 2003 / 019694, and documents cited therein.

[0111] The compounds of this invention are suitable for use in electronic devices, and particularly for use in organic electroluminescent devices such as OLEDs. Depending on the substitutions, the compounds can be used in different functions and layers.

[0112] Therefore, the present invention also provides the use of compounds of formula (I), or oligomers, polymers, or dendritic macromolecules containing one or more compounds of formula (I), or compositions containing one or more compounds of formula (I) and at least one other organic functional material as described above, in electronic devices. The electronic devices are preferably selected from: organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, and more preferably organic electroluminescent devices (EL devices). Preferred EL devices are organic light-emitting transistors (OLETs), organic field quenching devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs), with OLEDs being the most preferred.

[0113] As described above, the present invention also provides an electronic device comprising at least one compound of formula (I). The electronic device is preferably selected from the devices mentioned above.

[0114] Particularly preferably, the electronic device is an organic light-emitting diode (OLED), also known as an organic electroluminescent diode or device, the organic light-emitting diode (OLED) comprising an anode, a cathode and at least one organic layer formed between the anode and the cathode, characterized in that at least one organic layer comprises at least one compound of formula (I), the organic layer may be a light-emitting layer, a hole transport layer or another layer, preferably a light-emitting layer or a hole transport layer, particularly preferably a hole transport layer.

[0115] A hole transport layer is located between the anode and the light-emitting layer and supports the transport of holes that pass through it, enabling them to reach the light-emitting layer. Preferably, the OLED includes a hole transport region comprising one or more hole transport layers, including a hole injection layer, a hole transport layer, and an electron blocking layer. The hole injection layer (HIL) is preferably located between the anode and another hole transport layer. The hole injection layer injects holes into the adjacent hole transport layer. The electron blocking layer (EBL) (also called an auxiliary layer) is preferably located between the hole transport layer and the light-emitting layer, more preferably adjacent to the light-emitting layer. The electron blocking layer blocks electrons and confines them within the light-emitting layer. The electron blocking layer may comprise one or more electron blocking layers.

[0116] According to a preferred embodiment, the electronic device is an organic light-emitting diode (OLED), which includes an anode, at least one hole transport layer, at least one light-emitting layer, at least one electron transport layer, and a cathode, wherein the at least one hole transport layer comprises a compound of formula (I).

[0117] According to a highly preferred embodiment, the electronic device is an organic light-emitting diode (OLED), which includes an anode, at least one hole transport layer, at least one light-emitting layer, at least one electron transport layer and a cathode, wherein the at least one hole transport layer comprises a compound of formula (I), and wherein the at least one hole transport layer is formed between the anode and the light-emitting layer, and the at least one electron transport layer is formed between the light-emitting layer and the cathode.

[0118] According to a particularly preferred embodiment, the electronic device is an organic light-emitting diode (OLED), which includes an anode, a hole transport layer, an emissive layer, an electron transport layer, and a cathode. The hole transport layer comprises a first hole transport layer and a second hole transport layer, wherein the first hole transport layer is formed between the anode and the second hole transport layer, and the second hole transport layer is formed between the first hole transport layer and the emissive layer. The second hole transport layer comprises a compound of formula (I). Preferably, the second hole transport layer is an electron blocking layer. More preferably, the second hole transport layer is an electron blocking layer adjacent to the emissive layer. The electron blocking layer may comprise one, two, or more electron blocking layers, wherein one of the electron blocking layers comprises a compound of formula (I).

[0119] More specifically, the electronic device is preferably an organic light-emitting diode (OLED), which comprises the following components in the following order:

[0120] - Anode

[0121] - First Hole Transport Layer

[0122] - Electron blocking layer

[0123] - Emissive layer

[0124] - Electron transport layer

[0125] - Cathode,

[0126] At least one of the electron blocking layers contains a compound of formula (I).

[0127] According to a highly preferred embodiment, the order of the middle layers in the OLED is as follows:

[0128] Base,

[0129] anode,

[0130] The optional hole injection layer HIL is preferably p-type doped, p-HIL.

[0131] First Hole Transport Layer (HTL)

[0132] Electron blocking layer EBL1

[0133] Optional second electron blocking layer EBL2

[0134] Eluminating layer EML

[0135] Optional hole-blocking layer HBL,

[0136] Electronic transport layer (ETL),

[0137] Optional electron injection layer EIL, and

[0138] The cathode, wherein EBL1 or, when present, EBL2 comprises a compound of formula (I), and wherein other layers may additionally exist in the OLED.

[0139] In this invention, the term "organic layer" should be understood to mean any layer of an electronic device that contains one or more organic compounds as functional materials.

[0140] In addition to the cathode, anode, and the aforementioned layers, organic light-emitting diodes may also include other layers. These are selected from, for example, hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, and charge generation layers (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton organic EL device having charge generation layer ) and / or organic or inorganic p / n junctions.

[0141] The organic light-emitting diode of the present invention may contain two or more light-emitting layers. More preferably, in this case, these light-emitting layers collectively have multiple emission maximum values ​​between 380 nm and 750 nm, resulting in overall white emission; in other words, a variety of light-emitting compounds are used in the light-emitting layers, which may fluoresce or phosphorize, and emit blue, green, yellow, orange, or red light. Particularly preferred is a three-layer system, i.e., a system having three light-emitting layers, wherein the three layers exhibit blue, green, and orange or red emission (for the basic construction, see, for example, WO 2005 / 011013). The compounds of the present invention are preferably present in a hole transport layer, a hole injection layer, or an electron blocking layer, and most preferably in an electron blocking layer.

[0142] According to the present invention, it is preferred to use the compound of formula (I) in an electronic device comprising one or more phosphorescent compounds. In this case, the compound may be present in different layers, preferably in a hole transport layer, an electron blocking layer, a hole injection layer, or in a light-emitting layer.

[0143] The term "phosphorescent compound" generally refers to compounds that emit light through spin-forbidden transitions, such as from an excited triplet state or a state with a higher spin quantum number, such as a quintet state.

[0144] Suitable phosphorescent compounds (= triplet emitters) are particularly those that emit light when properly excited, preferably in the visible light region, and further contain at least one atom with an atomic number greater than 20, preferably greater than 38 but less than 84, more preferably greater than 56 but less than 80. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferred as phosphorescent compounds, especially those containing iridium, platinum, or copper. In the context of this invention, all luminescent iridium, platinum, or copper complexes are considered phosphorescent compounds.

[0145] Examples of the aforementioned luminescent compounds can be found in applications WO 00 / 70655, WO 01 / 41512, WO 02 / 02714, WO02 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, and US 2005 / 0258742. Generally, all phosphorescent complexes known to those skilled in the art for use in phosphorescent OLEDs and organic electroluminescent devices are suitable. Without inventive effort, those skilled in the art can also combine other phosphorescent complexes with compounds of formula (I) in organic electroluminescent devices. Other examples are listed in the table below.

[0146] According to the present invention, the compound of formula (I) can also be used in electronic devices containing one or more fluorescent compounds.

[0147] In a preferred embodiment of the invention, the compound of formula (I) is used as a hole transport material. In this case, the compound is preferably present in a hole transport layer, an electron blocking layer, or a hole injection layer. It is particularly preferred to use it in an electron blocking layer.

[0148] According to this application, the hole transport layer is a layer with hole transport function located between the anode and the light-emitting layer.

[0149] In the context of this application, hole injection layer and electron blocking layer should be understood as specific embodiments of hole transport layer. When multiple hole transport layers are located between the anode and the light-emitting layer, the hole injection layer is a hole transport layer that is directly adjacent to the anode or separated from it only by a single coating of the anode. When multiple hole transport layers are located between the anode and the light-emitting layer, the electron blocking layer is a hole transport layer that is directly adjacent to the light-emitting layer on the anode side. Preferably, the OLED of the present invention comprises two, three, or four hole transport layers between the anode and the light-emitting layer, preferably at least one of which contains a compound of formula (I), more preferably exactly one or two of which contain compounds of formula (I).

[0150] If the compound of formula (I) is used as a hole transport material in a hole transport layer, hole injection layer, or electron blocking layer, the compound can be used as a pure material in the hole transport layer, i.e., used in 100% proportion, or the compound can be used in combination with one or more other compounds. In a preferred embodiment, the organic layer containing the compound of formula (I) further contains one or more p-type dopants. The p-type dopants used according to the invention are preferably those organic electron acceptor compounds capable of oxidizing one or more other compounds in the mixture.

[0151] Particularly preferred embodiments of p-type dopants are the compounds disclosed in WO 2011 / 073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US 8057712, WO2009 / 003455, WO 2010 / 094378, WO 2011 / 120709, US 2010 / 0096600, WO 2012 / 095143 and DE102012209523.

[0152] Particularly preferred p-type dopants include: quinone dimethane compounds; azidofluorene dione; azidofluorene; azidotriphenylide; I₂; metal halides, preferably transition metal halides; metal oxides, preferably metal oxides containing at least one transition metal or a Group 3 metal; and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd, and Pt with ligands containing at least one oxygen atom as a bonding site. Transition metal oxides are also preferred as dopants, particularly oxides of rhenium, molybdenum, and tungsten, and more preferably Re₂O₇, MoO₃, WO₃, and ReO₃.

[0153] The p-type dopant is preferably substantially uniformly dispersed in the p-type doped layer. This can be achieved, for example, by co-evaporation of the p-type dopant and the hole transport material matrix.

[0154] Preferred p-type dopants are particularly the following compounds:

[0155]

[0156] In another preferred embodiment of the invention, the compound of formula (I) is used as a hole transport material in combination with a hexaaza-heterotriphenylide derivative as described in US 2007 / 0092755. It is particularly preferred to use the hexaaza-heterotriphenylide derivative in a separate layer.

[0157] The table below lists other hole transport materials that can be used in any layer requiring hole transport capabilities, such as hole injection layers (HIL), hole transport layers (HTL), electron blocking layers (EBL), or light-emitting layers (EML). The compounds can be readily prepared according to the published literature cited for each compound. Compounds HT-1 to HT-33 exhibit excellent stability, and electronic devices containing these compounds demonstrate high efficiency, low voltage, and improved lifetime.

[0158]

[0159]

[0160]

[0161] The teachings on the use of the compounds and methods of preparing the compounds contained in the aforementioned patent applications are expressly incorporated herein by reference. When used in OLEDs, compounds HT-1 to HT-33 exhibit excellent performance, particularly excellent lifetime and efficiency. This is especially true when they are used in the hole transport layer of OLEDs.

[0162] In another embodiment of the invention, the compound of formula (I) is used as a matrix material in combination with one or more luminescent compounds, preferably phosphorescent compounds, in the luminescent layer.

[0163] 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.

[0164] Accordingly, the proportion of the luminescent compound 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.

[0165] The emitting layer of an organic light-emitting diode (OLED) may also comprise a system containing multiple matrix materials (a mixed matrix system) and / or multiple luminescent compounds. In this case, typically, the luminescent compounds are those compounds in a smaller proportion of the system, and the matrix materials are those compounds in a larger proportion of the system. However, in some cases, the proportion of a single matrix material in the system may be less than the proportion of a single luminescent compound.

[0166] The compound of formula (I) is preferably used as a component of the mixed matrix system. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material with hole transport properties, and the other is a material with electron transport properties. The compound of formula (I) is preferably a matrix material with hole transport properties. However, the desired electron transport and hole transport properties of the mixed matrix components may also be primarily or completely incorporated into a single mixed matrix component, in which case the other mixed matrix component performs 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 organic light-emitting diodes. A source of more detailed information about the mixed matrix system is application WO 2010 / 108579.

[0167] The hybrid matrix system may contain one or more luminescent compounds, preferably one or more phosphorescent luminescent compounds. Typically, a hybrid matrix system is preferred in phosphorescent organic light-emitting diodes.

[0168] Particularly suitable matrix materials that can be combined with the compounds of the present invention as matrix components of a mixed matrix system are selected from preferred matrix materials specified below for phosphorescent compounds or preferred matrix materials specified below for fluorescent compounds, depending on the type of luminescent compound used in the mixed matrix system.

[0169] The preferred phosphorescent compounds used in the mixed matrix system are the same as those typically preferred phosphorescent materials, which are described in further detail elsewhere.

[0170] Preferred embodiments of different functional materials in electronic devices are listed below.

[0171] Preferred phosphorescent compounds are the following compounds:

[0172]

[0173]

[0174]

[0175]

[0176] Preferred fluorescent compounds are selected from arylamines. In the context of this invention, arylamines or aromatic amines should be understood as 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 pyrine amines, or aromatic pyrine diamines. Aromatic anthraceneamines should be understood as compounds in which a diaryl amino group is directly bonded to an anthracene group, preferably at the 9-position. Aromatic anthracene diamines should be understood as compounds in which two diaryl amino groups are directly bonded to an anthracene group, preferably at the 9- and 10-positions. Aromatic pyreneamines, pyrene diamines, pyrine amines, and pyrine diamines are similarly defined, wherein the diaryl amino groups are preferably bonded to pyrene at the 1-position or at the 1- and 6-positions. Other preferred luminescent compounds are: indolefluoreneamine or indolefluorenediamine, for example according to WO 2006 / 108497 or WO 2006 / 122630; benzo[a]indolefluoreneamine or benzo[a]indolefluorenediamine, for example according to WO 2008 / 006449; and dibenzo[a]indolefluoreneamine or dibenzo[a]indolefluorenediamine, for example according to WO 2007 / 140847; and indolefluorene 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 WO 2014 / 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.

[0177] Preferred matrix materials for fluorescent compounds include materials from various material classes. Preferred matrix materials are selected from the following categories: oligomeric aromatic compounds (e.g., 2,2',7,7'-tetraphenylspirodifluorene or dinafylanthracene according to EP 676461), especially oligomeric aromatic compounds containing fused aromatic groups; oligomeric aromatic vinyl compounds (e.g., DPVBi or spiro-DPPVBi according to EP 676461); multi-legged metal complexes (e.g., according to WO2004 / 081017); hole-conducting compounds (e.g., according to WO 2004 / 058911); electron-conducting compounds, especially ketones, phosphine oxides, sulfoxides, etc. (e.g., according to WO 2005 / 084081 and WO 2005 / 084082); transisomers (e.g., according to WO 2006 / 048268); boric acid derivatives (e.g., according to WO... (e.g., according to WO 2006 / 117052); or benzanthracene (e.g., according to WO 2008 / 145239). Particularly preferred matrix materials are selected from the following categories: oligomeric aromatic compounds, including naphthalene, anthracene, benzanthracene and / or pyrene, or trans-isomers of these compounds; oligomeric aromatic vinyl compounds; ketones; phosphine oxides; and sulfoxides. Very particularly preferred matrix materials are selected from the following categories: oligomeric aromatic compounds, including anthracene, benzanthracene, benzo[a]phenanthrene and / or pyrene, or trans-isomers of these compounds. In the context of this invention, oligomeric aromatic compounds should be understood to mean compounds in which at least three aryl or aromatic derivative groups are bonded to each other. Other preferred materials include: anthracene derivatives disclosed in WO 2006 / 097208, WO 2006 / 131192, WO 2007 / 065550, WO 2007 / 110129, WO 2007 / 065678, WO 2008 / 145239, WO 2009 / 100925, WO 2011 / 054442 and EP 1553154; pyrene compounds disclosed in EP 1749809, EP 1905754 and US 2012 / 0187826; benzo[a]anthracite compounds disclosed in WO 2015 / 158409; indo[a]benzo[a]furan disclosed in WO 2017 / 025165; and phenanthrene anthracene disclosed in WO 2017 / 036573.

[0178] Preferred matrix materials for phosphorescent compounds, in addition to compounds of formula (I), include: aromatic ketones, aromatic phosphine oxides, aromatic sulfoxides, or aromatic sulfones, for example, according to WO2004 / 013080, WO 2004 / 093207, WO 2006 / 005627, or WO 2010 / 006680; triarylamines, carbazole derivatives, such as CBP (N,N-dicarbazolyl biphenyl) or carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, or WO 2008 / 086851; indolocarbazole derivatives, for example, according to WO 2007 / 063754 or WO 2008 / 056746; and carbazole derivatives, for example, according to WO2010 / 136109, WO Indobenzocarbazole derivatives according to WO 2011 / 000455 or WO 2013 / 041176; azirazole derivatives according to EP1617710, EP 1617711, EP 1731584, JP 2005 / 347160; bipolar matrix materials according to WO 2007 / 137725; silanes according to WO 2005 / 111172; borazine or borate esters according to WO 2006 / 117052; triazine derivatives according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746; zinc complexes according to EP 652273 or WO 2009 / 062578; and so on. 2010 / 054729: silylated diazacyclopentane or silicotetrazacyclopentane derivatives; for example, phosphorus diazacyclopentane derivatives according to WO 2010 / 054730; for example, bridging carbazole derivatives according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107, WO 2011 / 088877 or WO 2012 / 143080; for example, triphenylene derivatives according to WO 2012 / 048781; or for example, lactams according to WO 2011 / 116865 or WO 2011 / 137951.

[0179] Suitable charge transport materials that can be used in the hole injection layer, hole transport layer, electron blocking layer, or electron transport layer of the electronic device of the present invention, in addition to the compounds of formula (I), 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.

[0180] Preferably, the OLED of the present invention comprises two or more distinct hole transport layers. The compound of formula (I) may be used in one or more of these layers, or in all of the hole transport layers. In a preferred embodiment, the compound of formula (I) is used in exactly one or exactly two hole transport layers, and other compounds, preferably aromatic amine compounds, are used in any additional hole transport layers present. Other compounds used with the compounds of formula (I), preferably other compounds used in the hole transport layer of the OLED of the present invention, especially: indene-fluoreneamine derivatives (e.g., according to WO 06 / 122630 or WO 06 / 100896), amine derivatives disclosed in EP 1661888, hexaazatriphenylide derivatives (e.g., according to WO 01 / 049806), amine derivatives having fused aromatic compounds (e.g., according to US 5,061,569), amine derivatives disclosed in WO 95 / 09147, monobenzo-indenefluoreneamine (e.g., according to WO 08 / 006449), dibenzo-indenefluoreneamine (e.g., according to WO 07 / 140847), spirodifluoreneamine (e.g., according to WO 2012 / 034627 and ... having fused aromatic compounds (e.g., according to WO 2012 / 034627 and WO 06 / 100896), 2013 / 120577), fluoreneamines (e.g., according to WO 2004 / 015937, WO 2014 / 015938, WO 2014 / 015935 and WO 2015 / 082056), spirodibenzopyranamines (e.g. according to WO 2013 / 083216), dihydroacridine derivatives (e.g. according to WO 2012 / 150001), spirodibenzofurans and spirodibenzothiophenes according to WO 2015 / 022051, WO 2016 / 102048 and WO 2016 / 131521, phenanthrene diarylamines according to WO 2015 / 131976, and so on. Spirotribenzocycloheptatrienolone according to 2016 / 087017, spirodifluorene having a m-phenylenediamine group according to WO2016 / 078738, spirobisacridine according to WO2015 / 158411, xanthondiarylamine according to WO2014 / 072017, and 9,10-dihydroanthracenespiro compounds having a diarylamino group according to WO2015 / 086108.

[0181] Spirodifluorene with a diarylamino group substituted at the 4-position is particularly preferred as a hole-transporting compound, especially those compounds claimed and 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 claimed and disclosed in WO 2012 / 034627.

[0182] The material used for the electron transport layer can be any material used as an electron transport material in an electron transport layer according to the prior art. Particularly suitable are aluminum complexes such as Alq3, zirconium complexes such as Zrq4, 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 compounds mentioned above, such as those disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975, and WO 2010 / 072300.

[0183] Preferred cathodes for electronic devices are metals with low work function, metal alloys composed of multiple metals, or multilayer structures. These metals are, for example, alkaline earth metals, alkali metals, group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Furthermore, alloys composed of alkali metals or alkaline earth metals and silver are suitable, such as alloys composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, other metals with relatively high work function, such as Ag or Al, can be used. In this case, combinations of these metals are typically used, such as Ca / Ag, Mg / Ag, or Ba / Ag. It is also preferable to introduce a thin interlayer of material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials suitable for this purpose are alkali metal fluorides or alkaline earth metal fluorides, and their corresponding oxides or carbonates (e.g., LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.). Lithium quinoline (LiQ) can also be used for this purpose. The thickness of this layer is preferably between 0.5 nm and 5 nm.

[0184] The preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, for this purpose, metals with high redox potentials, such as Ag, Pt, or Au, are suitable. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are also preferred. x Al / PtO xFor some applications, at least one of the electrodes must be transparent or partially transparent to allow for the illumination of organic materials (organic solar cells) or light emission (OLEDs, O-lasers). The preferred anode material here is a conductive mixed metal oxide. Indium tin oxide (ITO) or indium zinc oxide (IZO) is particularly preferred. Conductive doped organic materials, especially conductive doped polymers, are also preferred. Furthermore, the anode may also consist of two or more layers, for example, an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide, or vanadium oxide.

[0185] The device is appropriately structured (depending on the application), contact connections are provided, and finally it is sealed to eliminate the harmful effects of water and air.

[0186] In a preferred embodiment, the electronic device is characterized by coating one or more layers via a sublimation process. In this case, the layers are applied in 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, in this case, even lower, for example, less than 10... -7 An initial pressure of millibars is also feasible.

[0187] Another preferred electronic device is characterized by coating one or more layers using 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 spraying), 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).

[0188] Another preferred electronic 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, nozzle printing, or flatbed printing, but more preferably by LITI (photoinitiated thermal imaging, thermal transfer) or inkjet printing. For this purpose, a soluble compound of formula (I) is required. High solubility can be achieved by appropriate substitution of the compound.

[0189] It is also preferred that the electronic device of the present invention is manufactured by applying one or more layers from a solution and by applying one or more layers by sublimation.

[0190] According to the present invention, electronic devices comprising one or more compounds of formula (I) can be used in displays, as light sources in lighting applications, and as light sources in medical and / or cosmetic applications (e.g., phototherapy).

[0191] Compared with the prior art, the compounds according to the present invention and the electronic devices according to the present invention exhibit the following surprising and beneficial effects:

[0192] 1. The compounds according to the invention are particularly suitable as hole transport materials in electron blocking layers of electronic devices, such as electroluminescent devices, especially due to their excellent electron blocking and hole conduction properties.

[0193] 2. The compounds according to the invention are characterized by low sublimation temperature, high thermal stability, high oxidative stability, high glass transition temperature and high solubility, which are advantageous in terms of their processability, for example, from the liquid phase or from the gas phase, making them particularly suitable for use in electronic devices.

[0194] 3. When used in electronic devices, particularly as hole transport materials, the compounds according to the present invention exhibit excellent results in terms of device lifetime, operating voltage, and quantum efficiency.

[0195] 4. Deuterium compounds are more thermally stable, and devices containing these compounds exhibit longer lifetimes and improved efficiency.

[0196] The present invention will be described in more detail below with the aid of embodiments, which are not intended to limit the scope of the invention.

[0197] Example

[0198] A) Synthetic Example

[0199] A-1) Synthesis of basic symmetric structures

[0200] Step 1: 10-{[1,1'-biphenyl]-4-yl}-9,10-dihydroacridin-9-one 1a

[0201]

[0202] Under a protective atmosphere, 100 g (0.5 mol) of 10H-acridin-9-one, 140 g (0.6 mol) of 4-bromobiphenyl, 9.6 g (0.05 mol) of CuI, 104.0 g (0.75 mol) of potassium carbonate, and 22.0 ml (0.1 mol) of 2,2,6,6-tetramethylheptane-3,5-dione were dissolved in 600 ml of dimethylformamide. The reaction mixture was heated to boiling for 48 h under a protective atmosphere. Water was then added to the mixture. The solid was filtered off, washed with water and ethanol, and recrystallized from toluene.

[0203] Yield: 167 g (0.48 mol), 96% of the theoretical value.

[0204] The following compounds can be obtained similarly:

[0205]

[0206]

[0207] A-2) Synthesis of Asymmetric Acridinones

[0208] Step 1: 2-[bis({[1,1'-biphenyl]-4-yl})amino]-5-tert-butylbenzoate methyl ester 2a

[0209]

[0210] 50 g (155.5 mmol) of bisphenyl-4-ylamine, 66.9 g (246.9 mmol) of methyl 2-bromo-5-tert-butylbenzoate, 21.5 g (155.5 mmol) of potassium carbonate, 22.1 g (155.5 mmol) of sodium sulfate, and 0.9 g (15.5 mmol) of copper powder were suspended in 210 mL of nitrobenzene. The reaction mixture was heated at 220 °C for 6 h. After cooling, the mixture was filtered through diatomaceous earth, and the nitrobenzene was distilled off. The residue was filtered through silica gel (heptane / dichloromethane 1:1). The product was given in solid form. The yield was 64 g (80% of the theoretical value).

[0211] Step 2: 2-[bis({[1,1'-biphenyl]-4-yl})amino]-5-tert-butylbenzoic acid 3a

[0212]

[0213] 114.2 g (2722 mmol) of LiOH H₂O was added to a solution of 62 g (121.1 mmol) of methyl benzoate in 294 mL of dialkylene and 294 mL of water. The reaction mixture was heated at 105 °C for 16 h. After cooling, ethyl acetate was added, and the mixture was added to 1500 mL of 10% citric acid solution and extracted with ethyl acetate. The combined organic phases were dried and evaporated under vacuum. The residue was used in the next step without further purification.

[0214] Step 3: 10-{[1,1'-biphenyl]-4-yl}-2-tert-butyl-7-phenyl-9,10-dihydroacrylin-9-one 4a

[0215]

[0216] 62 g (124.5 mmol) of benzoic acid was dissolved in 364 ml of methanesulfonic acid, and the mixture was stirred overnight at 60 °C. After cooling, the mixture was slowly added to ice / water, and the precipitated solid was filtered off. The solid was dissolved in ethyl acetate and washed with 20% sodium bicarbonate solution. The combined organic phases were dried and evaporated under vacuum. The residue was recrystallized from MeOH. The yield was 56 g (94% of the theoretical yield).

[0217]

[0218] A-4) Formation of the screw unit

[0219] 10'-{[1,1'-biphenyl]-4-yl}-2-tert-butyl-10H,10'H-9,9'-spirodi[acridinium] 5a

[0220]

[0221] 42.6 g (140 mmol) of 2-bromo-N-(4-tert-butylphenyl)aniline was initially introduced into 350 mL of anhydrous THF, cooled to -78 °C, and 112 mL (280 mmol) of n-BuLi (2.5 M in THF) was added. The mixture was then thawed to -10 °C and stirred at this temperature for another 1 h. 30 g (86 mmol) of 10-biphenyl-4-yl-2,7-diphenyl-10H-acridin-9-one dissolved in 600 mL of THF was slowly added. The mixture was then stirred at room temperature for another 24 h. 100 mL of ammonium chloride solution was added, and the organic phase was separated by brief, continuous stirring, and the solvent was removed under vacuum. The residue was suspended in 750 mL of warm glacial acetic acid at 40 °C, and 60 mL of concentrated hydrochloric acid was added to the suspension, followed by stirring at room temperature for another 8 h. After cooling, the precipitated solid was filtered off, washed once with 100 ml of water, and three times with 100 ml of ethanol each time. Finally, it was recrystallized from heptane. Yield: 35.3 g (54 mmol), 74% of the theoretical value.

[0222]

[0223] A-5) Suzuki's reaction:

[0224] 10'-{[1,1'-biphenyl]-4-yl}-7'-tert-butyl-2-phenyl-10H,10'H-9,9'-spirobi[acridinium] 6a

[0225]

[0226] 5.4 g (44.3 mmol) of phenylboronic acid, 17.4 g (29.5 mmol) of 10-biphenyl-4-yl-2-chloro-9,9-dimethyl-9,10-dihydroacrylidine, and 8.9 g (59.1 mmol) of CsF were suspended in 250 mL of dimethyl ether. 1.1 g (1.5 mmol) of PdCl₂(PCy₃)₂ was added to the suspension, and the reaction mixture was heated under reflux for 16 h. After cooling, the mixture was filtered through silica gel, washed three times with 200 mL of water, and then evaporated to dryness. The residue was filtered through silica gel (heptane / ethyl acetate). The product was given in solid form. Yield: 16.7 g (90% of theoretical value).

[0227]

[0228] A-6) Buchwald reaction

[0229] 10,10'-bis({[1,1'-biphenyl]-4-yl})-2-tert-butyl-10H,10'H-9,9'-spirodi[acridinium] 7a

[0230]

[0231] 11.1 g (46.7 mmol) of 4-bromobiphenyl, 24.9 g (44.9 mmol) of spirodiacillin were dissolved in 480 ml of toluene and 11.9 g (121.3 mmol) of NaO. t The degassed suspension in Bu was saturated with N2 for 1 h. Then, 1.07 g (1.9 mmol) of DPPF and 1.38 g (1.9 mmol) of palladium(II) acetate were added. The reaction mixture was heated under reflux overnight. After cooling, the organic phase was filtered through silica gel and then evaporated to dryness. The residue was recrystallized from toluene / heptane. Yield: 15.7 g (49% of theoretical value).

[0232]

[0233]

[0234]

[0235] B) Device Examples

[0236] 1) General manufacturing process and characterization of OLEDs

[0237] An OLED is applied to a glass substrate coated with a 50 nm thick structured ITO (indium tin oxide).

[0238] OLEDs generally have the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emitting layer (EML) / electron transport layer, optionally with a second layer (ETL) / electron injection layer (EIL) and a final cathode. The cathode is formed of a 100 nm thick aluminum layer. The exact structure of an OLED can be found in the table below. The materials used to manufacture OLEDs are shown in the table below.

[0239] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the luminescent layer consists of at least one matrix material (host material) and luminescent dopants added to the matrix material by co-evaporation in a specific volume ratio. Details given in the form of H:SEB (95%:5%) indicate that the volume ratio of material H present in the layer is 95%, and the volume ratio of SEB is 5%.

[0240] Similarly, the electron transport layer and hole injection layer are also composed of a mixture of two materials. The structures of the materials used in OLEDs are shown in Table 3.

[0241] OLEDs were characterized using standard methods. For this purpose, electroluminescence spectra were measured; the external quantum efficiency (EQE, in %) as a function of luminescence density was calculated from the current-voltage-luminescence density characteristics under assumed Lambertian radiation properties; and lifetime was determined. Parameter EQE @ 10 mA / cm² 2 This refers to 10 mA / cm 2 The external quantum efficiency obtained at U @ 10 mA / cm². 2 This refers to 10 mA / cm 2 The operating voltage is specified. Lifetime LT is defined as the time required for the luminous density to decrease from its initial value to a certain percentage when operating at a constant current density. The LT80 symbol indicates that the lifetime reported here corresponds to the time required for the luminous density to decrease to 80% of its initial value. Symbol @ 60 mA / cm² 2 Or @ 40 mA / cm 2 This refers to a lifetime of 60 mA / cm². 2 Below or at 40 mA / cm 2 The measurement was taken below.

[0242]

[0243]

[0244] 1) The OLED of the present invention, containing a compound of formula (I) in the EBL of a green phosphorescent OLED.

[0245] Manufacture the devices shown in the table below:

[0246]

[0247] As shown in Table 3, compared with prior art compounds, the compounds of the present invention produce OLEDs with very good performance, especially with very good performance in terms of operating voltage, while having comparable or better efficiency and lifetime.

[0248]

[0249] 2) The OLED of the present invention, containing a compound of formula (I) in the HIL and HTL of the blue fluorescent OLED.

[0250] Manufacture the devices shown in the table below:

[0251]

[0252] As shown in Table 5, compared with prior art compounds, the compounds of the present invention produce OLEDs with very good performance, especially with very good performance in terms of operating voltage, while having comparable or better efficiency and lifetime.

[0253]

Claims

1. A compound of formula (I) Formula (I), The following applies to any symbols and markings that appear: A is either C or Si; Y is either N or P in each case, either the same or different. X is CR in each case, whether the same or different. 1 Or N; Ar 1 Ar 2 In each case, the same or different is that it can be controlled by one or more groups R. 2 Aromatic ring systems with 6 to 40 substituted aromatic ring atoms, or those that can be replaced by one or more R groups 2 Substituted heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two Ar groups 1 and Ar 2 At least one of them is: can be converted by one or more groups R 2 Aromatic ring systems with 12 to 40 substituted aromatic ring atoms, or those that can be replaced by one or more R groups 2 Substituted heteroaromatic ring systems with 12 to 40 aromatic ring atoms; R 3 R 4 R 5 R 6 In each case, the groups are selected, either identically or differently, from: D, F, C(=O)R, CF3, OCF3, CN, Si(R)3, N(R)2, P(=O)(R)2, S(=O)R, S(=O)2R, straight-chain alkyl, alkoxy, or thioalkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl, alkoxy, or thioalkyl groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, wherein the alkyl, alkoxy, alkenyl, and alkynyl groups in each case may be substituted by one or more groups R and wherein one or more H atoms of the groups mentioned above may be substituted by D or F; aromatic ring systems having 6 to 40 aromatic ring atoms that may be substituted by one or more groups R, or heteroaromatic ring systems having 5 to 40 aromatic ring atoms that may be substituted by one or more groups R; R 1 R 2 In each case, the groups are selected, either identically or differently, from: H, D, F, C(=O)R, CF3, OCF3, CN, Si(R)3, N(R)2, P(=O)(R)2, S(=O)R, S(=O)2R; straight-chain alkyl, alkoxy, or thioalkyl groups having 1 to 20 carbon atoms; branched or cyclic alkyl, alkoxy, or thioalkyl groups having 3 to 20 carbon atoms; alkenyl or alkynyl groups having 2 to 20 carbon atoms, wherein the alkyl, alkoxy, alkenyl, and alkynyl groups in each case may be substituted by one or more groups R and wherein one or more H atoms of the groups mentioned above may be substituted by D or F; aromatic ring systems having 6 to 40 aromatic ring atoms that may be substituted by one or more groups R; or heteroaromatic ring systems having 5 to 40 aromatic ring atoms that may be substituted by one or more groups R; wherein two or more groups R 1 or R 2 They can be linked together and can form rings; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, as well as the aromatic ring system and heteroaromatic ring system, can each be replaced by one or more groups R; and wherein one or more CH2 groups among the alkyl, alkoxy, alkenyl, and alkynyl groups can be replaced by -RC=CR-, -C≡C-, Si(R)2, C=O, C=NR, -C(=O)O-, -C(=O)NR-, NR, P(=O)(R), -O-, -S-, SO, or SO2; R is selected, in each case, either identically or differently, from: H, D, F, C(=O)R', CF3, OCF3, CN, Si(R')3, N(R')2, P(=O)(R')2, S(=O)R', S(=O)2R', straight-chain alkyl, alkoxy, or thioalkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl, alkoxy, or thioalkyl groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, wherein one or more H atoms in the groups mentioned above may be replaced by D or F, aromatic ring systems having 6 to 40 aromatic ring atoms, and... A heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more groups R can be linked to each other and can form a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, as well as the aromatic ring system and the heteroaromatic ring system, can each be substituted by one or more groups R'; and wherein one or more CH2 groups among the alkyl, alkoxy, alkenyl, and alkynyl groups can be replaced by -R'C=CR'-, -C≡C-, Si(R')2, C=O, C=NR', -C(=O)O-, -C(=O)NR'-, NR', P(=O)(R'), -O-, -S-, SO, or SO2; R´ is selected, in each case, either identically or differently, from: H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more groups R´ may be linked to each other and may form a ring; and wherein the alkyl group, aromatic ring system, and heteroaromatic ring system may be substituted with F or CN; a, b, c, and d are the same or different 0, 1, 2, 3, or 4 in each case; wherein at least one of a, b, c, and d is equal to 1; and The compound of formula (I) contains at least one group R. 3 R 4 R 5 or R 6 The at least one group R 3 R 4 R 5 or R 6 Representative: F, Si(R)3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 C atoms, wherein the alkyl, alkoxy, or thioalkyl group may in each case be substituted by one or more groups R and wherein one or more H atoms of the groups mentioned above may be substituted by D or F.

2. The compound according to claim 1, characterized in that... In formula (I), exactly one, two, three, or four of the labels a, b, c, and d are equal to 1 or 2.

3. The compound according to one or more of claims 1 or 2, characterized in that... A represents a carbon atom.

4. The compound according to one or more of claims 1 to 3, characterized in that... Y represents a nitrogen atom.

5. The compound according to one or more of claims 1 to 4, characterized in that... X equals CR 1 , where R 1 Selected from H and D, either the same or different.

6. The compound according to one or more of claims 1 to 5, characterized in that... Ar 1 and Ar 2 In each case, the same or different selections are made from substances that can be selected by one or more groups R. 2 A substituted aromatic ring system having 6 to 24 aromatic ring atoms, or selected from aromatic ring systems that can be substituted by one or more R groups. 2 Substituted heteroaromatic ring systems with 5 to 24 aromatic ring atoms, wherein two Ar groups 1 and Ar 2 At least one of them is: can be converted by one or more groups R 2 Aromatic ring systems with 12 to 24 substituted aromatic ring atoms, or those that can be replaced by one or more R groups 2 Substituted heteroaromatic ring systems with 12 to 24 aromatic ring atoms.

7. The compound according to one or more of claims 1 to 6, characterized in that... Ar group 1 and Ar 2 Both are selected, in each case, either identically or differently, from those that can be selected by one or more groups R. 2 Aromatic ring systems with 12 to 24 substituted aromatic ring atoms, and aromatic ring systems that can be substituted by one or more R groups 2 Substituted heteroaromatic ring systems with 12 to 24 aromatic ring atoms.

8. The compound according to one or more of claims 1 to 7, characterized in that... R 3 R 4 R 5 and R 6 The same or different means represent: a straight-chain alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl group may be substituted by one or more groups R in each case and wherein one or more H atoms of the groups mentioned above may be substituted by D or F.

9. The compound according to one or more of claims 1 to 7, characterized in that... The compounds of formula (I) include: At least one group R 3 R 4 R 5 or R 6 The at least one group R 3 R 4 R 5 or R 6 Representative: a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group may in each case be substituted by one or more groups R and wherein one or more H atoms of the groups mentioned above may be substituted by D or F, and At least one group R 3 R 4 R 5 or R 6 The at least one group R 3 R 4 R 5 or R 6 Representative: Aromatic ring systems having 6 to 18 aromatic ring atoms that can be substituted by one or more groups R, or heteroaromatic ring systems having 6 to 18 aromatic ring atoms that can be substituted by one or more groups R.

10. The compound according to one or more of claims 1 to 9, characterized in that... The compound of formula (I) conforms to one of formulas (I-1) to (I-7). The symbols and markings appearing therein are defined according to one or more of claims 1 to 9.

11. The compound according to one or more of claims 1 to 10, characterized in that... The compounds of formula (I) conform to one of formulas (I-1-1) to (I-7-1). The symbols and markings appearing therein are defined according to one or more of claims 1 to 9.

12. The compound according to claim 11, characterized in that... The compound is selected from compounds of formulas (I-1-1), (I-2-1), (I-3-1), (I-4-1), (I-5-1), (I-6-1), and (I-7-1), wherein: X represents CR 1 , where R 1 Selected from H and D, either the same or different.

13. The compound according to one or more of the preceding claims, characterized in that... The compound is a deuterated compound.

14. The compound according to one or more of the preceding claims, characterized in that... The compound has a deuteration degree of 20%, 40%, 60%, or 80%.

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

16. An organic light-emitting diode comprising an anode, a cathode, and an organic layer formed between the anode and the cathode, the organic layer comprising at least one compound according to one or more of claims 1 to 14.

17. The organic light-emitting diode according to claim 16, characterized in that... The organic layer is a hole transport layer.

18. The organic light-emitting diode according to claim 16 or 17, characterized in that... The organic light-emitting diode comprises, in the following order: an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode, wherein the hole transport layer comprises a first hole transport layer and a second hole transport layer. The first hole transport layer is formed between the anode and the second hole transport layer; The second hole transport layer is formed between the first hole transport layer and the light-emitting layer, and The second hole transport layer contains a compound of formula (I).

19. The organic light-emitting diode according to claim 18, characterized in that... The second hole transport layer is an electron blocking layer.

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