Nitrogen-containing compounds for organic electroluminescent devices

Abstract

The present invention relates to nitrogen-containing compounds suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing these compounds.

Description

Technical Field

[0001] The present invention relates to nitrogen-containing compounds for use in electronic devices, especially organic electroluminescent devices, and electronic devices, especially organic electroluminescent devices, containing these materials. Background Art

[0002] In organic electroluminescent devices, phosphorescent organometallic complexes are usually used as luminescent materials. Due to quantum mechanical reasons, the use of metal organic compounds as phosphorescent emitters can achieve up to four times the energy efficiency and power efficiency. In general, electroluminescent devices still have the need for improvement, especially electroluminescent devices that show triplet luminescence (phosphorescence). The characteristics of phosphorescent electroluminescent devices not only depend on the triplet emitters used. Other materials used, such as matrix materials, are also particularly important here. Therefore, the improvement of these materials can also significantly improve the performance of electroluminescent devices.

[0003] In addition, many electroluminescent devices include other layers in addition to the light-emitting layer, 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 (charge generation layers). These layers have a significant impact on the performance of the electroluminescent device.

[0004] Such an electroluminescent device is described, inter alia, in document WO 2014 / 015938 A1.

[0005] In general, there is still a need for improvement in these materials, for example as host materials, in particular with regard to the service life, but also with regard to the efficiency and operating voltage of the devices. Summary of the invention

[0006] It is therefore an object of the present invention to provide compounds suitable for use in organic electronic devices, in particular organic electroluminescent devices, which compounds give good device properties when used in such devices, and to provide corresponding electronic devices.

[0007] In particular, the object of the present invention is to provide compounds with long service life, high efficiency and low operating voltage. In particular, hole transport materials, hole injection materials or electron blocking materials contribute to these properties. In addition, the properties of the matrix material (also referred to herein as host material) have a significant impact on the service life and efficiency of the organic electroluminescent device.

[0008] Furthermore, it was an object of the present invention to provide compounds which feature a low refractive index (RI).

[0009] Another object of the present invention can be to provide compounds suitable for phosphorescent or fluorescent electroluminescent devices, in particular as matrix materials. In particular, the object of the present invention is to provide matrix materials suitable for green or blue phosphorescent electroluminescent devices and optionally also for red or yellow phosphorescent electroluminescent devices.

[0010] Furthermore, in particular when used as host materials, hole transport materials, hole injection materials or electron blocking materials in organic electroluminescent devices, these compounds should give devices having excellent color purity.

[0011] Another task may be to provide electronic components with excellent performance as cost-effectively as possible and with consistent quality.

[0012] Furthermore, electronic devices should be able to be used or adapted for a variety of purposes. In particular, the performance of electronic devices should be maintained over a wide temperature range.

[0013] Surprisingly, it has been found that the specific compounds described in more detail below solve this problem, are very suitable for electroluminescent devices, and obtain organic electroluminescent devices that show very good performance, especially in terms of service life, color purity, efficiency, operating voltage and refractive index. Therefore, the subject of the present invention is these compounds and electronic devices containing such compounds, in particular organic electroluminescent devices.

[0014] The subject of the present invention is a compound comprising at least one structure of formula (I), preferably a compound according to formula (I)

[0015]

[0016] The symbols represent:

[0017] Z a In each occurrence, the same or different representations of Ar, R c , L 1 -N(Ar)2 or L 1 -Q, preferably R c , L 1 -N(Ar)2 or L 1 -Q;

[0018] Ar is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be replaced by one or more radicals R d Substitution, wherein the two residues Ar bound to the same N atom may also be separated by a single bond or by a substitution selected from B(R d )、C(R d )2、Si(R d )2. C=O, C=NR d , C=C(R d2. R d C=CR d 、O、S、S=O、SO2、N(R d )、P(R d )、P(=O)R d and may be replaced by one or more residues R d The bridges of the substituted ortho-phenylene groups are bridged to each other, and the bridges are preferably selected from C(R d )2、O、N(R d ) and may be replaced by one or more residues R d Substituted ortho-bound phenylene, preferably Ar represents, identically or differently on each occurrence, an aryl or heteroaryl radical having 6 to 40 aromatic ring atoms, which may be substituted by one or more radicals R, wherein two radicals Ar bound to the same N atom may also be connected by a single bond or by a radical selected from B(R d )、C(R d )2、Si(R d )2. C=O, C=NR d , C=C(R d 2. R d C=CR d 、O、S、S=O、SO2、N(R d )、P(R d )、P(=O)R d and may be replaced by one or more residues R d The bridges of the substituted ortho-phenylene groups are bridged to each other, and the bridges are preferably selected from C(R d )2、O、N(R d ) and may be replaced by one or more residues R d substituted ortho-linked phenylene;

[0019] L 1 represents, identically or differently on each occurrence, a bond or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R;

[0020] R a is, identically or differently on each occurrence, a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 10 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 10 carbon atoms, which may each be replaced by one or more radicals R 2 substituted, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which may be replaced by one or more radicals R 2 substituted, preferably a linear alkyl radical having 1 to 10 carbon atoms or a branched or cyclic alkyl radical having 3 to 10 carbon atoms, which may be substituted by one or more radicals R 2 substituted; or phenyl, which may be substituted by one or more residues R2 Substituted, wherein two or more preferably adjacent substituents R a Can form ring systems with each other;

[0021] R b is, at each occurrence, identically or differently, H, D, a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 10 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 10 carbon atoms, which may each be replaced by one or more radicals R 2 substituted, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which may be respectively replaced by one or more radicals R 2 substituted, preferably H, D, a linear alkyl radical having 1 to 10 carbon atoms or a branched or cyclic alkyl radical having 3 to 10 carbon atoms or a phenyl radical, which may be substituted by one or more radicals R 2 Substituted, wherein two preferably adjacent substituents R b They can form a ring system with each other, and H or D is particularly preferred;

[0022] Q represents, identically or differently on each occurrence, an electron-transporting group, preferably a nitrogen-containing heteroaryl group having 5 to 12 ring atoms, particularly preferably having 6 to 12 ring atoms, which may be replaced by one or more radicals R e replace;

[0023] R, R c , R d , R e H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2, C(=O)N(Ar')2, C(=O)N(R 1 )2、C(Ar')3、C(R 1 )3、Si(Ar')3、Si(R 1 )3、B(Ar')2、B(R 1 )2, C(=O)Ar', C(=O)R 1 、P(=O)(Ar')2、P(=O)(R 1 )2、P(Ar')2、P(R 1 )2, S(=O)Ar', S(=O)R 1 、S(=O)2Ar'、S(=O)2R 1 、OSO2Ar'、OSO2R 1, a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 40 carbon atoms, an alkenyl or alkynyl radical having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl radical may be substituted by one or more residues R 1 substituted, wherein one or more non-adjacent CH2 groups may be replaced by R 1 C=CR 1 、C≡C、Si(R 1 )2. C=O, C=S, C=Se, C=NR 1 、C(=O)O、C(=O)NR 1 -、NR 1 ,P(=O)(R 1 ), -O-, S, SO or SO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be replaced by one or more radicals R 1 substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be replaced by one or more residues R 1 substitution, where two residues R, R d , R e They can also form a ring system with each other, or the residues R, R d , R e With other groups, in particular the residue R c Can form ring systems;

[0024] Ar' is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be replaced by one or more radicals R 1 Substitution, wherein two residues Ar' bound to the same C atom, Si atom, N atom, P atom or B atom may also be separated by a single bond or by a residue selected from B(R 1 )、C(R 1 )2、Si(R 1 )2. C=O, C=NR 1 , C=C(R 1 )2, O, S, S=O, SO2, N(R 1 )、P(R 1 ) and P(=O)R 1 The bridges are connected to each other;

[0025] R 1 H, D, F, Cl, Br, I, CN, NO2, N(Ar")2, N(R 2 )2、C(=O)Ar”、C(=O)R 2 ,P(=O)(Ar”)2,P(Ar”)2,B(Ar”)2,B(R2 )2、C(Ar”)3、C(R 2 )3、Si(Ar”)3、Si(R 2 )3. a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 40 carbon atoms, or an alkenyl radical having 2 to 40 carbon atoms, each of which may be substituted by one or more residues R 2 substituted, wherein one or more non-adjacent CH2 groups may be replaced by -R 2 C=CR 2 -、C≡C-、Si(R 2 )2. C=O, C=S, C=Se, C=NR 2 、C(=O)O-、C(=O)NR 2 -、NR 2 ,P(=O)(R 2 ), -O-, S, SO or SO2, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be replaced by one or more residues R 2 substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be replaced by one or more residues R 2 substituted, or an aralkyl or heteroaralkyl radical having 5 to 60 aromatic ring atoms, which may be replaced by one or more residues R 2 substitution, or a combination of these systems; wherein two or more preferably adjacent residues R 1 can form a ring system with each other, in which one or more residues R 1 can form a ring system with another part of the compound;

[0026] Ar" is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be replaced by one or more radicals R 2 substitution, wherein two residues Ar" bound to the same C atom, Si atom, N atom, P atom or B atom may also be bound by a single bond or by a residue selected from B(R 2 )、C(R 2 )2、Si(R 2 )2. C=O, C=NR 2 , C=C(R 2 )2, O, S, S=O, SO2, N(R 2 )、P(R 2 ) and P(=O)R 2 The bridges are connected to each other;

[0027] R 2is selected, identically or differently on each occurrence, from H, D, F, CN, an aliphatic hydrocarbon residue having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein one or more H atoms may be replaced by D, F, Cl, Br, I or CN and may be substituted by one or more alkyl radicals having 1 to 4 carbon atoms in each case, wherein two or more preferably adjacent substituents R 2 They can form a ring system with each other.

[0028] Aryl in the sense of the present invention contains 6 to 40 carbon atoms; heteroaryl in the sense of the present invention contains 3 to 40 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. Here, aryl or heteroaryl is understood to mean a simple aromatic ring (i.e. benzene) or a simple heteroaromatic ring (e.g. pyridine, pyrimidine, thiophene, etc.), or a condensed (annulated) aryl or heteroaryl, such as, for example, naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatic compounds which are linked to one another via single bonds, such as, for example, biphenyl, are not referred to as aryl or heteroaryl, but as aromatic ring systems.

[0029] Electron-poor heteroaryl in the sense of the present invention is a heteroaryl having at least one heteroaromatic six-membered ring, which has at least one nitrogen atom. Other aromatic or heteroaromatic five-membered or six-membered rings may also be fused to this six-membered ring. Examples of electron-poor heteroaryl are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline or quinoxaline.

[0030] The aromatic ring system in the sense of the present invention contains 6 to 60 carbon atoms in the ring system. The heteroaromatic ring system in the sense of the present invention contains 3 to 60 carbon atoms and at least one heteroatom in the ring system, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and / or S. The aromatic or heteroaromatic ring system in the sense of the present invention should be understood as a system that does not necessarily contain only aryl or heteroaryl, but in which multiple aryl or heteroaryl groups can also be connected by non-aromatic units such as C, N or O atoms. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, diphenylethylene can also be understood as aromatic ring systems in the sense of the present invention, and there are also systems in which two or more aryl groups are connected, for example, by short alkyl groups. Preferably, the aromatic ring system is selected from fluorene, 9,9'-spirobifluorene, 9,9-diarylamine or a group in which two or more aryl groups and / or heteroaryl groups are connected to each other by a single bond.

[0031] In the present invention, aliphatic hydrocarbon residues or alkyl or alkenyl or alkynyl groups which may contain 1 to 20 carbon atoms and in which individual H atoms or CH2 groups may also be substituted by the abovementioned groups are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloalkynyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. Alkoxy having 1 to 40 carbon atoms is preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. Thioalkyl having 1 to 40 carbon atoms is especially 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, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. Generally, the alkyl, alkoxy or thioalkyl according to the present invention may be linear, branched or cyclic, wherein one or more non-adjacent CH2 groups may be replaced by the above groups; in addition, one or more H atoms may also be replaced by D, F, Cl, Br, I, CN or NO2, preferably F, Cl or CN, further preferably F or CN, and particularly preferably CN.

[0032] Aromatic or heteroaromatic ring systems with 5 to 60 or 5 to 40 aromatic ring atoms, which may also be substituted by the abovementioned radicals and which may be attached to the aromatic or heteroaromatic structure via any position, especially radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, trimerized indene, isotrimerized indene, spirotrimerized indene, spiroisotrimerized indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine , quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthymidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthymidazole, anthraoxazole, phenanthroxiazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine , pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescein ring, naphthyridine, azocarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole 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, or radicals derived from combinations of these systems.

[0033] In the present specification, the expression that two or more residues can form a ring with each other particularly means that the two residues are linked to each other by a chemical bond while formally eliminating two hydrogen atoms. This is illustrated by the following formula.

[0034]

[0035] Furthermore, the above expression should also be understood as meaning that, in the case where one of the two residues represents hydrogen, the second residue is bound to the position where the hydrogen atom was originally bound to form a ring. This will be illustrated by the following formula:

[0036]

[0037] In a preferred design scheme, the compound according to the present invention may preferably contain at least one structure of formula (I-1) to (I-4), and is particularly preferably a compound selected from formula (I-1) to (I-4),

[0038]

[0039] The symbols Ar, Lr 1 , Q, R a , R b and R c has the meanings indicated above, in particular for formula (I).

[0040] It can also be provided that the radical Ar is selected, identically or differently on each occurrence, from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, which can each be replaced by one or more radicals R d The substituted group is preferably phenyl, biphenyl, fluorene, dibenzofuran, triphenylene, or indolocarbazole.

[0041] Preferably, it can be provided that the radical Ar is selected, identically or differently on each occurrence, from the formula (Ar a -1) to (Ar a -28) structure,

[0042]

[0043]

[0044]

[0045] where for the symbols used, the following holds:

[0046] Y 2 O, S, NR d or C(R d )2, preferably O, NR d or C(R d )2;

[0047] k is independently 0 or 1 at each occurrence;

[0048] i is independently 0, 1, or 2 at each occurrence;

[0049] j is independently 0, 1, 2 or 3 at each occurrence, preferably 0, 1 or 2;

[0050] h is independently 0, 1, 2, 3 or 4 at each occurrence, preferably 0, 1 or 2;

[0051] g is independently 0, 1, 2, 3, 4 or 5 at each occurrence, preferably 0, 1 or 2;

[0052] Rd has the meanings indicated above, in particular for formula (I), and the dashed bond marks the binding site.

[0053] Here, the formula (Ar a -1) to (Ar a -5), (Ar a -7) to (Ar a -13), (Ar a -18) to (Ar a -22), (Ar a -24), (Ar a -27) and (Ar a -28), particularly preferably (Ar a -1)、(Ar a -2), (Ar a -4), (Ar a -5), (Ar a -7) to (Ar a -9), (Ar a -12), (Ar a -13), (Ar a -19), (Ar a -21) and (Ar a -22), especially preferably a -1)、(Ar a -2), (Ar a -7) to (Ar a -9), (Ar a -12) and (Ar a -13) structure.

[0054] In a further preferred embodiment, it can be provided that the group L 1 represents a bond equally or differently, or is selected from the formula (L 1 -1) to (L 1 -22) structure,

[0055]

[0056]

[0057] where for the symbols used, the following holds:

[0058] Y is CR2, O, S or NR, preferably O or NR;

[0059] j is independently 0, 1, 2 or 3 at each occurrence, preferably 0, 1 or 2;

[0060] h is independently 0, 1, 2, 3 or 4 at each occurrence, preferably 0, 1 or 2

[0061] R has the meanings indicated above, in particular for formula (I), and the dashed bond marks the binding site.

[0062] Formula (Ar a -1) to (Ar a -28) and / or (L 1 -1) to (L 1 The sum of the indices i, j, h and g in the structure of -22) is preferably at most 6, particularly preferably at most 4, particularly preferably at most 2.

[0063] The radical Q represents, identically or differently on each occurrence, an electron-transporting group, wherein the electron-transporting group preferably represents a nitrogen-containing heteroaryl group having 5 to 12 ring atoms, particularly preferably a nitrogen-containing heteroaryl group having 6 to 12 ring atoms, which may be replaced by one or more radicals R e The radical Q preferably represents an electron-poor heteroaryl radical, wherein the electron-poor heteroaryl radical particularly preferably also has the properties given above and below.

[0064] Preferably, it can be provided that the group Q represents a nitrogen-containing heteroaryl group having 6 to 12 ring atoms, wherein there are at least two nitrogen atoms in the ring, which can be replaced by one or more residues R e Substitution wherein the carbon atoms adjacent to at least two nitrogen atoms located in the ring are not bonded to hydrogen atoms.

[0065] Electron transport groups are well known in the art and promote the ability of a compound to transport and / or conduct electrons. They include, in particular, nitrogen-containing heteroaryl groups having 5 to 12 ring atoms, particularly preferably 6 to 12 ring atoms, wherein they are usually electron-poor heteroaryl groups.

[0066] Furthermore, it may be provided that the radical Q represents a pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and / or benzimidazole radical, preferably a pyrimidine, pyrazine, triazine, quinazoline, quinoxaline and / or benzimidazole radical, particularly preferably a pyrimidine, triazine, quinazoline and / or quinoxaline radical, especially preferably a pyrimidine and / or triazine radical, especially preferably a radical which may be replaced by one or more radicals R e Substituted triazine groups.

[0067] In a particularly preferred embodiment, it can be provided that the radical Q represents a pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, imidazole and / or benzimidazole radical, preferably a pyrimidine, pyrazine, triazine, quinazoline, quinoxaline and / or benzimidazole radical, which may be replaced by one or more radicals R esubstituted, wherein the carbon atoms adjacent to at least two nitrogen atoms are attached to an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can be respectively substituted by one or more radicals R 1 replace.

[0068] In another embodiment, it can be provided that the group Q represents a pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, imidazole and / or benzimidazole group, preferably a pyrimidine, pyrazine, triazine, quinazoline, quinoxaline and / or benzimidazole group, which can be replaced by one or more residues R e substituted, wherein the carbon atoms adjacent to at least two nitrogen atoms are linked to a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group adjacent to the carbon atom to which the corresponding N atom is linked does not have an azide hydrogen atom and can be replaced by one or more residues R 1 Particular preference is given to embodiments in which the carbon atoms adjacent to the at least two nitrogen atoms are preferably linked to an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can each be substituted by one or more radicals R 1 replace.

[0069] In one embodiment, provision can be made for the group Ar to comprise no triazine groups, preferably no pyrimidine and / or triazine groups, particularly preferably no electron-transporting groups.

[0070] In one embodiment, the group L may be specified 1 It contains no triazine groups, preferably no pyrimidine and / or triazine groups, and particularly preferably no electron-transporting groups.

[0071] The group L 1 Compounds whose Ar and / or Ar do not contain electron-transporting groups are particularly suitable as hole-transporting materials, hole-injecting materials or electron-blocking materials for use in the corresponding layers, wherein this layer generally contains no emitting compounds.

[0072] In another embodiment, it may be provided that the group L 1 It comprises an electron transport group, preferably a pyrimidine and / or triazine group, and particularly preferably a triazine group.

[0073] In a further embodiment, provision can be made for the group Ar to comprise an electron-transporting group, preferably a pyrimidine and / or triazine group, particularly preferably a triazine group.

[0074] The group L 1 Compounds containing an electron transporting group and / or Ar are particularly suitable as host materials for use in combination with light-emitting compounds.

[0075] In another preferred design, it can be provided that the compound according to the present invention comprises the structure of formula (II-1) to (II-62), wherein the compound according to the present invention can be particularly preferably selected from the compounds of formula (II-2) to (II-62),

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087] The symbols R and R a , R b , R c and R d have the meanings indicated above, in particular for formula (I), and for the other symbols the following applies:

[0088] In case a group is attached to the structure, X represents N, CR or C identically or differently on each occurrence, preferably CR or C;

[0089] For a group to be bound to the structure, X 1 Represents N, CR the same or differently in each occurrence d or C, preferably CR d or C;

[0090] Y represents O, S, NR or C(R)2, preferably O, NR or C(R)2; and

[0091] Y 1 Represents O, S, BR d NR d 、Si(R d )2 or C(Rd )2, preferably O, NR d or C(R d )2.

[0092] Here, structures / compounds of formulae (II-1) to (II-24) and (II-50) to (II-53) are preferred, and structures / compounds of formulae (II-3) to (II-6), (II-8), (II-15) to (II-18), (II-52) and (II-53) are particularly preferred.

[0093] Preferably, in particular in the structures / compounds of the formulae (II-1) to (II-62), it can be provided that up to three, preferably up to two, groups X per ring represent N, preferably all X represent CR, preferably at least one, particularly preferably at least two, of the groups X per ring are selected from CH and CD.

[0094] Furthermore, in particular in the structures / compounds of the formulae (II-1) to (II-62), it may be provided that not more than four, preferably not more than two, radicals X represent N, particularly preferably all radicals X represent CR, wherein preferably up to 4, particularly preferably up to 3, and especially preferably up to 2, radicals CR represented by X are not equal to the radical CH.

[0095] In another embodiment, in particular in the structures / compounds of the formulae (II-1) to (II-62), it may be provided that up to three, preferably up to two, groups X per ring 1 represents N, preferably all X 1 Represents CR d , preferably each ring group X 1 At least one, particularly preferably at least two, are selected from CH and CD.

[0096] In another preferred embodiment, in particular in the structures / compounds of the formulae (II-1) to (II-62), no more than four, preferably no more than two, radicals X may be provided. 1 represents N, particularly preferably all groups X 1 represents CR, preferably up to 4, particularly preferably up to 3, particularly preferably up to 2 X 1 The group CR represented is not equal to the group CH.

[0097] In another preferred design, it can be provided that the compound according to the present invention comprises the structure of formula (III-1) to (III-62), wherein the compound according to the present invention can particularly preferably be selected from the compounds of formula (III-1) to (III-62),

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] The symbols R and R a , R b , R c and R d have the meanings given above, in particular for formula (I), and for the other symbols the following apply:

[0109] Y is O, S, NR or C(R)2, preferably O, NR or C(R)2;

[0110] Y 1 Represents O, S, BR d NR d or C(R d )2, preferably O, NR d or C(R d )2;

[0111] n is independently 0, 1, 2 or 3 at each occurrence, preferably 0, 1 or 2;

[0112] m is independently 0, 1, 2, 3 or 4 at each occurrence, preferably 0, 1 or 2;

[0113] l is independently 0, 1, 2, 3, 4 or 5 at each occurrence, preferably 0, 1 or 2.

[0114] Here, structures / compounds of formulae (III-1) to (III-24) and (III-50) to (III-53) are preferred, and structures / compounds of formulae (III-3) to (III-6), (III-8), (III-15) to (III-18), (III-52) and (III-53) are particularly preferred.

[0115] Furthermore, in particular in the structures / compounds of the formulae (III-1) to (III-62), the sum of the indices l, m and n can be provided to be up to 10, preferably up to 8, particularly preferably up to 6, particularly preferably up to 4.

[0116] In a preferred embodiment, the residues R, R a , R c , R d It does not include aromatic or heteroaromatic ring systems having three linearly fused aromatic six-membered rings, wherein preferably the residues R, R a , R c , R d None of the above comprises an aromatic or heteroaromatic ring system having three linearly fused aromatic six-membered rings.

[0117] Particularly preferably, the residues R, R a , R c , R d It does not include aromatic or heteroaromatic ring systems having three aromatic six-membered rings fused to one another, wherein preferably the residues R, R a , R c , R d None of the above comprises an aromatic or heteroaromatic ring system having three aromatic six-membered rings fused to each other.

[0118] Furthermore, it can be particularly preferred that the radical L1 does not comprise an aromatic or heteroaromatic ring system having three aromatic six-membered rings fused to one another.

[0119] Furthermore, it can be provided with particular preference that the radical Ar comprises no aromatic or heteroaromatic ring system having three aromatic six-membered rings fused to one another.

[0120] With particular preference it can be provided that the compound comprises no aromatic or heteroaromatic ring systems which have three aromatic six-membered rings which are fused to one another.

[0121] In a preferred refinement of the invention, it is possible to provide for at least two preferably adjacent residues R, R d With two residues R, R d The other groups combined form a fused ring, in which the two residues R, R d Forming at least one structure of formula (RA-1) to (RA-12),

[0122]

[0123] Where R 1 has the above meanings, and the dotted bond represents two residues R, R d The binding position on the atom of the bound group. Other symbols have the following meanings:

[0124] Y 3 C(R 1 )2、(R 1 )2C-C(R 1 )2、(R 1 )C=C(R 1 ), NR 1 , NAr', O or S, preferably C(R 1 )2、(R 1 )2C-C(R 1 )2、(R 1 )C=C(R 1 ), O or S;

[0125] R f in each case identically or differently F, straight-chain alkyl, alkoxy or thioalkoxy radicals having 1 to 40 carbon atoms, alkenyl or alkynyl radicals having 2 to 40 carbon atoms, or branched or cyclic alkyl, alkoxy or thioalkoxy radicals having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl radicals may each be replaced by one or more radicals R 2 substituted, wherein one or more non-adjacent CH2 groups may be replaced by R 2 C=CR2、C≡C、Si(R 2 )2. C=O, C=S, C=Se, C=NR 2 、C(=O)O、C(=O)NR 2 -、NR 2 ,P(=O)(R 2 ), -O-, S, SO or SO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be replaced by one or more radicals R 2 substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be replaced by one or more residues R 2 substitution; where two residues R f They can also form a ring system with each other, or a residue R f Can be combined with a residue R 1 or form a ring system with another group, where R 2 has the meaning set out in claim 1;

[0126] r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, particularly preferably 0 or 1;

[0127] s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2;

[0128] t is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2;

[0129] v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2.

[0130] Here, the structures of the formulae RA-1, RA-3, RA-4 and RA-5 are preferred, and the structures of the formulae RA-4 and RA-5 are particularly preferred.

[0131] In a preferred embodiment of the invention, preferably at least two preferably adjacent residues R, R d With two residues R, R d The other groups combined form a fused ring, in which the two residues R, R d Forming structures of formula (RA-1a) to (RA-4f),

[0132]

[0133] The dotted bond represents two residues R, R d The binding position on the bound radical atom, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the symbol R 1 , R 2 , R f and the indices s and t have the meanings indicated above, in particular, for formula (I) and / or formulae (RA-1) to (RA-12).

[0134] The structure of formula RA-4f is preferred herein.

[0135] Furthermore, it may be provided that at least two residues R, R forming structures of the formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) and forming a fused ring d represents the adjacent groups X, X 1 The residues R and R d , or residues R, R respectively bonded to adjacent carbon atoms d , wherein the carbon atoms are preferably connected by bonds.

[0136] In another preferred embodiment, at least two preferably adjacent residues R, R d With two residues R, R d The other groups combined form a fused ring, in which the two residues R, R d The structure of the formation formula (RB) is

[0137]

[0138] Where R 1 has the meanings given above, in particular for formula (I), the dashed bond represents the two residues R, R dThe binding position to be bound, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, Y 4 C(R 1 )2. NR 1 、NAr'、BR 1 , BAr', O or S, preferably C(R 1 )2, NAr' or O, particularly preferably C(R 1 )2 or O, wherein Ar' has the meanings indicated above, in particular, for formula (I).

[0139] Furthermore, it may be provided that at least two residues R, R forming a structure of the formula (RB) and forming a fused ring d represents the adjacent groups X, X 1 The residues R, R d , or residues R, R respectively bonded to adjacent carbon atoms d , wherein the carbon atoms are preferably connected by bonds.

[0140] In particular, it can be provided that, in preferred structures / compounds, the sum of the indices r, s, t, v, m and n is preferably 0, 1, 2 or 3, particularly preferably 1 or 2.

[0141] It is particularly preferred that the compound comprises at least one structure of formula (IV-1) to (IV-10), and it is particularly preferred that the compound is selected from the compounds of formula (IV-1) to (IV-10), wherein the compound has at least one fused ring,

[0142]

[0143]

[0144] The symbols R and R a , R b , R c and R d has the meanings given above, in particular for formula (I), the symbol o represents the fusion position of at least one fused ring, and the following holds true for the other indices used:

[0145] i is independently 0, 1 or 2 at each occurrence, preferably 0 or 1;

[0146] n is independently 0, 1, 2 or 3 at each occurrence, preferably 0, 1 or 2;

[0147] m is independently 0, 1, 2, 3 or 4 at each occurrence, preferably 0, 1 or 2; and

[0148] l is independently 0, 1, 2, 3, 4 or 5 at each occurrence, preferably 0, 1 or 2.

[0149] Furthermore, in particular in the structures / compounds of the formulae (IV-1) to (IV-10), the sum of the indices i, n, m and l can be provided to be up to 10, preferably up to 8, particularly preferably up to 6, particularly preferably up to 4.

[0150] In addition, in particular for the structures / compounds of formulae (IV-1) to (IV-10), it can be stipulated that the condensed ring is formed by the structures of formulae (RA-1) to (RA-12), (RA-1a) to (RA-4f) and / or (RB) as shown above, preferably by the structures of formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

[0151] Preferably, it can be provided that the compound has at least two fused rings, wherein at least one fused ring is formed by the structure of formula (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f), and the other ring is formed by the structure of formula (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB).

[0152] Furthermore, it can be provided that the substituents R, R c , R d , R e and R 1 With substituents R, R c , R d , R e and R 1 The ring atoms of the bound ring systems do not form a fused aromatic or heteroaromatic ring system. This includes the formation of a ring system with possible substituents R 1 and R 2 The fused aromatic or heteroaromatic ring system of c , R d , R e and R 1 Combine.

[0153] Residue R a , R b , R c It is preferred that no ring system is formed with other groups. a form a ring system with each other, the ring preferably consists of exactly two residues R bonded to a carbon atom a form.

[0154] If the compounds according to the invention consist of aromatic or heteroaromatic groups R, R c , R d , R e , R 1 or R 2Substitution, it is preferred that they have no aryl or heteroaryl groups with two or more aromatic six-membered rings fused directly to one another. It is particularly preferred that the substituents have no aryl or heteroaryl groups with six-membered rings fused directly to one another at all. This preference is due to the low triplet energy of such structures. Fused aryl groups with two or more aromatic six-membered rings fused directly to one another that are also suitable according to the invention are phenanthrene and triphenylene, since they also have a high triplet energy level.

[0155] Furthermore, it can be provided that the residues R, R c , R d , R e , R 1 or R 2 No aromatic or heteroaromatic ring systems having three linearly fused aromatic six-membered rings are included, wherein preferably no residue R comprises any aromatic or heteroaromatic ring system having 3 linearly fused aromatic six-membered rings.

[0156] Preferably, group Z a , L 1 -N(Ar)2、L 1 Q may be combined with a group Z according to formula (I) a , L 1 -N(Ar)2、L 1 The groups to which Q or a preferred embodiment of the formula is bound form continuous conjugation. Once direct bonds are formed between adjacent aromatic or heteroaromatic rings, continuous conjugation of the aromatic or heteroaromatic system is formed. Further connections between the above conjugated groups, for example via S-, N- or O-atoms or carbonyl groups, do not impair the conjugation.

[0157] Furthermore, it can be provided that the substituents R, R c , R d , R e and R 1 With the ring atoms of the ring system, no fused aromatic or heteroaromatic ring system is formed, preferably no fused ring system is formed. This includes the formation of a possible substituent R 1 and R 2 The substituents may be fused to the residues R, R c , R d , R e , R 1 Combine.

[0158] If in particular it can be selected from R, R c , R d , R e , R 1 and / or R 2If two residues of form a ring system with each other, they can be monocyclic or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic rings. In this case, the residues that form a ring system with each other can be adjacent, i.e., they are bound to the same carbon atom or to carbon atoms that are directly bound to each other, or they can be further away from each other. In addition, the substituents R, R d , R e , R 1 and / or R 2 The ring systems of can also be linked to one another via bonds, thereby enabling ring formation.

[0159] Furthermore, it may be provided that at least one of the residues R, R d , R e are selected, at each occurrence, identically or differently, from the group consisting of: a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms or an aromatic or heteroaromatic ring system selected from the following formulae Ar-1 to Ar-76, preferably, the substituents R, R d , R e Either a fused ring is formed, preferably a fused ring according to the structure of formula (RA-1) to (RA-12) or (RB), or the substituents R, R d , R e is selected, at each occurrence, identically or differently, from the group consisting of: an aromatic or heteroaromatic ring system selected from the following formulae Ar-1 to Ar-76, and / or the group Ar' is selected, at each occurrence, identically or differently, from the following radicals Ar-1 to Ar-76,

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168] Where R 1 Having the above meanings, dashed bonds indicate attachment at the corresponding radical, and the following also holds true:

[0169] Ar 1is, identically or differently on each occurrence, a divalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, which may be respectively replaced by one or more radicals R 1 replace;

[0170] A is C(R 1 )2. NR 1 , O or S;

[0171] p is 0 or 1, wherein p=0 represents the group Ar 1 absent, the corresponding aromatic or heteroaromatic group is directly bonded to the corresponding residue;

[0172] q is 0 or 1, where q = 0 means that no group A is bound at this position, but a residue R is present instead. 1 Combined with the corresponding carbon atom.

[0173] The previously described structures of formulae (Ar-1) to (Ar-76) represent preferred designs of the residue Ar, for example the residue Ar defined in the structure of formula (I), wherein in this case, the substituent R of formulae (Ar-1) to (Ar-76) is 1 Will be R d Substitute, where R d has the meanings given above, in particular for formula (I).

[0174] The above described structures of formula (Ar-1) to (Ar-76) represent the residue L 1 The preferred design scheme is as defined for the residue L of the structure of formula (I) 1 , wherein in this case, the substituent R of formula (Ar-1) to (Ar-76) 1 will be replaced by R, wherein R has the meanings given above, in particular for formula (I). In addition, the residue L 1 Another binding position is included.

[0175] Here, formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-40), (Ar-41), (Ar-42), (Ar-43), (Ar-44), (A r-45), (Ar-46), (Ar-69), (Ar-70), and (Ar-76) structures, particularly preferably the structures of formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16).

[0176] If the above-mentioned groups of the structures of the formulae (Ar-1) to (Ar-76) have a plurality of groups A, all combinations of the definitions of A are considered for this purpose. A preferred embodiment is one in which a group A represents NR 1 , another group A represents C(R 1 )2, or wherein both groups A represent NR 1 Or wherein both radicals A represent O.

[0177] If A represents NR 1 , then the substituent R bound to the nitrogen atom 1 Preferably represents an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be replaced by one or more radicals R 2 In a particularly preferred embodiment, the substituent R 1 represents, identically or differently on each occurrence, an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, in particular with 6 to 18 aromatic ring atoms, which has no fused aryl and fused heteroaryl radicals in which two or more aromatic or heteroaromatic six-membered ring radicals are directly fused to one another and which can also be replaced by one or more radicals R 2 Phenyl, biphenyl, terphenyl and quaterphenyl are preferred. Also preferred are triazines, pyrimidines and quinazolines, as listed above for Ar-47 to Ar-50, Ar-57 and Ar-58, wherein these structures may be replaced by one or more residues R 2 Instead of residue R 1 replace.

[0178] If A represents C(R 1 )2, then the substituent R bound to the carbon atom 1 preferably represents, identically or differently on each occurrence, a linear alkyl radical having 1 to 10 carbon atoms, or a branched or cyclic alkyl radical having 3 to 10 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be replaced by one or more radicals R 2 Particularly preferably, R 1 represents a methyl group or a phenyl group. 1 They can also form ring systems with one another, which give rise to spiro ring systems.

[0179] Preferred substituents R, R a , R b , R c , R d , R e and R f .

[0180] It may be preferably provided that for the symbols used in particular in formulae (I), (I-1) to (I-4) etc., the following holds:

[0181] R, R c , R d H, D, N(Ar')2, N(R 1 )2、C(Ar')3、C(R 1 )3、Si(Ar')3、Si(R 1 )3、B(Ar')2、B(R 1 ) 2. a straight-chain alkyl radical having 1 to 40 carbon atoms or a branched or cyclic alkyl radical having 3 to 20 carbon atoms, wherein the alkyl radical may be substituted by one or more residues R 1 substituted, wherein one or more non-adjacent CH2 groups may be replaced by R 1 C=CR 1 、C≡C、Si(R 1 )2. C=O, C=S, C=Se, C=NR 1 、C(=O)O、C(=O)NR 1 -、NR 1 ,P(=O)(R 1 ), SO or SO2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be replaced by one or more radicals R 1 substitution; here, the two residues R, R d They can also form a ring system or a residue R, R d with another group, in particular the residue R c Can form a ring system.

[0182] In a preferred embodiment of the present invention, R, R d , R e is selected, identically or differently at each occurrence, from H, D, F, CN, NO2, Si(R 1 )3. B(OR 1 ) 2. a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group may be substituted by one or more residues R 1 substituted, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may each be replaced by one or more radicals R 1 replace.

[0183] In a further preferred embodiment of the present invention, the substituents R, R d , R e is selected, identically or differently on each occurrence, from H, D, F, a straight-chain alkyl radical having 1 to 20 carbon atoms or a branched or cyclic alkyl radical having 3 to 20 carbon atoms, wherein the alkyl radical may be replaced by one or more radicals R 1substituted, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may each be replaced by one or more radicals R 1 replace.

[0184] Furthermore, it may be provided that at least one of the residues R, R d , R e , preferably substituents R, R d , R e , selected identically or differently on each occurrence from H, D, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be replaced by one or more radicals R 1 Substituents, or groups N(Ar')2, particularly preferably at least one substituent R, R d , R e are selected, identically or differently on each occurrence, from an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be replaced by one or more radicals R 1 Substituents, or groups N(Ar')2. Particularly preferably, at least one substituent R, R d , R e are selected, identically or differently on each occurrence, from an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be replaced by one or more radicals R 1 In a further preferred embodiment of the present invention, either the substituent R, R d , R e The rings of the structures of formula (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB) are formed, or the substituents R, R d , R e is selected, identically or differently on each occurrence, from H, D, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be replaced by one or more radicals R 1 Substitution, or the group N(Ar')2. Particularly preferred are the residues R, R d , R e , preferably substituents R, R d , R e , are selected, identically or differently on each occurrence, from H or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, particularly preferably having 6 to 13 aromatic ring atoms, which can each be replaced by one or more radicals R 1 replace.

[0185] Furthermore, it may be provided that at least one of the residues R, R d , R e represents an aromatic or heteroaromatic ring system having 5 to 13 aromatic ring atoms, which may be replaced by one or more radicals R 1 replace.

[0186] Preferably, it can be provided that at least one radical, preferably a substituent R, R d , R e is selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which may be substituted by one or more residues R 1 Substitution. The term "substituent" here means in particular that R is not H. Furthermore, if two or more radicals are present from the abovementioned aromatic or heteroaromatic radicals, the substituents R may be identical or different.

[0187] Furthermore, it may be provided that the radical R bonded to a carbon atom a same.

[0188] Furthermore, it may be provided that the radicals R bonded to different carbon atoms a same.

[0189] Furthermore, it can be provided that the groups R bonded to different carbon atoms a are different.

[0190] It may be preferred to provide that the radical R bonded to the carbon atom a can be selected from a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, which can be respectively replaced by one or more residues R 2 Substituted, preferably deuterated, wherein two or more preferably adjacent substituents R a can form a ring system with each other. If the adjacent substituents R a form a ring system with each other, the ring preferably consists of two residues R a form.

[0191] Furthermore, it can preferably be provided that the radical R bonded to the carbon atom a is selected from aromatic or heteroaromatic ring systems having 5 to 20 aromatic ring atoms, each of which may be replaced by one or more radicals R 2 substituted, preferably represents phenyl, which can be respectively replaced by one or more residues R 2 Substituted, preferably deuterated, wherein two or more preferably adjacent substituents R a can form a ring system with each other. If the adjacent substituents R a form a ring system with each other, the ring preferably consists of exactly two residues R a form.

[0192] Preferably, the group R may be specified arepresents methyl, ethyl, propyl, phenyl, or two groups R bound to the same carbon atom a Forming a cycloalkyl radical having 5 or 6, preferably 5, carbon atoms, wherein the radical R a Preference is given to methyl, wherein these groups may be deuterated.

[0193] Preferably, the group R may be specified b represents a methyl, ethyl, propyl group, or two residues R bound to the same carbon atom b Forming a cycloalkyl radical having 5 or 6, preferably 5, carbon atoms, wherein the radical R b Preferably represents H, D, methyl, ethyl, propyl, wherein these radicals may be deuterated, wherein the radical R b It particularly preferably represents H or D.

[0194] Preferably, the group R may be specified c represents H, D, methyl, ethyl, propyl, wherein these groups may be deuterated, wherein the group R c Preferably it represents H or D.

[0195] In a preferred embodiment of the present invention, R f are selected, identically or differently on each occurrence, from straight-chain alkyl radicals having 1 to 20 carbon atoms or branched or cyclic alkyl radicals having 3 to 20 carbon atoms, wherein the alkyl radicals may each be replaced by one or more radicals R 1 substituted, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, which may each be substituted by one or more radicals R 2 replace.

[0196] In another preferred embodiment of the present invention, R f are selected, identically or differently on each occurrence, from straight-chain alkyl radicals having 1 to 10 carbon atoms or branched or cyclic alkyl radicals having 3 to 10 carbon atoms, wherein the alkyl radicals may each be replaced by one or more radicals R 2 substituted, aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be replaced by one or more radicals R 2 Particularly preferably, R f are selected, identically or differently on each occurrence, from straight-chain alkyl radicals having 1 to 5 carbon atoms or branched or cyclic alkyl radicals having 3 to 5 carbon atoms, wherein the alkyl radicals may each be replaced by one or more radicals R 2 substituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, particularly preferably having 6 to 13 aromatic ring atoms, which may each be replaced by one or more radicals R 2 replace.

[0197] In a preferred embodiment of the present invention, R f are selected, identically or differently on each occurrence, from straight-chain alkyl radicals having 1 to 6 carbon atoms or cyclic alkyl radicals having 3 to 6 carbon atoms, wherein the alkyl radicals may each be replaced by one or more radicals R 2 substituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may be respectively substituted by one or more radicals R 2 substitution; here, the two residues R f They may also form a ring system with each other. It is particularly preferred that R f is selected, identically or differently on each occurrence, from a linear alkyl radical having 1, 2, 3 or 4 carbon atoms or a branched or cyclic alkyl radical having 3 to 6 carbon atoms, wherein the alkyl radical can be replaced by one or more radicals R 2 substituted, but preferably unsubstituted, or an aromatic ring system with 6 to 12 aromatic ring atoms, in particular with 6 aromatic ring atoms, which may each be replaced by one or more preferably non-aromatic radicals R 2 substituted, but preferably unsubstituted; here, the two residues R f can form a ring system with each other. It is particularly preferred that R f is selected, identically or differently on each occurrence, from a linear alkyl radical having 1, 2, 3 or 4 carbon atoms, or a branched alkyl radical having 3 to 6 carbon atoms. f represents a methyl group or represents a phenyl group, wherein two phenyl groups may together form a ring system, wherein a methyl group is more preferred than a phenyl group.

[0198] Substituents R, R c , R d , R e , R f The preferred aromatic or heteroaromatic ring system represented by Ar or Ar' is selected from phenyl, biphenyl (especially ortho-, meta- or para-biphenyl), terphenyl (especially ortho-, meta-, para- or branched terphenyl), quaterphenyl, fluorene (which can be attached via the 1-, 2-, 3- or 4-position), spirobifluorene (which can be attached via the 1-, 2-, 3- or 4-position), naphthalene (especially 1- or 2-position), connected naphthalene), indole, benzofuran, benzothiophene, carbazole (which may be connected via the 1-, 2-, 3- or 4-position), dibenzofuran (which may be connected via the 1-, 2-, 3- or 4-position), dibenzothiophene (which may be connected via the 1-, 2-, 3- or 4-position), indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, anthracene, pyrene, perylene, Phenanthrene or triphenylene, which may be respectively replaced by one or more residues R, R 1 or R 2Particularly preferred are the structures Ar-1 to Ar-76 listed above, among which the structures of formula (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), (Ar-76), and the structures of formula (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) are particularly preferred. It should be noted that regarding the structures Ar-1 to Ar-76, they are substituted with the substituent R 1 In the case of the ring system Ar, these substituents R 1 Replaced by R, in R f In the case of these substituents R 1 By R 2 replace.

[0199] Other suitable groups R, R d , R e It is Ar 4 -N(Ar 2 )(Ar 3 ) group, wherein Ar 2 ,Ar 3 and Ar 4 represents, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can in each case be replaced by one or more radicals R 1 Here, Ar 2 ,Ar 3 and Ar 4 The total number of aromatic ring atoms is at most 60, preferably at most 40.

[0200] Here, by selecting C(R 1 )2. NR 1 , O or S group, Ar 4 and Ar 2 can be connected to each other, and / or Ar 2 and Ar 3 Preferably, Ar 4 and Ar 2 Connection or Ar 2 and Ar 3 The connection to each other is carried out at the ortho position of the connection position of the nitrogen atom. In another embodiment of the present invention, the group Ar 2 ,Ar 3 or Ar 4 None are connected to each other.

[0201] Ar 4Preferably, it is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, which can be respectively replaced by one or more radicals R 1 Ar is particularly preferred. 4 is selected from ortho-, meta- or para-phenylene or ortho-, para- or meta-biphenyl, which can be respectively replaced by one or more residues R 1 It is particularly preferred that Ar 4 is an unsubstituted phenylene group.

[0202] Preferably, Ar 2 and Ar 3 is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each case be replaced by one or more radicals R 1 Particularly preferred groups Ar 2 or Ar 3 is selected, identically or differently on each occurrence, from the group consisting of benzene, ortho-, meta-, para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-, 3- or 4-carbazole, 1-, 2-, 3- or 4-dibenzofuran, 1-, 2-, 3- or 4-dibenzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2-, 4- or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene or triphenylene, each of which may be replaced by one or more residues R 1 Particularly preferably, Ar 2 and Ar 3 is selected, identically or differently on each occurrence, from benzene, biphenyl (especially ortho-, meta- or para-biphenyl), terphenyl (especially ortho-, meta-, para- or branched terphenyl), quaterphenyl (especially ortho-, meta-, para- or branched quaterphenyl), fluorene (especially 1-, 2-, 3- or 4-fluorene) or spirobifluorene (especially 1-, 2-, 3- or 4-spirobifluorene).

[0203] In another preferred embodiment of the present invention, R 1 is selected, identically or differently on each occurrence, from H, D, F, CN, a straight-chain alkyl radical having 1 to 10 carbon atoms or a branched or cyclic alkyl radical having 3 to 10 carbon atoms, wherein the alkyl radical may be replaced by one or more radicals R 2 substituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may be respectively substituted by one or more radicals R 2 In a particularly preferred embodiment of the present invention, R 1is selected, identically or differently on each occurrence, from H, straight-chain alkyl having 1 to 6 carbon atoms, in particular straight-chain alkyl having 1, 2, 3 or 4 carbon atoms, or branched or cyclic alkyl having 3 to 6 carbon atoms, wherein the alkyl radical may be replaced by one or more radicals R 2 substituted, but preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, which may be respectively replaced by one or more radicals R 5 substituted, but preferably unsubstituted.

[0204] In another preferred embodiment of the present invention, R 2 Identically or differently on each occurrence is H, alkyl having 1 to 4 carbon atoms or aryl having 6 to 10 carbon atoms, which may be substituted by alkyl having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0205] In the compounds according to the invention processed by vacuum evaporation, the alkyl group preferably has not more than 5 carbon atoms, particularly preferably not more than 4 carbon atoms, and especially preferably not more than 1 carbon atom. Also suitable for compounds processed from solution are compounds which are substituted by alkyl groups having up to 10 carbon atoms, in particular branched alkyl groups, or by oligoarylene groups, for example ortho-, meta-, para- or branched terphenyl or quaterphenyl groups.

[0206] If the compound of the formula (I) or the preferred embodiments is used as matrix material for a phosphorescent emitter or in a layer directly adjacent to the phosphorescent layer, it is further preferred that the compound does not contain fused aromatic or heteroaryl groups in which more than two six-membered rings are fused directly to one another. An exception to this are phenanthrene and triphenylene, which, despite the presence of fused aromatic six-membered rings, may be preferred due to their high triplet energy.

[0207] Furthermore, it can be provided that the compound comprises exactly two or exactly three structures according to formula (I).

[0208] In a preferred design, the compound is selected from the group consisting of (D-1),

[0209]

[0210] The group L 2 represents a linking group, preferably a bond, or an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, aromatic ring atoms, which may be substituted by one or more radicals R, and the other symbols and indices used have the meanings given in claim 1, wherein the radical L 2 Instead of hydrogen atoms or substituents forming bonds to the basic structure, preferably the radical L 2 With residue L 1 , Ar, Z a Combine.

[0211] In another preferred embodiment of the present invention, L 2 represents a bond or an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms, which may be substituted by one or more residues R, but is preferably unsubstituted, wherein R may have the meanings indicated above, in particular for formula (I), particularly preferably, L 2 represents an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, which may be respectively substituted by one or more radicals R 1 substituted, but preferably unsubstituted, wherein R 1 may have the meanings given above, in particular for formula (I).

[0212] It is further preferred that the symbol L shown in formula (D1) 2 represents, identically or differently on each occurrence, a bond or an aryl or heteroaryl radical having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, particularly preferably 6 to 10 ring atoms, such that the aromatic or heteroaromatic radical in the aromatic or heteroaromatic ring system is bonded directly to the corresponding atom of the other radical, i.e. via an atom of the aromatic or heteroaromatic radical.

[0213] Furthermore, it can be provided that the group L represented by formula (D1) 2 Contains an aromatic ring system with up to four, preferably up to three, particularly preferably up to two fused aromatic and / or heteroaromatic six-membered rings, preferably no fused aromatic or heteroaromatic ring systems. Therefore, naphthyl structures are preferred over anthracene structures. In addition, fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structures are preferred over naphthyl structures.

[0214] Particularly preferred are those having no condensed structures such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0215] Suitable aromatic or heteroaromatic ring systems L 2 Examples are selected from the group consisting of ortho-, meta- or para-phenylene, ortho-, meta- or para-biphenylene, terphenylene, in particular branched terphenylene, quaterphenylene, in particular branched quaterphenylene, fluorenylene, spirobifluorenylene, dibenzofuranylene, dibenzothienylene and carbazolylene, each of which may be substituted by one or more residues R 1 substituted, but preferably unsubstituted.

[0216] According to a preferred design, the compound according to the present invention can be represented by at least one of the structures according to formula (I), (I-1) to (I-4), (II-1) to (II-62), (III-1) to (III-62) and / or (IV-1) to (IV-10). Preferably, the compound according to the present invention, preferably comprising the structure according to formula (I), (I-1) to (I-4), (II-1) to (II-62), (III-1) to (III-62) and / or (IV-1) to (IV-10), has a molecular weight of less than or equal to 5000 g / mol, preferably less than or equal to 4000 g / mol, particularly preferably less than or equal to 3000 g / mol, especially preferably less than or equal to 2000 g / mol, more preferably less than or equal to 1200 g / mol, especially preferably less than or equal to 900 g / mol.

[0217] Preferred compounds according to the invention are furthermore characterized in that they are sublimable. These compounds generally have a molar mass of less than about 1200 g / mol.

[0218] Preferably, it may be provided that the compound does not comprise alkoxy, thioalkoxy or hydroxyl groups.

[0219] In a further preferred embodiment, provision can be made that the compound contains no cyclobutyl residues to which two oxygen atoms are bonded.

[0220] Preferably, provision can also be made that the compound contains no thiadiazine groups.

[0221] Compounds can also be specified:

[0222]

[0223] Not protected.

[0224] Furthermore, it can be provided that the ratio of hole-transporting groups, preferably N(Ar) 2 groups, to the phenyl groups fused to the two cyclopentyl radicals is at least 0.6, preferably at least 0.8 and particularly preferably at least 0.9.

[0225] Furthermore, it can be provided that the ratio of hole-transporting groups, preferably N(Ar) 2 groups, to the phenyl groups condensed on the two cyclopentyl radicals is not more than 10, preferably not more than 4, particularly preferably not more than 1.5.

[0226] Hole-transporting groups are well known in the technical field and include, in particular, diarylamine and triarylamine groups, carbazole groups and groups having similar properties.

[0227] It can also be provided that the compound comprising the structure according to formula (I), preferably the compound according to formula (I) or preferred embodiments of this structure / compound is not in direct contact with the metal atom and preferably does not constitute a ligand of a metal complex.

[0228] The above-mentioned preferred embodiments can be combined with each other arbitrarily within the limits defined in claim 1. In a particularly preferred embodiment of the invention, the above-mentioned preferred embodiments occur simultaneously.

[0229] Examples of preferred compounds according to the above embodiments are the compounds listed in the following table.

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241] The basic structure of the compound according to the invention can be represented in the manner outlined in the following scheme. Here, the individual synthesis steps, for example the coupling reactions to obtain CC connections and / or CN connections, are known in principle to those skilled in the art. It includes in particular the BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA and HIYAMA reactions.

[0242] Further information on the synthesis of the compounds according to the invention can be obtained from the synthesis examples.

[0243] The following schemes describe the compounds according to the invention by using an explicit phenyl compound to which one cyclopentyl, preferably two cyclopentyls are fused. This use is to be understood as exemplary, and thus other compounds according to the invention can be obtained by analogous synthetic routes, which proceed from other basic structures.

[0244] The synthesis of phenyl compounds with cyclopentyl, preferably two cyclopentyls condensed thereon is well known in the art. Many of these compounds are commercially available. For example, it includes the compounds mentioned in the synthetic examples.

[0245] The compounds according to the invention having an amine group, in particular compounds comprising a structure according to formula (I), can be obtained starting from a phenyl compound (1) to which a cyclopentyl group, preferably two cyclopentyl groups, are condensed by the following synthetic route:

[0246] 1) According to M.Oi et al., Chem.Sci., 2019, 10, 6107, organocopper chloride (3) is obtained by lithiation (2) and transition metalation with copper (I) chloride, followed by oxygen-mediated CN coupling with diarylamide lithium LiNAr2 according to H.Yamamoto et al., J.Org.Chem., 1980, 45, 2739:

[0247]

[0248] 2) According to M.Oi et al., Chem.Sci., 2019, 10, 6107, organocopper chloride (3) is obtained by lithiation (2) and transition metalation with copper (I) chloride, followed by CC coupling with bromo or iodoarylamine or carbazole X-Ar-NAr2 mediated by palladium-phosphine:

[0249]

[0250] If the radical X on the phenyl compound (1) to which the cyclopentyl, preferably two cyclopentyls, are condensed is (1) a bromine atom, the reaction sequence 1) or 2) can be repeated successively to give compounds according to the invention which are symmetrically or asymmetrically disubstituted with NAr2 or -Ar-NAr2 groups.

[0251] Schemes (1) and (2) are to be understood as exemplary, and therefore other groups X are also suitable, as shown in the examples.

[0252] The meanings of the symbols used in the above schemes correspond essentially to those defined for formula (I), wherein numbering as well as the complete representation of all symbols have been omitted for the sake of clarity.

[0253] A further object of the present invention is therefore a process for preparing the compounds according to the invention, wherein a phenyl compound to which a cyclopentyl group, preferably two cyclopentyl groups, are fused is synthesized and at least one aromatic or heteroaromatic residue is introduced, preferably by a nucleophilic aromatic substitution reaction or a coupling reaction.

[0254] By this process, optionally followed by purification, such as recrystallization or sublimation, it is possible to obtain compounds according to the invention in high purity, preferably greater than 99% (by 1 H-NMR and / or HPLC determination).

[0255] Compounds according to the present invention can also be mixed with polymers. These compounds can also be covalently integrated into polymers. This is especially possible for compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boric acid or boric esters or by reactive polymerizable groups such as olefins or oxetanes. They can be used as monomers for producing corresponding oligomers, dendritic macromolecules or polymers. Oligopolymerization or polymerization is preferably carried out by halogen functional groups or boric acid functional groups or by polymerizable groups at this. It is also possible to crosslink polymers by this group. Compounds according to the present invention and polymers can be used as crosslinked layers or non-crosslinked layers.

[0256] Therefore, another subject of the present invention is an oligomer, polymer or dendrimer comprising one or more structures of formula (I) and preferred embodiments of the above formula or compounds according to the invention, wherein there are one or more bonds between the compounds according to the invention or the structures of formula (I) and preferred embodiments of the above formula and the polymer, oligomer or dendrimer. Thus, according to the connection of the structures of formula (I) and preferred embodiments of the above formula or compounds, they form side chains of the oligomer or polymer, or are connected to the main chain. The polymer, oligomer or dendrimer may be conjugated, partially conjugated or non-conjugated. The oligomer or polymer may be linear, branched or dendritic. For the repeating units of the compounds according to the invention in the oligomers, dendrimers and polymers, the same preferences as above apply.

[0257] To prepare oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Preference is given to copolymers in which the units according to formula (I) or the preferred embodiments described above and below are present in an amount of 0.01 to 99.9 mol %, preferably 5 to 90 mol %, particularly preferably 20 to 80 mol %. Suitable and preferred comonomers for forming the polymer backbone are selected from fluorene (for example according to EP 842208 or WO 2000 / 022026), spirobifluorene (for example according to EP 707020, EP 894107 or WO 2006 / 061181), p-phenylene (for example according to WO 92 / 18552), carbazole (for example according to WO 2004 / 070772 or WO 2004 / 113468), thiophene (for example according to EP 1028136), dihydrophenanthrene (for example according to WO 2005 / 014689), cis- and trans-indenofluorene (for example according to WO 2004 / 041901 or WO 2004 / 113412), ketone (for example according to WO 2005 / 040302), phenanthrene (for example according to WO 2005 / 104264 or WO 2007 / 017066) or a combination of these units. The polymers, oligomers and dendrimers may also contain other units, such as hole transport units, in particular hole transport units based on triarylamines, and / or electron transport units.

[0258] Of particular interest are also compounds according to the invention that are characterized by a high glass transition temperature. In this regard, particular preference is given to compounds according to the invention that include structures according to formula (I) or the preferred embodiments described above and below, whose glass transition temperature, determined according to the DIN 51005 standard (2005-08 edition), is at least 70° C., particularly preferably at least 110° C., very particularly preferably at least 125° C., and especially preferably at least 150° C.

[0259] For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, formulations of the compounds according to the invention are required. For example, these formulations can be solutions, dispersions or emulsions. For this reason, a mixture of two or more solvents can preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methylbenzoates, mesitylene, tetralin, veratrol, tetrahydrofuran, methyltetrahydrofuran, THP, chlorobenzene, dioxane, phenoxytoluene (especially 3-phenoxytoluene), (-)-fennel, 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, -terpineol, benzothiazole, butylbenzoate, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, Decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-isopropylbenzyl methane, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or a mixture of these solvents.

[0260] Therefore, another subject of the present invention is a preparation or composition, which contains at least one compound according to the present invention and at least one other compound. The other compound can be, for example, a solvent, in particular one of the above-mentioned solvents or a mixture of these solvents. If the other compound includes a solvent, the mixture is referred to as a preparation herein. However, the other compound can also be at least one other organic or inorganic compound, such as a luminescent compound and / or another matrix material, which is also used in electronic devices. Preferably, it can be specified that at least one other compound is selected from fluorescent emitters, phosphorescent emitters, luminophores showing TADF, host materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, electron blocking materials and hole blocking materials, preferably host materials.

[0261] Another subject of the present invention is the use of the compounds according to the invention in electronic devices, in particular in organic electroluminescent devices. Preferably, it can be provided that the compounds according to the invention are used as host materials, hole transport materials, hole injection materials or electron blocking materials in electronic devices.

[0262] Another subject of the present invention is to provide an electronic device comprising at least one compound according to the invention. An electronic device in the sense of the present invention is a device comprising at least one layer comprising at least one organic compound. Here, the component can also comprise an inorganic material or a layer consisting entirely of an inorganic material.

[0263] Particularly preferred are electronic devices selected from the following: organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), preferably organic light-emitting diodes (OLED), small molecule-based organic light-emitting diodes (sOLED), polymer-based organic light-emitting diodes (PLED), light-emitting electrochemical cells (LEC), organic laser diodes (O Laser), "organic plasma emission devices" (DM Koller et al., Nature Photonics 2008, 1-4); 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 (OSC), organic optical detectors, organic photoreceptors, organic field quenching devices (O FQD) and organic electrical sensors, preferably organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), particularly preferably organic light-emitting diodes (OLED), small molecule-based organic light-emitting diodes (sOLED), polymer-based organic light-emitting diodes (PLED), in particular phosphorescent OLED.

[0264] The organic electroluminescent device comprises a cathode, an anode and at least one luminescent layer. In addition to these layers, it can also include other layers, such as one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, charge blocking layers and / or charge generation layers (Charge-Generation Layers). It is also possible to introduce an intermediate layer such as an exciton blocking function between two luminescent layers. However, it should be noted that not each of these layers must exist. Here, the organic electroluminescent device can include a luminescent layer, or can include multiple luminescent layers. If there are multiple luminescent layers, they preferably have a total of multiple luminescent maxima between 380nm and 750nm, thereby producing overall white luminescence, that is, using different luminescent compounds that can emit fluorescence or phosphorescence in the luminescent layer. Particularly preferred is a system with three luminescent layers, wherein the three layers show blue, green and orange or red luminescence. The organic electroluminescent device according to the present invention can also be a cascade electroluminescent device, particularly for white light-emitting OLED.

[0265] Here, depending on the exact structure, the compounds according to the invention can be used in different layers. Preferred is an organic electroluminescent device: it contains a compound according to formula (I) or the above preferred embodiment as a phosphorescent emitter or a luminescent body showing TADF (thermally activated delayed fluorescence), in particular a matrix material for a phosphorescent emitter in the emitting layer. In addition, the compounds according to the invention can also be used in a hole transport layer and / or an exciton blocking layer. It is particularly preferred that the compounds according to the invention are used as a matrix material for a phosphorescent emitter in the emitting layer, in particular for a red, orange, blue, green or yellow phosphorescent emitter, preferably for a blue or green phosphorescent emitter, as a host material, a hole transport material, a hole injection material or an electron blocking material.

[0266] Preferably, carbazole can be used as a host material. For example, arylamines not constituting carbazole shown in formula (II-1), (II-3), (II-4), etc. can be preferably used as hole transport materials, hole injection materials, or electron blocking materials.

[0267] Preferably, provision can be made that the organic electroluminescent device comprises at least one emitting layer and at least one hole-transport layer, and that the hole-transport layer comprises the compound according to the invention.

[0268] When the compound according to the invention is used as matrix material for phosphorescent compounds in an emitting layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). Phosphorescence in the sense of the present invention refers to luminescence from excited states with higher spin multiplicity, i.e. spin states>1, in particular luminescence from excited triplet states. For the purposes of this application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.

[0269] The mixture of the compound according to the invention and the emitting compound contains 99 to 1% by volume, preferably 98 to 10% by volume, particularly preferably 97 to 60% by volume, in particular 95 to 80% by volume of the compound according to the invention, relative to the total mixture of emitter and matrix material. Thus, the mixture contains 1 to 99% by volume, preferably 2 to 90% by volume, particularly preferably 3 to 40% by volume, in particular 5 to 20% by volume of emitter, relative to the total mixture of emitter and matrix material.

[0270] In one embodiment of the invention, the compounds according to the invention here are employed as sole matrix material (“single host”) for a phosphorescent emitter.

[0271] A further embodiment of the present invention is the use of the compounds according to the invention in combination with a further matrix material as matrix material for a phosphorescent emitter. Suitable matrix materials which can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, carbazole derivatives, for example CBP (N,N-biscarbazolylbiphenyl), or according to WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176, indolocarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, for example according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, azocarbazole 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, azaboroles or boron esters, for example according to WO 2006 / 117052, triazine derivatives, for example according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, zinc complexes, for example according to EP 652273 or WO 2009 / 062578, diazathiole or tetraazathiole derivatives, for example according to WO 2010 / 054729, diazaphosphole derivatives, for example according to WO 2010 / 054730, bridged carbazole derivatives, for example according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080, triphenylene derivatives, for example according to WO 2012 / 048781, dibenzofuran derivatives, for example according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565, or bicarbazoles, for example according to JP 3139321 B2.

[0272] Likewise, a further phosphorescent emitter which emits at a shorter wavelength than the actual emitter may be present in the mixture as cohost. Particularly good results are obtained when a red phosphorescent emitter is used as emitter and a yellow phosphorescent emitter is used as cohost in combination with the compounds according to the invention.

[0273] In addition, compounds that do not participate or do not significantly participate in charge transport (such as described in WO 2010 / 108579) can be used as co-hosts. In particular, compounds with large band gaps and that do not participate or at least do not significantly participate in the charge transport of the light-emitting layer are suitable for being combined with the compounds according to the present invention as co-matrix materials. Such materials are preferably pure hydrocarbons. Examples of such materials are, for example, found in WO 2009 / 124627 or WO 2010 / 006680. It should be noted in this regard that compounds according to the present invention without special functional groups (such as hole transport groups and / or electron transport groups) have favorable properties.

[0274] Particularly suitable phosphorescent compounds (=triplet emitters) are compounds which emit light under suitable excitation, preferably in the visible range, and which also contain at least one atom, in particular a metal, having an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium are used as phosphorescent emitters, in particular compounds containing iridium or platinum.

[0275] Examples of the above-mentioned luminophores can be found in applications WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626、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, WO 2016 / 124304, WO 2017 / 032439 and WO 2018 / 011186. Generally speaking, all phosphorescent complexes used in the prior art for phosphorescent electroluminescent devices and known to those skilled in the art in the field of organic electroluminescence are suitable, and those skilled in the art may use other phosphorescent complexes without any creative effort.

[0276] Examples of phosphorescent dopants are listed in the table below.

[0277]

[0278]

[0279]

[0280]

[0281] The compounds according to the invention are also particularly suitable as matrix materials for phosphorescent emitters in organic electroluminescent devices, as described in WO 98 / 24271, US 2011 / 0248247 and US 2012 / 0223633. In these multicolor display components, an additional blue-emitting layer is evaporated over the entire surface of all pixels, including those that are not blue.

[0282] In another embodiment of the invention, the organic electroluminescent device according to the invention does not comprise a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, i.e. the emitting layer is directly adjacent to the hole injection layer or the anode, and / or the emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. In addition, metal complexes identical or similar to the metal complexes in the emitting layer can be used directly adjacent to the emitting layer as hole transport or hole injection materials, as described in WO 2009 / 030981.

[0283] In other layers of the organic electroluminescent device according to the present invention, all materials commonly used according to the prior art can be used. Therefore, those skilled in the art can combine all materials known to the organic electroluminescent device with the compound according to the present invention according to formula (I) or the above-mentioned preferred embodiment without creative work.

[0284] It is further preferred that the organic electroluminescent device is characterized in that one or more layers are applied by a sublimation process. -5 mbar, preferably less than 10 -6 However, it is also possible that the initial pressure is lower, for example less than 10 -7 millibar.

[0285] It is also preferred that the organic electroluminescent device is characterized in that one or more layers are applied by an OVPD (organic vapor phase deposition) process or by sublimation with the aid of a carrier gas. -5 A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the material is applied directly through a nozzle and thus structured.

[0286] It is also preferred that the organic electroluminescent device is characterized in that one or more layers are manufactured from solution, for example by spin coating or using any printing method, such as screen printing, flexographic printing, offset printing, LITI (light induced thermal imaging, thermal transfer printing), inkjet printing (inkjet printing) or nozzle printing. For this purpose, soluble compounds are required, which are obtained, for example, by appropriate substitution.

[0287] The formulations for applying the compounds according to formula (I) or the preferred embodiments thereof described above are novel, and therefore another subject of the present invention is a formulation comprising at least one solvent and a compound according to formula (I) or the preferred embodiments thereof described above.

[0288] Furthermore, hybrid methods are possible in which, for example, one or more layers are applied from solution and one or more additional layers are evaporated.

[0289] These processes are generally known to the person skilled in the art and can be applied without inventive step to organic electroluminescent devices which contain the compounds according to the invention.

[0290] The compounds according to the invention and the organic electroluminescent devices according to the invention are characterized by a low refractive index (refractive index RI) compared to the prior art. In addition, these compounds and the organic electroluminescent devices obtained therefrom have an improved service life. At the same time, other electronic properties of the electroluminescent device, such as efficiency or operating voltage, are at least as good. In another variant, the compounds according to the invention and the organic electroluminescent devices according to the invention are characterized by improved efficiency and / or operating voltage and a higher service life compared to the prior art.

[0291] The electronic device according to the present invention, in particular the organic electroluminescent device, has one or more of the following surprising advantages compared to the prior art:

[0292] 1. Electronic devices, in particular organic electroluminescent devices, containing compounds according to formula (I) or the preferred embodiments described above and below, in particular as matrix materials or hole-conducting materials, have outstanding efficiency. In this case, the compounds according to the invention according to formula (I) or the preferred embodiments described above and below, when used in electronic devices, produce low operating voltages.

[0293] 2. Electronic devices, in particular organic electroluminescent devices, containing compounds according to formula (I) or the preferred embodiments described above and below, in particular as matrix materials or hole-conducting materials, have very good service lives. These compounds produce a low roll-off, i.e. a small drop in the energy efficiency of the device at high brightness.

[0294] 3. The compounds according to the invention according to formula (I) or the preferred embodiments described above and below exhibit very high stability and service life.

[0295] 4. Electronic devices, in particular organic electroluminescent devices, which contain the compounds according to formula (I) or the preferred embodiments specified above and below, in particular as matrix material or hole-conducting material, have a very low refractive index.

[0296] 5. With the compounds according to formula (I) or the preferred embodiments described above and below, the formation of optical loss channels in electronic devices, in particular organic electroluminescent devices, can be avoided. These devices are therefore characterized by high PL efficiency of the emitter, and thus high EL efficiency, and excellent energy transfer from the matrix to the dopant.

[0297] 6. The compounds according to formula (I) or the preferred embodiments described above and below have excellent glass film forming ability.

[0298] 7. The compounds according to formula (I) or the preferred embodiments described above and below form very good films from solution.

[0299] The above advantages are not accompanied by excessive degradation of other electronic properties.

[0300] It should be noted that variations of the embodiments described in the present invention belong to the scope of the present invention. Unless explicitly excluded, any feature disclosed in the present invention may be replaced by an alternative feature for the same, equivalent or similar purpose. Therefore, unless otherwise specified, each feature disclosed in the present invention may be regarded as an example of a general sequence, or as an equivalent or similar feature.

[0301] All features of the present invention can be combined in any way, unless some features and / or steps are mutually exclusive. This is especially applicable to the preferred features of the present invention. Likewise, features of non-essential combinations can be used alone (rather than in combination).

[0302] It should also be noted that many features, especially those of the preferred embodiments of the present invention, should be considered as inventive in themselves, rather than just part of the embodiments of the present invention. For these features, independent protection may be sought as a supplement or alternative to the invention currently claimed.

[0303] The teachings of the technical operations disclosed in the present invention may be abstracted and combined with other examples. DETAILED DESCRIPTION

[0304] The present invention will be explained in more detail by the following examples, without wishing to be limited thereto. Those skilled in the art can implement the present invention according to the description in the entire disclosure, and produce other compounds according to the present invention and use them in electronic devices, or apply the method according to the present invention, without creative work.

[0305] Example:

[0306] Unless otherwise specified, the following syntheses were carried out in dry solvents under a protective gas atmosphere. Metal complexes were additionally handled under light-protected conditions or under yellow light. Solvents and reagents can be used, for example, from Sigma-ALDRICH or ABCR. The information given in square brackets or the numbers given for the individual compounds refer to the CAS numbers of the compounds known in the literature. In compounds that may have multiple enantiomers, diastereomers or tautomers, one form is representatively represented.

[0307] Synthetic LS known in the literature:

[0308]

[0309]

[0310] Synthesis of compounds according to the invention:

[0311] Examples A, B and Synthesis S:

[0312] Embodiment A1:

[0313]

[0314] Organocopper chloride was produced according to M. Oi et al., Chem. Sci., 2019, 10, 6107 and oxygen-mediated CN coupling was performed according to H. Yamamoto et al., J. Org. Chem., 1980, 45, 2739.

[0315] Rind-CuCl was prepared from 3.49g (10mmol) LS1, as described in M.Oi et al., Chem.Sci., 2019, 10, 6107, Example 36. After being heated to 0°C and stirred for 1 hour, the Rind-CuCl solution was cooled to -20°C, and then, under good stirring, a freshly prepared diphenylamine lithium solution of 1.6M n-butyl lithium of 1.86g (11mmol) diphenylamine [122-39-4] in 30ml THF and 6.9ml n-hexane was added, and stirred for 2 hours. Then, an oxygen flow was guided through the solution via a glass dropper for 5 minutes, stirred for 20 minutes, quenched with 50ml saturated ammonium chloride solution, 200ml ethyl acetate was added, the organic phase was separated, and the solvent was removed under vacuum. The crude product was further purified by chromatography and repeated hot extractive crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-dichloromethane (DCM), 1:3 to 3:1 vv) and fractional sublimation or annealing in high vacuum, respectively. Yield: 3.1 g (6.9 mmol) 69%; purity: about 99.9%. HPLC.

[0316] The yield depends on the steric requirement of LS1 to LS8, where the following decreasing sequence LS1-LS2-LS3>LS4>LS5-LS6-LS7-LS8 is usually observed, and on the steric requirement of the secondary amine, which is usually in the range of 50-80%.

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335] Examples C, D and E:

[0336] Example C1:

[0337]

[0338] According to M.Oi et al., Chem.Sci., 2019, 10, 6107, Example 36.

[0339] Method: 34.9 g (100 mmol) LS1, 40.8 g (110 mmol) [38257-52-2] 4-iodotriphenylamine instead of methyl 4-iodobenzoate, in a stirred autoclave, 120 ° C, 24 hours. The crude product is purified by chromatography and / or repeated hot extraction crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) and fractional sublimation or annealing in high vacuum. Yield: 33.4 g (65 mmol) 65%; purity: about 99.9%. HPLC.

[0340] Similarly, the following compounds can be prepared, where the stoichiometry is adjusted according to the CC bond to be bonded when using dibromides and tribromides. The yields depend on the steric requirements of LS1 to LS8, where the following decreasing sequence LS1-LS2-LS3>LS4>LS5-LS6-LS7-LS8 is generally observed. On the other hand, for arylaminohalogen coupling agents of bromides, they are generally in the range of 40-60%, and for iodides, they are in the range of 50-70%.

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366] Example: Production of OLEDs

[0367] 1) Vacuum treatment equipment:

[0368] The OLEDs according to the invention and the OLEDs used as reference were produced according to the general process described in WO 2004 / 058911, which was adapted to the conditions described there (layer thickness variation, materials used).

[0369] The results of different OLEDs are given in the following examples. Purified glass sheets (cleaned in a Miele laboratory washer, Merck Extran cleaning agent) were coated with structured ITO (indium tin oxide) with a thickness of 50 nm, and the glass sheets were pretreated with UV ozone for 25 minutes (UV ozone generator PR-100, UVP company). These coated glass sheets formed the substrate on which the OLED was applied.

[0370] 1a) Blue Fluorescent OLED Component - BF:

[0371] The compounds according to the present invention can be used in hole injection layers (HILs), hole transport layers (HTLs) and electron blocking layers (EBLs). All materials are thermally evaporated in a vacuum chamber. Here, the light-emitting layer (EML) is always composed of at least one matrix material (main material, main material) SMB (see Table 1) and a luminescent dopant (dopant, luminophore) D, and the luminescent dopant is mixed into one or more matrix materials in a certain volume ratio by co-evaporation. Here, for example, the data of SMB:D (97:3%) means that the SMB material is present in the layer in a volume ratio of 97% and the dopant D is present in the layer in a volume ratio of 3%. Similarly, the electron transport layer can also be composed of a mixture of two materials, see Table 1. The materials used to manufacture OLEDs are shown in Table 5, or refer to the above-mentioned synthesis examples.

[0372] OLEDs are characterized in accordance with the standards. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in percent) (depending on the brightness) and the lifetime are determined. The external quantum efficiency is calculated from the current-voltage-luminance characteristic curve (IUL characteristic curve) assuming Lambertian radiation characteristics. The EQE in % and the voltage in V at 1000 cd / m 2 The service life is given at a brightness of 10000cd / m 2 The measured time for the reference luminance to fall to 80% of the initial luminance is set as 100%. The service life of OLED components containing the compounds according to the invention is given as a percentage relative to the reference.

[0373] OLEDs have the following layer structure:

[0374] Base

[0375] Hole injection layer (HIL), made of HTM1 doped with 5% NDP-9 (available from Novaled), 20 nm

[0376] Hole transport layer (HTL), see Table 1

[0377] Electron blocking layer (EBL), see Table 1

[0378] Emission layer (EML), see Table 1

[0379] Electron transport layer (ETL), see Table 1

[0380] Electron injection layer (EIL) made of ETM2, 1nm

[0381] Aluminum cathode, 100nm

[0382] Table 1: Structure of blue fluorescent OLED components

[0383]

[0384]

[0385] Table 2: Results of blue fluorescent OLED components

[0386]

[0387] 1b) Phosphorescent OLED components:

[0388] The compound A according to the invention can be used as a matrix material (host material, main material) M (see Table 5) or A (see materials according to the invention) in a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL) and an emitting layer (EML). To this end, all materials are thermally evaporated in a vacuum chamber. Here, the emitting layer is always composed of at least one or more matrix materials M and a phosphorescent dopant Ir, the latter being mixed into one or more matrix materials in a certain volume ratio by co-evaporation. For example, the data of M1:M2:Ir (55%:35%:10%) means here that the material M1 is present in the layer in a volume ratio of 55%, M2 in a volume ratio of 35%, and Ir in a volume ratio of 10%. Similarly, the electron transport layer can also consist of a mixture of two materials. The exact structure of the OLED can be seen in Table 3. The materials used to produce the OLED are shown in Table 5, or refer to the above-mentioned synthesis examples.

[0389] OLEDs are characterized in accordance with the standards. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in percent) (depending on the brightness) and the lifetime are determined. The external quantum efficiency is calculated from the current-voltage-luminance characteristic curve (IUL characteristic curve) assuming Lambertian radiation characteristics. The EQE in % and the voltage in V at 1000 cd / m 2 The service life is given at a brightness of 1000cd / m2 in blue and red. 2 , green and yellow are 10000cd / m 2 The measured time for the reference luminance to fall to 80% of the initial luminance is set as 100%. The service life of OLED components containing the compounds according to the invention is given as a percentage relative to the corresponding reference.

[0390] OLEDs have the following layer structure:

[0391] Base

[0392] Hole injection layer (HIL), made of HTM1 doped with 5% NDP-9 (available from Novaled), 20 nm

[0393] Hole transport layer (HTL), see Table 3

[0394] Electron blocking layer (EBL), see Table 3

[0395] Emission layer (EML), see Table 3

[0396] Hole blocking layer (HBL), see Table 3

[0397] Electron transport layer (ETL): made of ETM1:ETM2 (50%:50%), 30nm Electron injection layer (EIL), made of ETM2, 1nm

[0398] Aluminum cathode, 100nm

[0399] Table 3: Structure of phosphorescent OLED components

[0400]

[0401]

[0402]

[0403]

[0404] Table 4: Results for phosphorescent OLED components

[0405]

[0406]

[0407]

[0408] Table 5: Structural formula of materials used

[0409]

[0410]

[0411]

[0412]

Claims

1. A compound comprising at least one structure of formula (I), The symbols represent: Z a In each occurrence, the same or different representations of Ar, R c , L 1 -N(Ar)2 or L 1 -Q; Ar is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can be replaced by one or more radicals R d Substitution, wherein the two residues Ar bound to the same N atom can also be separated by a single bond or by a substitution selected from B(R d )、C(R d )2、Si(R d )2. C=O, C=NR d , C=C(R d 2. R d C=CR d 、O、S、S=O、SO2、N(R d )、P(R d )、P(=O)R d and can be replaced by one or more residues R d The bridges of the substituted ortho-linked phenylene groups are bridged to each other; L 1 represents, identically or differently on each occurrence, a bond or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R; R a is, identically or differently on each occurrence, a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 10 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 10 carbon atoms, each of which can be replaced by one or more radicals R 2 substituted, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which can be replaced by one or more radicals R 2 substituted, wherein two or more substituents R a Can form ring systems with each other; R b is, at each occurrence, identically or differently, H, D, a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 10 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 10 carbon atoms, each of which can be replaced by one or more radicals R 2 substituted, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which can be replaced by one or more radicals R 2 Substitution, where two substituents R b Able to form ring systems with each other; Q, identically or differently on each occurrence, represents an electron transport group, preferably a nitrogen-containing heteroaryl group having 5 to 12 ring atoms, which can be replaced by one or more residues R e replace; R, R c , R d , R e H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2, C(=O)N(Ar')2, C(=O)N(R 1 )2、C(Ar')3、C(R 1 )3、Si(Ar')3、Si(R 1 )3、B(Ar')2、B(R 1 )2, C(=O)Ar', C(=O)R 1 、P(=O)(Ar')2、P(=O)(R 1 )2、P(Ar')2、P(R 1 )2, S(=O)Ar', S(=O)R 1 、S(=O)2Ar'、S(=O)2R 1 、OSO2Ar'、OSO2R 1 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group can be replaced by one or more residues R 1 Substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 1 C=CR 1 、C≡C、Si(R 1 )2. C=O, C=S, C=Se, C=NR 1 、C(=O)O、C(=O)NR 1 -、NR 1 ,P(=O)(R 1 ), -O-, S, SO or SO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can be replaced by one or more radicals R 1 substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which can be replaced by one or more radicals R 1 substitution, where two residues R, R d , R e can also form a ring system with each other, or residues R, R d , R e With other groups, in particular the residue R c Can form ring systems; Ar' is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can be replaced by one or more radicals R 1 Substitution, wherein two residues Ar' bound to the same C atom, Si atom, N atom, P atom or B atom can also be separated by a single bond or by a residue selected from B(R 1 )、C(R 1 )2、Si(R 1 )2. C=O, C=NR 1 , C=C(R 1 )2, O, S, S=O, SO2, N(R 1 )、P(R 1 ) and P(=O)R 1 The bridges are connected to each other; R 1 H, D, F, Cl, Br, I, CN, NO2, N(Ar")2, N(R 2 )2、C(=O)Ar”、C(=O)R 2 ,P(=O)(Ar”)2,P(Ar”)2,B(Ar”)2,B(R 2 )2、C(Ar”)3、C(R 2 )3、Si(Ar”)3、Si(R 2 )3. a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which can be replaced by one or more residues R 2 Substitution, where one or more non-adjacent CH2 groups can be replaced by -R 2 C=CR2-、C≡C-、Si(R 2 )2. C=O, C=S, C=Se, C=NR 2 、C(=O)O-、C(=O)NR 2 -、NR 2 ,P(=O)(R 2 ), -O-, S, SO or SO2, and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can be replaced by one or more residues R 2 substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which can be replaced by one or more radicals R 2 substituted, or an aralkyl or heteroaralkyl radical having 5 to 60 aromatic ring atoms, which can be replaced by one or more radicals R 2 substitution, or a combination of these systems; wherein two or more residues R 1 can form a ring system with each other, in which one or more residues R 1 capable of forming a ring system with another part of the compound; Ar" is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which can be replaced by one or more radicals R 2 substitution, wherein two residues Ar" bound to the same C atom, Si atom, N atom, P atom or B atom can also be separated by a single bond or by a residue selected from B(R 2 )、C(R 2 )2、Si(R 2 )2. C=O, C=NR 2 , C=C(R 2 )2, O, S, S=O, SO2, N(R 2 )、P(R 2 ) and P(=O)R 2 The bridges are connected to each other; R 2 is selected, identically or differently on each occurrence, from H, D, F, CN, an aliphatic hydrocarbon residue having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein one or more H atoms can be replaced by D, F, Cl, Br, I or CN and can be substituted by one or more alkyl radicals having 1 to 4 carbon atoms, wherein two or more substituents R 2 can form a ring system with each other.

2. The compound according to claim 1, comprising at least one structure of formula (I-1) to (I-4), The symbols Ar, Lr 1 ,Q,R a , R b and R c Has the meaning set out in claim 1.

3. The compound according to claim 1 or 2, characterized in that The group Ar is selected, identically or differently on each occurrence, from the formula (Ar a -1) to (Ar a -28) structure, where the following holds for the symbols used: Y 2 O, S, NR d or C(R d )2; k is independently 0 or 1 at each occurrence; i is independently 0, 1, or 2 at each occurrence; j is independently 0, 1, 2, or 3 at each occurrence; h is independently 0, 1, 2, 3, or 4 at each occurrence; g is independently 0, 1, 2, 3, 4, or 5 at each occurrence; R d has the meaning given above, in particular for claim 1 , and the dashed key marks the binding position.

4. Compounds according to one or more of claims 1 to 3, characterized in that The compounds do not contain an aromatic or heteroaromatic ring system having three aromatic six-membered rings which are fused to one another.

5. The compound according to at least one of the preceding claims 1 to 4, characterized in that The compound does not contain a cyclobutyl residue having two oxygen atoms bonded thereto, and the compound also does not contain a thiadiazine group.

6. The compound according to at least one of the preceding claims 1 to 5, characterized in that The compounds do not contain alkoxy, thioalkoxy or hydroxyl groups.

7. Compounds according to one or more of claims 1 to 6, characterized in that Group L 1 Identically or differently represent a bond or are selected from the formula (L 1 -1) to (L 1 -22) structure, where the following holds for the symbols used: Y is CR2, O, S or NR; j is independently 0, 1, 2, or 3 at each occurrence; h is independently 0, 1, 2, 3, or 4 at each occurrence; R has the meaning given above, in particular for claim 1 , and the dashed bond marks the binding site.

8. A compound according to one or more of claims 1 to 7, comprising at least one structure of formula (II-1) to (II-62), The symbols R and R a , R b , R c and R d has the meaning given in claim 1, and for the other symbols the following applies: In the case where a group is attached to the structure, X represents N, CR or C identically or differently at each occurrence; For a group to be bound to the structure, X 1 Represents N, CR the same or differently in each occurrence d or C; Y represents O, S, NR or C(R)2, preferably O, NR or C(R)2; and Y 1 Represents O, S, BR d NR d 、Si(R d )2 or C(R d )2.

9. A compound according to any one of claims 1 to 8, comprising at least one structure of formula (III-1) to (III-62), The symbols R and R a , R b , R c and R d has the meaning given in claim 1, and the following applies to the symbols used: Y is O, S, NR or C(R)2; Y 1 Represents O, S, BR d NR d 、Si(R d )2 or C(R d )2; n is independently 0, 1, 2, or 3 at each occurrence; m is independently 0, 1, 2, 3, or 4 at each occurrence; l is independently 0, 1, 2, 3, 4, or 5 at each occurrence.

10. The compound according to at least one of the preceding claims 1 to 9, characterized in that Residue R c represents H, D, methyl, ethyl, propyl, wherein these groups can be deuterated.

11. Compound according to at least one of the preceding claims 1 to 10, characterized in that For the symbols the following holds: R, R c , R d H, D, N(Ar')2, N(R 1 )2、C(Ar')3、C(R 1 )3、Si(Ar')3、Si(R 1 )3、B(Ar')2、B(R 1 ) 2. a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group can be replaced by one or more residues R 1 Substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 1 C=CR 1 、C≡C、Si(R 1 )2. C=O, C=S, C=Se, C=NR 1 、C(=O)O、C(=O)NR 1 -、NR 1 ,P(=O)(R 1 ), SO or SO2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which can be replaced by one or more radicals R 1 substitution; here, the two residues R, R d They can also form a ring system or a residue R, R d with another group, in particular the residue R c Capable of forming a ring system.

12. The compound according to at least one of the preceding claims 1 to 11, characterized in that The compound has a molecular weight of less than or equal to 5000 g / mol, preferably less than or equal to 4000 g / mol, particularly preferably less than or greater than 3000 g / mol, particularly preferably less than or equal to 2000 g / mol, more particularly preferably less than or equal to 1200 g / mol, and especially preferably less than or equal to 900 g / mol.

13. Oligomer, polymer or dendrimer containing one or more compounds according to any one of claims 1 to 12, wherein instead of a hydrogen atom or a substituent there are one or more bonds of said compound to the polymer, oligomer or dendrimer.

14. Preparation containing at least one compound according to one or more of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13 and at least one further compound, wherein the further compound is preferably selected from one or more solvents.

15. A composition comprising at least one compound according to one or more of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF, host materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, electron blocking materials and hole blocking materials, preferably host materials.

16. Process for preparing compounds according to one or more of claims 1 to 12, characterized in that A phenyl compound having a cyclopentyl group fused thereto is synthesized, and at least one aromatic or heteroaromatic residue is introduced, preferably by a nucleophilic aromatic substitution reaction or a coupling reaction.

17. Use of a compound according to one or more of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13 in electronic devices, preferably as host material, hole transport material, hole injection material or electron blocking material.

18. An electronic device comprising at least one compound according to one or more of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13.

19. The electronic device according to claim 18, wherein: The electronic device is an organic electroluminescent device, characterized in that the organic electroluminescent device comprises at least one light-emitting layer and at least one hole transport layer, and the hole transport layer comprises a compound according to one or more of claims 1 to 13 or an oligomer, polymer or dendrimer according to claim 14.

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