Nitrogen-containing heterocyclic compounds for organic electroluminescent devices

Abstract

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

Description

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

[0002] The luminescent material used in organic electroluminescent devices is usually a phosphorescent organometallic complex. For reasons of quantum mechanics, the use of organometallic compounds as phosphorescent emitters can achieve up to four times the energy efficiency and power efficiency. In electroluminescent devices, especially in electroluminescent devices that also exhibit triplet luminescence (phosphorescence), improvements are usually still needed. The properties of phosphorescent electroluminescent devices do not only depend on the triplet emitters used. More particularly, other materials such as matrix materials used are also particularly important here. Thus, the improvement of these materials can also lead to a significant improvement in the performance of electroluminescent devices.

[0003] In addition, many electroluminescent devices, in addition to the light-emitting layer, also contain other layers, such as one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers and / or charge generation layers. These layers have a considerable influence on the performance of the electroluminescent device.

[0004] The electroluminescent device described in detail above is the subject matter of the document WO 2014 / 015938 A1.

[0005] In general, in the case of these materials used, for example, as matrix materials, there is still a need for improvement, in particular with regard to the lifetime and with regard to the efficiency and operating voltage of the components.

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

[0007] More particularly, the purpose of the present invention is to provide compounds that lead to long life, good efficiency and low operating voltage. In particular, the contribution to these properties is achieved by electron injection materials, electron transport materials and hole blocking materials. In addition, the properties of the matrix material, also referred to as the host material herein, also have a significant impact on the life and efficiency of the organic electroluminescent device.

[0008] Another object of the present invention is to provide compounds having a low refractive index (RI).

[0009] Another object of the present invention that can be considered is to provide compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, especially as host materials. In particular, one object of the present invention is to provide host materials suitable for green- or blue-phosphorescent electroluminescent devices, and also for red- or yellow-phosphorescent electroluminescent devices.

[0010] Furthermore, the compounds, especially when used as host materials, electron injection materials, electron transport materials or hole blocking materials in organic electroluminescent devices, should provide the devices with excellent color purity.

[0011] Another object that can be considered is to provide an electronic device having excellent performance which is very inexpensive and of stable quality.

[0012] Furthermore, it should be possible to use or modify electronic devices for many purposes. More particularly, the performance of electronic devices should be maintained over a wide temperature range.

[0013] It has been surprisingly found that the specific compounds described in detail below achieve this object and are very suitable for use in electroluminescent devices and lead to organic electroluminescent devices showing very good properties, especially in terms of lifetime, color purity, efficiency, operating voltage and refractive index. Therefore, the present invention provides these compounds and electronic devices comprising such compounds, especially organic electroluminescent devices.

[0014] The present invention provides a compound comprising at least one structure of formula (I), preferably a compound of formula (I),

[0015]

[0016] Formula (I)

[0017] The symbols are as follows:

[0018] Z a are the same or different in each case and are Ar, R c , L 1 -Q or L 1 -N(Ar)2, preferably R c , L 1 -Q or L 1 -N(Ar)2;

[0019] Q is identical or different in each case and is an electron transport group, preferably having 5 to 12 ring atoms, more preferably 6 to 12 ring atoms and can be replaced by one or more R d a nitrogen-containing heteroaryl group substituted with a radical;

[0020] L 1are identical or different in each case and are a bond or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups;

[0021] R a are identical or different in each case and are: a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10 carbon atoms, each of which may be replaced by one or more R 2 or have 5 to 20 aromatic ring atoms and may be substituted by one or more R 2 The aromatic or heteroaromatic ring system substituted by a group is preferably a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be substituted by one or more R 2 A phenyl group, which may be substituted with one or more R 2 Substitution by groups, wherein two or more, preferably adjacent, substituents R a Can form a ring system together;

[0022] R b are in each case identical or different and are: H, D, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10 carbon atoms, each of which may be replaced by one or more R 2 or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which may be replaced by one or more R 2 The alkyl group is preferably substituted by: H, D, a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms or a phenyl group, each of which may be substituted by one or more R 2 Substitution by groups, wherein two, preferably adjacent, substituents R b can together form a ring system, more preferably H or D;

[0023] Ar is identical or different in each case and is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups, wherein two Ar groups bonded to the same nitrogen atom may also be bridged to one another via a single bond or a bridging group selected from the group consisting of B(R), C(R)2, Si(R)2, C=O, C=NR, C=C(R)2, RC=CR, O, S, S=O, SO2, N(R), P(R), P(=O)R and ortho-attached phenylene groups which may be substituted by one or more R groups, preferably selected from the group consisting of C(R)2, O, N(R) and ortho-attached phenylene groups which may be substituted by one or more R groups, wherein wherein Ar is preferably identical or different in each case and is an aryl or heteroaryl group having 6 to 40 aromatic ring atoms and which may be substituted by one or more R groups, wherein two Ar groups bonded to the same nitrogen atom may also be bridged to one another via a single bond or a bridging group selected from B(R), C(R)2, Si(R)2, C=O, C=NR, C=C(R)2, RC=CR, O, S, S=O, SO2, N(R), P(R), P(=O)R and ortho-bound phenylene groups which may be substituted by one or more R groups, preferably selected from C(R)2, O, N(R) and ortho-bound phenylene groups which may be substituted by one or more R groups;

[0024] R, R c , R d are in each case identical or different and are: 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 may be replaced by one or more R1 group, 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 has 5 to 60 aromatic ring atoms and can be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and which may be replaced by one or more R 1 A substituted aryloxy or heteroaryloxy group, wherein two R, R d The groups together or one R, R d The groups and other groups, especially R c The groups together may also form a ring system;

[0025] Ar' is identical or different in each case and is an aromatic ring having 5 to 60 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group, wherein two Ar' groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom can also be connected by a single bond or 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 bridging groups in the bridge each other;

[0026] R 1 are in each case identical or different and are: 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, 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 may be substituted by one or more R 2 group, 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 hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or have 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and which may be replaced by one or more R 2 substituted aryloxy or heteroaryloxy groups, or having 5 to 60 aromatic ring atoms and which may be replaced by one or more R 2 substituted aralkyl or heteroaralkyl groups, or combinations of these systems, in which two or more, preferably adjacent, R 1 The groups may together form a ring system in which one or more R 1 The group may form a ring system with other parts of the compound;

[0027] Ar'' is identical or different in each case and is a cyclic aromatic ring having 5 to 30 atoms and may be replaced by one or more R 2 Aromatic or heteroaromatic ring system substituted with a group, wherein two Ar'' groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom can also be connected by a single bond or 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 bridging groups in the bridge each other;

[0028] R 2are in each case identical or different and are selected from: H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl radicals each having 1 to 4 carbon atoms, wherein two or more, preferably adjacent, substituents R 2 Can form a ring system together.

[0029] Aryl groups in the context of the present invention contain 6 to 40 carbon atoms; heteroaryl groups in the context of the present invention contain 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 groups or heteroaryl groups are understood to mean: simple aromatic rings, i.e. benzene; or simple heteroaromatic rings, such as pyridine, pyrimidine, thiophene, etc.; or fused (annulated) aryl or heteroaryl groups, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatic compounds which are linked to one another by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0030] The electron-deficient heteroaryl group in the context of the present invention is a heteroaryl group having at least one heteroaromatic six-membered ring with at least one nitrogen atom. Other aromatic or heteroaromatic five-membered rings or six-membered rings can be fused to the six-membered ring. Examples of electron-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline or quinoxaline.

[0031] The aromatic ring system in the context of the present invention contains 6 to 60 carbon atoms in the ring system. The heteroaromatic ring system in the context 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. An aromatic or heteroaromatic ring system in the context of the present invention is understood to refer to a system in which it does not necessarily contain only aryl or heteroaryl groups, but in which two or more aryl or heteroaryl groups may also be connected via non-aromatic units such as carbon, nitrogen or oxygen atoms. For example, in the context of the present invention, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. should also be regarded as aromatic ring systems, as well as systems in which two or more aryl groups are connected, for example, via 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 and / or heteroaryl groups are linked to each other via a single bond.

[0032] In the context of the present invention, an aliphatic hydrocarbyl radical or an alkyl radical or an alkenyl or alkynyl radical which may contain 1 to 20 carbon atoms and in which individual hydrogen atoms or CH2 groups may also be replaced by the abovementioned radicals is preferably understood as meaning a 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, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl radical. Alkoxy groups having 1 to 40 carbon atoms are preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. Thioalkyl radicals having 1 to 40 carbon atoms are understood to mean in particular 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 group 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 hydrogen atoms may also be replaced by D, F, Cl, Br, I, CN or NO2, preferably by F, Cl or CN, also preferably by F or CN, and particularly preferably by CN.

[0033] Aromatic or heteroaromatic ring systems having 5 to 60 or 5 to 40 aromatic ring atoms and which may in each case also be substituted by the abovementioned radicals and which can be attached to the aromatic or heteroaromatic system via any desired position are understood as meaning in particular radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, lettuce, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylylidene, terphenyl, biphenylylidene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene ... indenocarbazole, cis- or trans-indolecarbazole, 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, phenazine, pyrazole, indazole, imidazole, benzimidazole, naphthymidazole, phenanthroimidazole, pyridimidazole, pyrazinimidazole, quinoxaline Imidazole, oxadiazole, benzooxadiazole, naphthooxadiazole, anthraoxadiazole, phenanthrazine, isoxadiazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazaterphenylene, 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, phenazine, phenothiazine, fluorescein ring, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-Triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, and benzothiadiazole.

[0034] In the context of this specification, the expression that two or more groups together can form a ring is understood to mean in particular that the two groups are connected to each other by a chemical bond under the conditions of formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0035] .

[0036] In addition, however, the above wording is also understood to mean that if one of the two groups is hydrogen, the second group is bonded to the position to which the hydrogen atom is bonded, thereby forming a ring. This will be illustrated by the following scheme:

[0037] .

[0038] In a preferred configuration, the compound of the present invention may preferably contain at least one structure of formula (I-1) to (I-4) and more preferably be selected from compounds of formula (I-1) to (I-4),

[0039]

[0040] The symbols Ar, Lr 1 ,Q,R a , R b and R c has the meanings given above, in particular for formula (I).

[0041] The Q groups are identical or different in each case and are electron-transporting groups, wherein the electron-transporting groups preferably have 5 to 12 ring atoms, more preferably 6 to 12 ring atoms and can be replaced by one or more R d The Q group is preferably an electron-deficient heteroaryl group, wherein the latter more preferably also has the properties detailed above and below.

[0042] Particular advantages can be achieved when the Q group is a nitrogen-containing heteroaryl group having 6 to 12 ring atoms and at least two nitrogen atoms in the ring, which can be replaced by one or more R d The radical is substituted wherein the carbon atoms adjacent to at least two nitrogen atoms in the ring are not bonded to hydrogen atoms.

[0043] Electron transport groups are well known in the art and can improve the ability of a compound to transport and / or conduct electrons. These groups include, in particular, nitrogen-containing heteroaryl groups having 5 to 12 ring atoms, more preferably 6 to 12 ring atoms, wherein these groups are typically electron-deficient heteroaryl groups.

[0044] Preferably, the Q group is a pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and / or benzimidazole group, preferably a pyrimidine, pyrazine, triazine, quinazoline, quinoxaline and / or benzimidazole group, more preferably a pyrimidine, triazine, quinazoline and / or quinoxaline group, more preferably a pyrimidine and / or triazine group, most preferably a triazine group, which may be replaced by one or more R d Group substitution.

[0045] More preferably, the Q group is a pyrimidine, pyrazine, triazine, quinazoline, quinoxaline and / or benzimidazole group, more preferably a pyrimidine, triazine, quinazoline and / or quinoxaline group, more preferably a pyrimidine and / or triazine group, most preferably a triazine group, which may be replaced by one or more R dThe radical is substituted wherein the carbon atoms adjacent to at least two nitrogen atoms in the ring are not bonded to hydrogen atoms.

[0046] In a particularly preferred embodiment, it is possible that the Q group is a pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, imidazole and / or benzimidazole group, preferably a pyrimidine, pyrazine, triazine, quinazoline, quinoxaline and / or benzimidazole group, which may be replaced by one or more R d A radical in which the carbon atoms adjacent to at least two nitrogen atoms are substituted with an aromatic ring having 5 to 60 atoms and which may be substituted with one or more R 1 The aromatic or heteroaromatic ring system substituted by the radical is bonded.

[0047] Particular advantages that can be achieved with this embodiment include, among other things, a longer lifetime of the electronic components.

[0048] Thus, it is very particularly advantageous if the Q radical is 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 R d A radical in which the carbon atoms adjacent to at least two nitrogen atoms are substituted with an aromatic ring having 5 to 60 atoms and which may be substituted with one or more R 1 Aromatic or heteroaromatic ring system bonded to a radical-substituted

[0049] Alternatively, the Q group is a pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, imidazole and / or benzimidazole group, preferably a pyrimidine, pyrazine, triazine, quinazoline, quinoxaline and / or benzimidazole group, which may be replaced by one or more R d A substituted radical, wherein the carbon atoms adjacent to at least two nitrogen atoms are bonded to 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 adjacent to the carbon atom bonded to the respective nitrogen atom does not have any acidic hydrogen atoms and can in each case be replaced by one or more R 1 Group substitution,

[0050] wherein the carbon atoms adjacent to the at least two nitrogen atoms are preferably connected to a carbon ring having 5 to 60 aromatic ring atoms and which can be replaced by one or more R 1 The aromatic or heteroaromatic ring system substituted by the radical is bonded.

[0051] In a further preferred configuration, it is possible that the Q radicals are identical or different in each case and are selected from the structures of the formulae (Q-1) to (Q-16),

[0052]

[0053]

[0054]

[0055]

[0056] Where R d With the definitions given above, especially for formula (I), the dashed bond represents the attachment site, and the other symbols are defined as follows:

[0057] Y 1 O, S, NR d or C(R d )2, preferably O, NR d or C(R d )2;

[0058] n is independently at each occurrence 0, 1, 2 or 3, preferably 0, 1 or 2; and

[0059] m is independently 0, 1, 2, 3 or 4 at each occurrence, preferably 0, 1 or 2.

[0060] In this context, structures (Q-1) to (Q-14) are preferred, structures (Q-1) to (Q-8) are particularly preferred, and structures (Q-1), (Q-4), (Q-7) and (Q-12) are particularly preferred, and structure (Q-1) is most preferred.

[0061] In a further preferred configuration, it is possible that the Q radicals are identical or different in each case and are selected from the structures of the formulae (Q-1′) to (Q-15′),

[0062]

[0063]

[0064]

[0065]

[0066] Where R d With the definitions given above, especially for formula (I), the dashed bond represents the attachment point, and the other symbols are defined as follows:

[0067] R e are identical or different in each case and are N(AR')2 radicals or have 5 to 60 aromatic ring atoms and may be replaced by one or more R 1Aromatic or heteroaromatic ring system substituted with a radical, wherein both R e Group together or one R e The group and other groups, especially R e The groups together may also form a ring system;

[0068] Y 1 O, S, NR d or C(R d )2, preferably O, NR d or C(R d )2; n is independently 0, 1, 2 or 3 at each occurrence, and

[0069] n is independently 0, 1, 2 or 3 at each occurrence, preferably 0, 1 or 2, and

[0070] m is independently 0, 1, 2, 3 or 4 at each occurrence, preferably 0, 1 or 2.

[0071] In this context, structures (Q'-1) to (Q'-14) are preferred, structures (Q'-1) to (Q'-12) are particularly preferred, and structures (Q'-1), (Q'-4), (Q'-7) and (Q'-12) are particularly preferred, with structure (Q'-1) being most preferred.

[0072] In a further preferred configuration, it is possible that the Q radicals are identical or different in each case and are selected from the structures of the formula (Q-1a), (Q-1b), (Q-1c), (Q-1d), (Q-1e), (Q-1f), (Q-1g), (Q-1h), (Q-1i), (Q-1j), (Q-1k), (Q-1l), (Q-1m) and / or (Q-1n),

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080] Where R 1 With the definitions given above, in particular for formula (I), dashed bonds mark the attachment positions and the notations used are as follows:

[0081] j is independently 0, 1, 2 or 3 at each occurrence, preferably 0, 1 or 2;

[0082] h is independently 0, 1, 2, 3 or 4 at each occurrence, preferably 0, 1 or 2;

[0083] l is independently 0, 1, 2, 3, 4 or 5 at each occurrence, preferably 0, 1 or 2.

[0084] Furthermore, it is possible that the Ar groups are identical or different in each case and are selected 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 terphenylidene, each of which may be substituted by one or more R groups, preferably phenyl, biphenyl, fluorene, dibenzofuran, terphenylidene or indolocarbazole.

[0085] In a further preferred configuration, it is feasible that L 1 The groups are the same or different and are bonds or are selected from the formula (L 1 -1) to (L 1 -22) structure,

[0086]

[0087]

[0088] The symbols used are as follows:

[0089] Y is CR2, O, S or NR, preferably O or NR;

[0090] j is independently 0, 1, 2 or 3 at each occurrence, preferably 0, 1 or 2;

[0091] h is independently 0, 1, 2, 3 or 4 at each occurrence, preferably 0, 1 or 2;

[0092] R has the meanings given above, in particular for formula (I), and the dashed bond marks the point of attachment.

[0093] Formula (L 1 -1) to (L 1 The sum of the indices i, j and h in the structure of -22) is preferably not more than 6, particularly preferably not more than 4, and more preferably not more than 2.

[0094] In one embodiment, it is possible that the Q group does not contain any carbazole group, preferably does not contain any carbazole group and / or any of the formula N(Ar')2, N(R 1 )2, more preferably does not contain any hole transporting group.

[0095] In one embodiment, it is feasible that L 1 The group does not contain any carbazole group, preferably does not contain any carbazole group and / or any of the formula N(Ar')2, N(R 1 )2, more preferably does not contain any hole transporting group.

[0096] Where L 1 Compounds whose Q groups do not contain any hole-transporting groups are particularly suitable as electron-injecting materials, electron-transporting materials or hole-blocking materials for use in the corresponding layers, which generally do not contain any emitting compounds.

[0097] In another embodiment, it is possible that L 1 The group comprises a hole transport group, preferably comprises a carbazole group and / or a substituent of the formula N(Ar')2, and more preferably comprises a carbazole group.

[0098] In another embodiment, it is possible that the Q group comprises a hole transport group, preferably a carbazole group and / or a substituent of the formula N(Ar')2, more preferably a carbazole group.

[0099] Where L 1 Compounds whose Q groups contain hole transport groups are particularly suitable as host materials for use in combination with light-emitting compounds.

[0100] Hole-transporting groups are well known in the art and include, in particular, di- or tri-arylamine groups, carbazole groups and groups having similar properties.

[0101] In a further preferred embodiment, it is feasible that the compound of the present invention comprises the structure of formula (II-1) to (II-44), wherein the compound of the present invention may be more preferably selected from the compounds of formula (II-1) to (II-44),

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] The symbols R and R a , R b , R c and R d has the definitions given above, especially for formula (I), and the other symbols are as follows:

[0111] X is identical or different at each occurrence and is N, CR, or, if the group is bonded to the structure, C;

[0112] X 1 Same or different in each case and N or CR d , preferably N;

[0113] X 2 Same or different in each case and N or CR d , preferably CR d ;

[0114] Y is O, S, NR or C(R)2, preferably O, NR or C(R)2; and

[0115] Y 1 O, S, NR d or C(R d )2, preferably O, NR d or C(R d )2.

[0116] Here, structures / compounds of formula (II-1), (II-2), (II-3), (II-6), (II-7), (II-12), (II-17), (II-18), (II-23), (II-28), (II-29), (II-34), (II-39) and (II-40) are preferred, and structures / compounds of formula (II-1), (II-6), (II-7), (II-12) and (II-34) are particularly preferred.

[0117] It is preferred that, especially in the structures / compounds of formulae (II-1) to (II-44), no more than three, preferably no more than two X groups on each ring are N, and preferably all X are CR; preferably at least one, more preferably at least two X groups on each ring are selected from CH and CD.

[0118] It is also possible that, especially in the structures / compounds of the formulae (II-1) to (II-44), no more than four, preferably no more than two, X groups are N; more preferably, all X groups are CR, wherein preferably no more than 4, more preferably no more than 3, and especially preferably no more than 2 of the CR groups represented by X are not CH groups.

[0119] In another embodiment, especially in the structures / compounds of formula (II-1) to (II-44), it is possible that no more than three, preferably no more than two X are present on each ring. 2 The group is N, and preferably all X 2 All CR d Preferably at least one, more preferably at least two X on each ring 2 The group is selected from CH and CD.

[0120] In a further preferred configuration, in particular in the structures / compounds of the formulae (II-1) to (II-44), it is possible that not more than four, preferably not more than two, X 2 The group is N; more preferably, all X 2 All groups are CR d , where X 2 Preferably not more than 4, more preferably not more than 3 and especially preferably not more than 2 of the CR groups represented are not CH groups.

[0121] In a further preferred embodiment, it is feasible that the compound of the present invention comprises the structure of formula (III-1) to (III-48), wherein the compound of the present invention may be more preferably selected from the compounds of formula (III-1) to (III-48),

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131] The symbols R and R a , R b , R c and R d has the definitions given above, especially for formula (I), and the other symbols are as follows:

[0132] Y is O, S, NR or C(R)2, preferably O, NR or C(R)2;

[0133] Y 1 O, S, NR d or C(R d )2, preferably O, NR d or C(R d )2;

[0134] n is independently 0, 1, 2 or 3 at each occurrence, preferably 0, 1 or 2;

[0135] m is independently 0, 1, 2, 3 or 4 at each occurrence, preferably 0, 1 or 2.

[0136] Preferred here are structures / compounds of formula (III-1), (III-2), (III-3), (III-4), (III-7), (III-8), (III-13), (III-19), (III-20), (III-25), (III-31), (III-32), (III-37), (III-43) and (III-44), and particularly preferred are structures / compounds of formula (III-1), (III-7), (III-8), (III-13) and (III-37).

[0137] Furthermore, especially in the structures / compounds of the formulae (III-1) to (III-48), it is possible that the sum of the indices m and n does not exceed 10, preferably does not exceed 8, particularly preferably does not exceed 6, and more preferably does not exceed 4.

[0138] In a preferred embodiment, it is feasible that R, R a , R c , R d The group does not contain any aromatic or heteroaromatic ring system having three linear fused aromatic 6-membered rings, wherein preferably, R, R a , R c , R d None of the radicals contain an aromatic or heteroaromatic ring system having three linear fused aromatic 6-membered rings.

[0139] A more preferred situation is that R, R a , R c , Rd The group does not contain any aromatic or heteroaromatic ring system having three aromatic 6-membered rings fused to each other, wherein preferably, R, R a , R c , R d None of the radicals contain an aromatic or heteroaromatic ring system having three aromatic 6-membered rings which are fused to one another.

[0140] Furthermore, it may be more preferable that L 1 The radical does not contain any aromatic or heteroaromatic ring system having three aromatic 6-membered rings which are fused to one another.

[0141] Furthermore, it can be further preferred that the Q group does not contain any aromatic or heteroaromatic ring system having three aromatic 6-membered rings which are fused to one another.

[0142] Furthermore, it can be further preferred that the Ar group does not contain any aromatic or heteroaromatic ring system having three aromatic 6-membered rings which are fused to one another.

[0143] It may be most preferred that the compound does not contain any aromatic or heteroaromatic ring system having three aromatic 6-membered rings fused to each other.

[0144] In a preferred embodiment of the present invention, it is feasible that at least two, preferably adjacent, R, R d The group and the two R, R d The other groups to which the group is bonded together form a fused ring, wherein the two R, R d The groups form at least one structure of formula (RA-1) to (RA-12):

[0145]

[0146] Where R 1 With the definitions given above, the dashed bond represents the bond between two R, R d The attachment point of the atom of the group to which the group is bonded, and other symbols have the following definitions:

[0147] Y 3 are identical or different in each case and are 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;

[0148] R f are in each case identical or different and are: F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or 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 in each case may be replaced by one or more R 2 group, 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, or has 5 to 60 aromatic ring atoms and can be replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 A substituted aryloxy or heteroaryloxy group, wherein the two R f The groups can also be together or one R f Group and R 1 The groups together or with other groups form a ring system, wherein R 2 Having the definition given in claim 1;

[0149] r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1;

[0150] s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0151] t is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0152] v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2.

[0153] Preference is given here to structures of the formulae RA-1, RA-3, RA-4 and RA-5, particular preference to structures of the formulae RA-4 and RA-5.

[0154] In a preferred embodiment of the present invention, preferably at least two, preferably adjacent, R, R dThe group and the two R, R d The other groups to which the group is bonded together form a fused ring, in which two R, R d The groups form structures of formula (RA-1a) to (RA-4f):

[0155]

[0156] The dotted bond represents the two R, R d The attachment site of the atom of the group to which the group is bonded, the reference 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 definitions given above, in particular for formula (I) and / or formulae (RA-1) to (RA-12).

[0157] The structure of formula RA-4f is preferred herein.

[0158] It is also possible that at least two R, R d The group is derived from adjacent X, X 2 The R and R d groups, or R, R each bonded to adjacent carbon atoms d A group in which the carbon atoms are preferably connected via bonds.

[0159] In a further preferred configuration, preferably at least two, preferably adjacent, R, R d The group and the two R, R d The other groups to which the group is bonded together form a fused ring, wherein the two R, R d The structure of the group forming formula (RB):

[0160]

[0161] Formula RB

[0162] Where R 1 Having the above definitions, especially for formula (I), the dashed bond represents two R, R d The bonding site of the group bonding, the label m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y 4 C(R 1 )2. NR 1 、NAr'、BR 1 , BAr', O or S, preferably C(R 1 )2, NAr' or O, more preferably C(R1 )2 or O, wherein Ar' has the meaning given above, in particular for formula (I).

[0163] It is also possible that at least two R, R d The group is derived from adjacent X, X 2 The R and R d groups, or R, R each bonded to adjacent carbon atoms d A group in which the carbon atoms are preferably connected via bonds.

[0164] More particularly, it is possible that in preferred structures / compounds the sum of the indices r, s, t, v, m and n is preferably 0, 1, 2 or 3, more preferably 1 or 2.

[0165] More preferably, the compound comprises at least one structure of formula (IV-1) to (IV-4); more preferably, the compound is selected from compounds of formula (IV-1) to (IV-4), wherein the compound has at least one fused ring,

[0166]

[0167] The symbols R and R a , R b , R c and R d Having the definitions given above, in particular for formula (I), the symbol o represents the fusion site of at least one fused ring, and the other indices used are as follows:

[0168] i is independently 0, 1 or 2 at each occurrence, preferably 0 or 1.

[0169] It is also possible that, especially for structures / compounds of formulae (IV-1) to (IV-4), the fused ring is formed by structures of formulae (RA-1) to (RA-12), (RA-1a) to (RA-4f) and / or (RB), as shown above, preferably by structures of formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

[0170] Preferably, 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).

[0171] It is also possible that the substituents R, R c , R d, R e and R 1 Not with the substituents R, R c , R d , R e and R 1 The ring atoms of the ring system to which they are bonded form a fused aromatic or heteroaromatic ring system. This includes the substituents R, R c , R d , R e and R 1 Possible substituents R bonded 1 and R 2 A fused aromatic or heteroaromatic ring system is formed.

[0172] R a , R b , R c The group preferably does not form any ring system with other groups. a form a ring system with each other, the ring preferably consists of exactly two R bonded to one carbon atom a Group formation.

[0173] When the compounds of the present invention are aromatic or heteroaromatic R, R c , R d , R e , R 1 or R 2 When the radicals are substituted, it is preferred that these radicals do not have any aryl or heteroaryl groups with more than two aromatic six-membered rings directly fused to each other. More preferably, the substituents do not have any aryl or heteroaryl groups with six-membered rings directly fused to each other at all. The reason for this preference is that the triplet energy of such structures is low. Fused aryl groups with more than two aromatic six-membered rings directly fused to each other but still suitable according to the present invention are phenanthrene and terphenylene formate, because they also have high triplet energy levels.

[0174] It is also possible that R, R c , R d , R e , R 1 or R 2 The radical does not contain any aromatic or heteroaromatic ring system having three linear fused aromatic 6-membered rings, wherein preferably no R radical contains any aromatic or heteroaromatic ring system having three linear fused aromatic 6-membered rings.

[0175] Preferably, Z a , L 1 -Q, L 1 The -N(Ar)2 group may be combined with Z in formula (I) or in a preferred embodiment of the formula a , L 1 -Q, L1 The groups to which the -N(Ar)2 groups are bonded form complete conjugation. Complete conjugation of the aromatic or heteroaromatic system is achieved as long as direct bonds are formed between adjacent aromatic or heteroaromatic rings. Other bonds between the above conjugated groups, for example via sulfur, nitrogen or oxygen atoms or carbonyl groups, are not detrimental to the conjugation.

[0176] It is also possible that the substituents R, R c , R d , R e and R 1 does not form a fused aromatic or heteroaromatic ring system with the ring atoms of the ring system, preferably does not form any fused ring system. This includes c , R d , R e , R 1 Possible substituents R for group bonding 1 and R 2 A fused ring system is formed.

[0177] When it can be especially selected from R, R c , R d , R e , R 1 and / or R 2 When two groups of R and R form a ring system with each other, the ring system may be monocyclic or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. In this case, the groups that together form the ring system may be adjacent, which means that these groups are bonded to the same carbon atom or to carbon atoms that are directly bonded to each other, or they may be further away from each other. d , R e , R 1 and / or R 2 The ring systems of may also be linked to one another via bonds, such that this enables ring closure.

[0178] It is also possible that at least one of R, R d The radicals are identical or different in each case and are selected from branched or cyclic alkyl, alkoxy or thioalkoxy radicals having 3 to 20 carbon atoms or aromatic or heteroaromatic ring systems of radicals selected from the following formulae Ar-1 to Ar-76; preferably, the substituents R, R d To form a fused ring, preferably according to the structure of formula (RA-1) to (RA-12) or (RB), or the substituents R, R d , R e an aromatic or heteroaromatic ring system which is identical or different in each case and is selected from the group consisting of the following formulae Ar-1 to Ar-76, and / or an Ar' group which is identical or different in each case and is selected from the group consisting of the following formulae Ar-1 to Ar-76,

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207] Where R 1 Having the definitions given above, the dashed bonds represent the bonds to the corresponding radicals, and in addition:

[0208] Ar 1 are identical or different in each case and are a divalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms and may be replaced in each case by one or more R 1 Group substitution;

[0209] A is identical or different in each case and is C(R 1 )2. NR 1 , O or S;

[0210] p is 0 or 1, wherein p=0 means Ar 1 The group is not present and the corresponding aromatic or heteroaromatic group is directly bonded to the corresponding group;

[0211] q is 0 or 1, where q=0 means that no A group is bonded to this position, but R 1 The groups are bonded to the corresponding carbon atoms.

[0212] The detailed structures of the above formulae (Ar-1) to (Ar-76) are preferred configurations of the Ar group, as defined in the structure of, for example, formula (I), in which case the substituents R in formulae (Ar-1) to (Ar-76) are 1 Should be R d Replace, where R d has the meanings given above, in particular for formula (I).

[0213] The detailed structures of the above formulae (Ar-1) to (Ar-76) are L 1 The preferred configuration of the radicals is as defined, for example, for the structure of formula (I), in which case the substituents R in formulae (Ar-1) to (Ar-76) are 1 is replaced by R, wherein R has the meanings given above, in particular for formula (I). In addition, L 1 The group includes additional attachment sites.

[0214] Here, preferred formulas are (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), (Ar -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).

[0215] When the above groups with respect to the structures of formula (Ar-1) to (Ar-76) have two or more A groups, the possible options for these groups include all combinations in the definition of A. In this case, a preferred embodiment is that one of the A groups is NR 1 and the other A group is C(R 1 )2 or wherein both A groups are NR 1 Or wherein both A groups are O.

[0216] When A is NR 1 When the substituent R bonded to the nitrogen atom 1 Preferably, the aromatic ring has 5 to 24 atoms and may also be replaced by one or more R 2 In a particularly preferred embodiment, the R 1 The substituents are identical or different in each case and are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, in particular 6 to 18 aromatic ring atoms, which do not have any fused aryl groups and any fused heteroaryl groups in which two or more aromatic or heteroaromatic 6-membered ring groups are directly fused to one another, and which may in each case also be replaced by one or more 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 R 2 The group is substituted instead of R 1 replace.

[0217] When A is C(R 1 )2, the substituent R bonded to the carbon atom 1 are preferably identical or different in each case and are a straight-chain 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 R 2 Most preferably, R1 is a methyl group or a phenyl group. In this case, R 1 The groups may also form a ring system together, thereby forming a spiro ring system.

[0218] Next, preferred substituents R, R a , R b , R c , R d , R e and R f .

[0219] Preferably, the symbols used in formula (I), (I-1) to (I-4), etc. are as follows:

[0220] R, R c , R d are in each case identical or different and are: 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 may be replaced by one or more R 1 group, 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 has 5 to 30 aromatic ring atoms and can be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a radical, wherein two R, R d The groups together or one R, R d The group and other groups, especially R c The groups together may also form a ring system.

[0221] In a preferred embodiment of the present invention, R, R d are identical or different at each occurrence and are selected 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 replaced by one or more R 1 or have 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and may in each case be substituted with one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0222] In a further preferred embodiment of the present invention, the substituents R, R d are identical or different in each case and are selected from: H, D, F, 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 replaced by one or more R 1 or have 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and may in each case be substituted with one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0223] It is also possible that at least one of R, R d group, preferably a substituent R, R d are identical or different at each occurrence and are selected from: H, D, having 6 to 30 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group, or N(Ar')2 group; more preferably, at least one substituent R, R d are identical or different in each case and are selected from a group consisting of a group having 6 to 30 aromatic ring atoms and which may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with a radical, or N(Ar')2 groups. Particularly preferably, at least one substituent R, R d are identical or different in each case and are selected from a group consisting of a group having 6 to 30 aromatic ring atoms and which may be replaced by one or more R 1 In other preferred embodiments of the present invention, the substituents R, R d The ring having the structure of formula (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB) is formed, or the substituents R, R d are identical or different at each occurrence and are selected from: H, D, having 6 to 30 aromatic ring atoms and may be replaced by one or more R 1 More preferably, R, R d The group, preferably the substituent R, R dare identical or different in each case and are selected from H or have 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms and can be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0224] It is also possible that at least one of R, R d , R e A radical is a radical having 5 to 13 aromatic ring atoms and can be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0225] In view of the above limitations, d The listed preferences also apply to R e .

[0226] It is preferred that at least one group, preferably one substituent R, R d , R e is selected 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 terphenylene, each of which may be substituted by one or more R 1 The expression "substituent" here means more particularly that R is not H. Furthermore, if two or more substituents are present selected from the aromatic or heteroaromatic radicals, the substituents R may be identical or different.

[0227] It is also possible that R bonded to a carbon atom a The groups are the same.

[0228] It is also possible that R bonded to different carbon atoms a The groups are the same.

[0229] It is also possible that R bonded to different carbon atoms a The groups are different.

[0230] It is preferred that R bonded to the carbon atom a The group is 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, each of which may be replaced by one or more R 2 substituted, preferably deuterated, wherein two or more, preferably adjacent, substituents R a If the adjacent substituents R a form a ring system with each other, the ring preferably consists of exactly two R a Group formation.

[0231] It is also preferred that R bonded to a carbon atom a The radical is selected from the group consisting of aromatic rings having 5 to 20 atoms and in each case being replaceable by one or more R 2 Aromatic or heteroaromatic ring systems substituted with radicals and preferably in each case with one or more R 2 A phenyl group substituted with a radical, preferably a deuterated radical, wherein two or more, preferably adjacent, substituents R a If the adjacent substituents R a form a ring system with each other, the ring preferably consists of exactly two R a Group formation.

[0232] The preferred situation is that R a The group is methyl, ethyl, propyl, phenyl, or two R groups bonded to the same carbon atom. a The group forms a cycloalkyl group having 5 or 6, preferably 5, carbon atoms, wherein R a The radicals are preferably methyl, whereby these radicals may be deuterated.

[0233] The preferred situation is that R b The group is methyl, ethyl, propyl, or two R groups bonded to the same carbon atom b The group forms a cycloalkyl group having 5 or 6, preferably 5, carbon atoms, wherein R b The groups are preferably H, D, methyl, ethyl, propyl, wherein these groups may be deuterated, wherein R b The group is more preferably H or D.

[0234] The preferred situation is that R c The groups are H, D, methyl, ethyl, propyl, wherein these groups may be deuterated, wherein R c The group is preferably H or D.

[0235] In a preferred embodiment of the present invention, R f are identical or different in each case and are selected from: straight-chain alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, wherein the alkyl groups in each case may be replaced by one or more R 1 or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and in each case being substituted by one or more R 2 Aromatic or heteroaromatic ring systems substituted with radicals.

[0236] In a further preferred embodiment of the present invention, R fare identical or different in each case and are selected from: straight-chain alkyl groups having 1 to 10 carbon atoms or branched or cyclic alkyl groups having 3 to 10 carbon atoms, wherein the alkyl groups in each case may be replaced by one or more R 2 substituted with 6 to 30 aromatic ring atoms and may be substituted with one or more R 2 More preferably, R f are identical or different in each case and are selected from: straight-chain alkyl groups having 1 to 5 carbon atoms or branched or cyclic alkyl groups having 3 to 5 carbon atoms, wherein the alkyl groups in each case may be replaced by one or more R 2 or having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms and in each case may be substituted by one or more R 2 Aromatic or heteroaromatic ring systems substituted with radicals.

[0237] In a preferred embodiment of the present invention, R f are identical or different in each case and are selected from: straight-chain alkyl groups having 1 to 6 carbon atoms or cyclic alkyl groups having 3 to 6 carbon atoms, wherein the alkyl groups in each case may be replaced by one or more R 2 or have 6 to 24 aromatic ring atoms and may be substituted by one or more R 2 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two R f The groups may also form a ring system together. More preferably, R f are identical or different at each occurrence and are selected from: straight-chain alkyl groups having 1, 2, 3 or 4 carbon atoms or branched or cyclic alkyl groups having 3 to 6 carbon atoms, wherein the alkyl groups at each occurrence may be replaced by one or more R 2 or an aromatic ring system having 6 to 12 aromatic ring atoms, in particular 6 aromatic ring atoms and which may in each case be substituted with one or more, preferably non-aromatic R 2 Groups are substituted, but preferably are unsubstituted; at the same time, the two R f The groups may together form a ring system. Most preferably, R f are identical or different at each occurrence and are selected from a straight-chain alkyl group having 1, 2, 3 or 4 carbon atoms or a branched-chain alkyl group having 3 to 6 carbon atoms. Most preferably, R f is a methyl group or a phenyl group, wherein two phenyl groups can form a ring system together, and the methyl group is preferred to the phenyl group.

[0238] 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 o-, m- or p-biphenyl; terphenyl, especially o-, m- or p-terphenyl or branched terphenyl; quaterphenyl, especially o-, m- or p-quaterphenyl or branched 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-bonded naphthalene; indole; benzofuran; benzothiophene; carbazole which may be attached via the 1, 2, 3 or 4 position; dibenzofuran which may be attached via the 1, 2, 3 or 4 position; dibenzothiophene which may be attached via the 1, 2, 3 or 4 position; indenocarbazole; indolocarbazole; pyridine; pyrimidine; pyrazine; pyridazine; triazine; quinoline; isoquinoline; quinazoline; quinoxaline; anthracene; pyrene; perylene; lettuce; phenanthrene or terphenylene, each of which may be attached via one or more R, R 1 or R 2 The above structures Ar-1 to Ar-76 are particularly preferred, and 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) are preferred, and the structures of formula (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) are particularly preferred. Regarding the structures Ar-1 to Ar-76, it should be noted that these structures show the substituent R 1 In the case of the ring system Ar, these substituents R 1 should be replaced by R, and in R f In the case of these substituents R 1 Should be R 2 replace.

[0239] Other suitable R, R d , R e The group is of formula -Ar 4 -N(Ar 2 )(Ar 3 ) group, wherein Ar 2 ,Ar 3 and Ar 4 are identical or different in each case and are aromatic rings having 5 to 24 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a radical. 2 ,Ar 3 and Ar 4 The total number of aromatic ring atoms in does not exceed 60, preferably does not exceed 40.

[0240] Ar 4 and Ar 2 and / or Ar 2 and Ar 3 Here, it is also possible to select C(R 1 )2. NR 1 , O and S groups are bonded to each other. Preferably, Ar 4 and Ar 2 and Ar 2 and Ar 3 In other embodiments of the present invention, Ar is connected to each other at the corresponding ortho position of the bond connected to the nitrogen atom. 2 ,Ar 3 and Ar 4 None of the groups are bonded to each other.

[0241] Preferably, Ar 4 is a ring having 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms and can be replaced by one or more R 1 More preferably, Ar 4 is selected from o-, m- or p-phenylene or o-, m- or p-biphenyl, each of which may be replaced by one or more R 1 Most preferably, Ar 4 is an unsubstituted benzylidene group.

[0242] Preferably, Ar 2 and Ar 3 are identical or different in each case and are aromatic rings having 6 to 24 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with a group. Particularly preferred Ar 2 and Ar 3 The radicals are identical or different in each case and are selected from: benzene; o-, m- or p-biphenyl; o-, m- or p-terphenyl or branched terphenyl; o-, m- or p-quaterphenyl 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 terphenylidene, each of which may be replaced by one or more R 1 Most preferably, Ar 2 and Ar 3are in each case identical or different and are selected from: benzene; biphenyl, in particular o-, m- or p-biphenyl; terphenyl, in particular o-, m- or p-terphenyl or a branched terphenyl; quaterphenyl, in particular o-, m- or p-quaterphenyl or a branched quaterphenyl; fluorene, in particular 1-, 2-, 3- or 4-fluorene; or spirobifluorene, in particular 1-, 2-, 3- or 4-spirobifluorene.

[0243] In a further preferred embodiment of the present invention, R 1 are identical or different at each occurrence and are selected 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 R 2 or have 6 to 24 aromatic ring atoms and may be substituted by one or more R 2 In a particularly preferred embodiment of the present invention, R 1 are identical or different in each case and are selected from: H; a linear alkyl group having 1 to 6 carbon atoms, in particular a straight-chain alkyl group having 1, 2, 3 or 4 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl group may be replaced by one or more R 2 or having 6 to 13 aromatic ring atoms and in each case may be replaced by one or more R 5 The aromatic or heteroaromatic ring system may be substituted, but preferably unsubstituted.

[0244] In a further preferred embodiment of the present invention, R 2 are identical or different in each case and are: H; an alkyl radical having 1 to 4 carbon atoms or an aryl radical having 6 to 10 carbon atoms, which may be substituted by an alkyl radical having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0245] At the same time, in the compounds of the present invention processed by vacuum evaporation, the alkyl group preferably has no more than 5 carbon atoms, more preferably no more than 4 carbon atoms, most preferably no more than 1 carbon atom. With regard to compounds processed from solution, suitable compounds are also compounds substituted with alkyl groups having up to 10 carbon atoms, especially branched alkyl groups; or compounds substituted with oligomeric arylene groups such as o-, m-, p-terphenyl or branched terphenyl or quaterphenyl groups.

[0246] When the compounds of formula (I) or the preferred embodiments are used as matrix materials for phosphorescent emitters or in a layer directly adjacent to a phosphorescent layer, it is also preferred that the compounds do not contain any fused aromatic or heteroaryl groups in which more than two six-membered rings are directly fused to one another. Phenanthrene and terphenylidene are exceptions, since their triplet energy is high, and they may be preferred despite the presence of fused aromatic six-membered rings.

[0247] It is also possible that the compound comprises exactly two or exactly three structures of the formula (I).

[0248] In a preferred configuration, the compound is selected from compounds of formula (D-1),

[0249]

[0250] Formula (D-1)

[0251] Where L 2 The group is a linking group, preferably a bond or an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30 aromatic ring atoms and which may be substituted by one or more R groups, and the other symbols and indices used have the meanings given in claim 1, wherein L 2 The group forms a bond with the basic structure to replace a hydrogen atom or a substituent; preferably, L 2 Group and L 1 , Q, Z a Group bonding.

[0252] In a further preferred embodiment of the present invention, L 2 is a bond or an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably having 6 to 12 carbon atoms and which may be substituted by one or more R groups, but is preferably an unsubstituted aromatic ring system, wherein R may have the definitions given above, in particular for formula (I). More preferably, L 2 is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which may be replaced by one or more R 1 substituted with, but preferably unsubstituted with, R 1 It may have the definitions given above, in particular for formula (I).

[0253] Also preferably, the symbol L shown in formula (D1) 2 In particular, the aromatic or heteroaromatic radicals are in each case identical or different and are a bond or an aryl or heteroaryl radical having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, so that the aromatic or heteroaromatic radical of the aromatic or heteroaromatic ring system is bonded directly, i.e. via an atom of the aromatic or heteroaromatic radical, to the corresponding atom of the other radical.

[0254] It is also possible that L shown in formula (D1) 2 The group comprises an aromatic ring system having no more than four, preferably no more than three, more preferably no more than two fused aromatic and / or heteroaromatic 6-membered rings, preferably without any fused aromatic or heteroaromatic ring system. Therefore, a naphthyl structure is preferred over anthracene structure. In addition, a fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structure is preferred over a naphthyl structure.

[0255] Particularly preferred are unfused structures, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0256] Suitable aromatic or heteroaromatic ring systems L 2 Examples of are selected from: o-, m- or p-phenylene; o-, m- or p-biphenylene; terphenylene, especially branched terphenylene; quaterphenylene, especially branched quaterphenylene; fluorene; spirobifluorene; dibenzofuranene; dibenzothiophene; and carbazole; each of which may be substituted by one or more R 1 The group is substituted, but is preferably unsubstituted.

[0257] In a preferred configuration, the compound of the present invention can be represented by at least one structure of formula (I), (I-1) to (I-4), (II-1) to (II-44), (III-1) to (III-48) and / or (IV-1) to (IV-4). Preferably, the molecular weight of the compound of the present invention, which preferably includes the structure of formula (I), (I-1) to (I-4), (II-1) to (II-44), (III-1) to (III-48) and / or (IV-1) to (IV-4), is not more than 5000 g / mol, preferably not more than 4000 g / mol, particularly preferably not more than 3000 g / mol, especially preferably not more than 2000 g / mol, more particularly preferably not more than 1200 g / mol, and most preferably not more than 900 g / mol.

[0258] Furthermore, a feature of the preferred compounds of the invention is that they are sublimable. The molar mass of these compounds is generally less than about 1200 g / mol.

[0259] It may be preferred that the compound does not contain any alkoxy, thioalkoxy or hydroxy groups.

[0260] In a further preferred embodiment, it is feasible that the compound does not contain any cyclobutyl groups having two oxygen atoms bonded thereto.

[0261] It is also preferred that the compound does not contain any thiadiazyl groups.

[0262] It is also possible that the ratio of electron transport groups, preferably pyrimidine, triazine, quinazoline and / or quinoxaline groups, to the phenyl groups to which the two cyclopentyl groups are fused is at least 0.6, preferably at least 0.8, more preferably at least 0.9.

[0263] It is also possible that the ratio of electron-transporting groups, preferably pyrimidine, triazine, quinazoline and / or quinoxaline groups, to the phenyl groups to which the two cyclopentyl groups are fused is at most 10, preferably at most 4, more preferably at most 1.5.

[0264] It is also possible that the compound comprising the structure of formula (I), preferably the compound of formula (I) or preferred embodiments of this structure / compound is not in direct contact with the metal atom and is preferably not a ligand of the metal complex.

[0265] The above-mentioned preferred embodiments can be combined with each other as required within the limits defined in claim 1. In a particularly preferred embodiment of the present invention, the above-mentioned preferences occur simultaneously.

[0266] Examples of preferred compounds according to the above detailed embodiments are the compounds detailed in the following table:

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276] The basic structure of the compounds of the present invention can be prepared by the route outlined in the following scheme. The various synthesis steps herein, for example the coupling reactions leading to the formation of CC bonds and / or the formation of CN bonds, are in principle known to those skilled in the art. These include BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA and HIYAMA reactions.

[0277] More information on the synthesis of the compounds of the invention can be found in the Synthesis Examples.

[0278] The following scheme describes the preparation of compounds of the present invention by using a well-defined phenyl compound, which is fused with a cyclopentyl group, preferably two cyclopentyl groups. This use should be considered as exemplary, and other compounds of the present invention can therefore be obtained by similar synthetic routes starting from different basic structures.

[0279] The synthesis of phenyl compounds fused to one cyclopentyl group, preferably two cyclopentyl groups, is well known in the art. Many such compounds are commercially available. These compounds include, for example, the compounds cited in the synthesis examples.

[0280] The compound having an electron transport group of the present invention, especially the compound comprising the structure of formula (I), can be obtained from a phenyl compound (1) fused with one cyclopentyl group, preferably two cyclopentyl groups, by the following synthetic route:

[0281] 1) Prepared according to M. Oi et al., Chem. Sci., 2019, 10, 6107, by lithiation (2), transmetallation with cuprous chloride (I) to obtain organic copper chloride (3), followed by palladium-phosphine-mediated CC coupling to chloro, bromo or iodo heterocyclic X-HetAr (HetAr: heterocyclic compounds containing pyridine, pyrimidine, triazine, quinazoline, quinoxaline, etc.):

[0282]

[0283] R: alkyl, aryl

[0284] X: H, D, alkyl, aryl, Br

[0285] If the X group on the phenyl compound (1) fused to one cyclopentyl group, preferably to two cyclopentyl groups, is (1) a bromine atom, reaction sequence 1) or 2) can be repeated successively to give compounds of the invention which are symmetrically or asymmetrically disubstituted by -NAr2 or -Ar-NAr2 groups.

[0286] Scheme (1) is to be understood by way of example, such that other X groups are equally applicable, as shown in the examples.

[0287] The definitions of the symbols used in the above schemes basically correspond to those of formula (I), and for the sake of clarity, the numbering and complete representation of all symbols are omitted.

[0288] The present invention therefore also provides a process for preparing the compounds according to the invention, wherein a phenyl compound fused to one cyclopentyl group, preferably two cyclopentyl groups, is synthesized and at least one aromatic or heteroaromatic group is introduced, preferably by a nucleophilic aromatic substitution reaction or coupling reaction.

[0289] By these methods, if necessary followed by purification, for example by recrystallization or sublimation, it is possible to obtain high purity, preferably greater than 99% (by 1 H NMR and / or HPLC determination) of the compounds of the present invention.

[0290] Compounds of the present invention may also be mixed with polymers. Similarly, these compounds may be covalently incorporated into polymers. This is particularly useful 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. It has been found that they may be used as monomers for making corresponding oligomers, dendritic macromolecules or polymers. The oligomerization or polymerization is preferably implemented by halogen functional groups or boric acid functional groups or by polymerizable groups. Crosslinked polymers may also be carried out by such groups. Compounds of the present invention and polymers may be used in the form of crosslinked or uncrosslinked layers.

[0291] The present invention therefore also provides an oligomer, polymer or dendrimer containing one or more of the above detailed structures of formula (I) and preferred embodiments of the formula or compounds of the invention, wherein there is one or more bonds of the compounds of the invention or the structures of formula (I) and preferred embodiments of the formula to the polymer, oligomer or dendrimer. According to the connection of the structures of formula (I) and preferred embodiments of the formula or compounds, they thus form side chains of the oligomer or polymer or are bonded within 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 of the invention in the oligomers, dendrimers and polymers, the same preferences as described above apply.

[0292] To prepare oligomers or polymers, the monomers of the invention are homopolymerized or copolymerized with other monomers. Preference is given to copolymers in which the units of formula (I) or the preferred embodiments described above and below are present in a range of 0.01 to 99.9 mol %, preferably 5 to 90 mol %, more preferably 20 to 80 mol %. Suitable and preferred comonomers for forming the basic backbone of the polymer are selected from the group consisting of: 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 2004 / 070772 or WO 2004 / 113468), 2005 / 104264 or WO 2007 / 017066) or a plurality of these units. The polymers, oligomers and dendrimers may also contain other units, for example: hole transport units, especially units based on triarylamines; and / or electron transport units.

[0293] In addition, particular interest is given to compounds of the invention which are characterized by a high glass transition temperature. In this regard, particular preference is given to compounds of the invention which comprise the structure of formula (I) or the preferred embodiments described above and below, and which have a glass transition temperature of at least 70° C., more preferably at least 110° C., still more preferably at least 125° C., and particularly preferably at least 150° C., the glass transition temperature being determined according to DIN 51005 (2005-08 edition).

[0294] In order to process the compounds of the present invention from the liquid phase, for example, by spin coating or by printing, preparations of the compounds of the present invention are required. These preparations can be, for example, 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; methyl benzoate; mesitylene; tetralin; veratrol; THF; methyl-THF; THP; chlorobenzene; dioxane; phenoxytoluene, in particular 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; α-terpineol; benzothiazole; butyl benzoate; isopropylbenzene; cyclohexanol; cyclohexanone; cyclohexyl Benzene; decalin; dodecylbenzene; ethyl benzoate; indane; NMP; p-cymene; phenethyl ether; 1,4-diisopropylbenzene; dibenzyl ether; diethylene glycol butyl methyl ether; triethylene glycol butyl methyl ether; diethylene glycol dibutyl ether; triethylene glycol dimethyl ether; diethylene glycol monobutyl ether; tripropylene glycol dimethyl ether; tetraethylene glycol dimethyl ether; 2-isopropylnaphthalene; pentylbenzene; hexylbenzene; heptylbenzene; octylbenzene; 1,1-bis(3,4-dimethylphenyl)ethane; 2-methylbiphenyl; 3-methylbiphenyl; 1-methylnaphthalene; 1-ethylnaphthalene; ethyl octanoate; diethyl sebacate; octyl octanoate; heptylbenzene; menthyl isovalerate; cyclohexyl hexanoate; or a mixture of these solvents.

[0295] Therefore, the present invention also provides a preparation or composition comprising at least one inventive compound and at least one other compound. Other compounds may be, for example, solvents, in particular one of the above-mentioned solvents or a mixture of these solvents. If other compounds contain solvents, the mixture is referred to as a preparation in this article. Other compounds may alternatively be at least one other organic or inorganic compound, such as a luminescent compound and / or other matrix material, also used in electronic devices. Preferably, at least one other compound is selected from fluorescent emitters, phosphorescent emitters, luminescent bodies showing TADF, host materials, electron transport materials, electron injection materials, hole conduction materials, hole injection materials, electron blocking materials and hole blocking materials, preferably host materials.

[0296] The present invention also provides the use of the compound of the present invention in electronic devices, especially in organic electroluminescent devices. Preferably, the compound of the present invention is used as a host material, an electron transport material, an electron injection material or a hole blocking material in the electronic device.

[0297] The present invention also provides an electronic device comprising at least one compound according to the invention. An electronic device in the context of the present invention is a device comprising at least one layer comprising at least one organic compound. The component may also comprise inorganic materials or layers formed entirely of inorganic materials.

[0298] The electronic device is more preferably selected from: 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 light emitting 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 (O-SC), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQD) and organic electrical sensors, preferably organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), more preferably organic light emitting diodes (OLED), small molecule-based organic light emitting diodes (sOLED), polymer-based organic light emitting diodes (PLED), especially phosphorescent OLED.

[0299] The organic electroluminescent device comprises a cathode, an anode and at least one luminescent layer. In addition to these layers, the organic electroluminescent device may also comprise other layers, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers and / or charge generation layers in various cases. It is also feasible to introduce an intermediate layer having, for example, an exciton blocking function between two luminescent layers. However, it should be noted that each of these layers does not necessarily have to be present. In this case, the organic electroluminescent device may contain one luminescent layer, or it may contain multiple luminescent layers. If there are multiple luminescent layers, it is preferred that these luminescent layers generally have multiple luminescent peaks between 380 nm and 750 nm, so that the overall result is white luminescence; in other words, a variety of luminescent compounds that emit fluorescence or phosphorescence can be used in the luminescent layer. Particularly preferred is a system with three luminescent layers, wherein the three layers display blue, green and orange or red luminescence. The organic electroluminescent device of the present invention may also be a tandem electroluminescent device, especially for white-light-emitting OLEDs.

[0300] The compounds of the present invention can be used in different layers according to the exact structure. It is preferred that the organic electroluminescent device comprises the compound of formula (I) or the above preferred embodiment in the luminescent layer as a host material of a phosphorescent emitter or a luminescent body exhibiting TADF (thermally activated delayed fluorescence), especially a host material of a phosphorescent emitter. In addition, the compounds of the present invention can also be used in an electron transport layer and / or a hole blocking layer. More preferably, the compounds of the present invention are used as a host material of a phosphorescent emitter in the luminescent layer, especially a host material for a red-, orange-, blue-, green- or yellow-phosphorescent emitter, especially a host material of a blue- or green-phosphorescent emitter, as a host material, an electron transport material, an electron injection material or a hole blocking material.

[0301] It may be preferred that the organic electroluminescent device comprises at least one emitting layer and at least one electron-transport layer, and that it is the electron-transport layer that contains the compound according to the invention.

[0302] When the compounds of the invention are used as matrix materials for phosphorescent compounds in an emitting layer, the compounds are preferably used in combination with one or more phosphorescent materials (triplet emitters). In the context of the present invention, phosphorescence is understood to mean luminescence from excited states with higher spin multiplicity, i.e. spin state>1, in particular luminescence from excited triplet states. In the context of the present application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum and copper complexes, should be considered as phosphorescent compounds.

[0303] Based on the total mixture of luminophore and matrix material, the mixture of the compound of the present invention and the luminescent compound contains 99% to 1% by volume, preferably 98% to 10% by volume, more preferably 97% to 60% by volume and especially 95% to 80% by volume of the compound of the present invention. Correspondingly, based on the total mixture of luminophore and matrix material, the mixture contains 1% to 99% by volume, preferably 2% to 90% by volume, more preferably 3% to 40% by volume and especially 5% to 20% by volume of luminophore.

[0304] In one embodiment of the invention, the compounds according to the invention are employed here as sole matrix material (“single host”) for a phosphorescent emitter.

[0305] A further embodiment of the present invention is the use of the compounds according to the invention in combination with other matrix materials as matrix material for phosphorescent emitters. 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-dicarbazolylbiphenyl) or the carbazole derivatives disclosed in 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; 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160; bipolar matrix materials, for example according to WO 2007 / 137725; silanes, for example according to WO 2005 / 111172; borazolidines or boric acid esters, for example according to WO 2006 / 117052; for example according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO triazine derivatives according to WO 2011 / 060859 or WO 2011 / 060877; zinc complexes according to EP 652273 or WO 2009 / 062578; siladiazolidine or siladiazolidine derivatives according to WO 2010 / 054729; phosphodiazolidine derivatives according to WO 2010 / 054730; bridged carbazole derivatives according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080; terphenylidene derivatives according to WO 2012 / 048781; terphenylidene derivatives according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565; or biscarbazoles, for example according to JP 3139321 B2.

[0306] It is likewise possible that further phosphorescent emitters which emit at shorter wavelengths than the actual emitter are present as cohosts in the mixture. Particularly good results are obtained when the emitter used is a red phosphorescent emitter and the cohost used in combination with the compounds according to the invention is a yellow phosphorescent emitter.

[0307] In addition, the co-host used can be a compound that participates in charge transport but not to a significant extent, as described in, for example, WO 2010 / 108579. Particularly suitable as a co-host material in combination with the compounds of the present invention are compounds with a large band gap and that themselves participate in the charge transport of the light-emitting layer but at least not to a significant extent. Such materials are preferably pure hydrocarbons. Examples of such materials can be found in, for example, WO 2009 / 124627 or WO 2010 / 006680. In this context, it should be emphasized that the compounds of the present invention have advantageous properties without requiring specific functional groups such as hole transport groups and / or electron transport groups.

[0308] Suitable phosphorescent compounds (=triplet emitters) are, in particular, compounds which emit light when suitably excited, preferably in the visible region, and which also contain at least one atom, in particular a metal with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. Phosphorescent emitters preferably used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum.

[0309] Examples of such emitters can be found in the following applications: WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626、WO 2011 / 066898、WO 2011 / 157339、WO 2012 / 007086、WO 2014 / 008982、WO 2014 / 023377、WO 2014 / 094961、WO 2014 / 094960、WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439 and WO 2018 / 011186. In general, all phosphorescent complexes known to the person skilled in the art for use in phosphorescent electroluminescent devices according to the prior art and in the field of organic electroluminescence are suitable, and the person skilled in the art will be able to use other phosphorescent complexes without inventive step.

[0310] Examples of phosphorescent dopants are listed in the following table:

[0311]

[0312]

[0313]

[0314]

[0315]

[0316] The compounds according to the invention are also particularly suitable as matrix materials for phosphorescent emitters in organic electroluminescent devices, as described, for example, in WO 98 / 24271, US 2011 / 0248247 and US 2012 / 0223633. In these multicolor display components, an additional blue-emitting layer is applied by vapor deposition over the entire area to all pixels, including those with non-blue colors.

[0317] In other embodiments of the invention, the organic electroluminescent device according to the invention does not comprise any separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, which means that the light-emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light-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. It is also possible to use metal complexes identical or similar to the metal complexes in the light-emitting layer as hole transport or hole injection materials directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0318] In other layers of the organic electroluminescent device of the present invention, any material commonly used in the prior art can be used. Therefore, without paying creative work, those skilled in the art will be able to use any material known about the organic electroluminescent device in a manner combined with the inventive compound of formula (I) or the above-mentioned preferred embodiments.

[0319] Also preferred is an organic electroluminescent device, characterized in that one or more layers are applied by sublimation. In this case, the organic electroluminescent device is applied by sublimation in a vacuum sublimation system at a temperature of less than 10 -5 mbar, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of 10 mbar. However, for much lower pressures, for example below 10 -7 Initial pressures of mbar are also possible.

[0320] Likewise preferred is an organic electroluminescent device, characterized in that one or more layers are applied by OVPD (organic vapor phase deposition) or by sublimation with the aid of a carrier gas. -5 The material is applied at a pressure of 100 mbar to 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle, whereby the material is structured.

[0321] In addition, an organic electroluminescent device is preferably used, characterized in that one or more layers are made from a solution, for example by spin coating or by any printing method such as screen printing, flexographic printing, offset printing, LITI (light induced thermal imaging, thermal transfer printing), inkjet printing or nozzle printing. For this purpose, soluble compounds are required, which are obtained, for example, by appropriate substitution.

[0322] The formulations applying the compounds of formula (I) or preferred embodiments thereof as detailed above are novel. The present invention therefore also provides formulations containing at least one solvent and the compounds of formula (I) or preferred embodiments thereof as detailed above.

[0323] Furthermore, hybrid methods are possible in which, for example, one or more layers are applied from solution and one or more other layers are applied by vapor deposition.

[0324] The person skilled in the art is generally aware of these processes and is able to apply them without inventive step to organic electroluminescent devices comprising the compounds according to the invention.

[0325] The compounds of the present invention and the organic electroluminescent device of the present invention have a low refractive index (RI) particularly significantly relative to the prior art. In addition, these compounds and the organic electroluminescent device obtained therefrom show an improved lifespan. At the same time, other electronic properties of the electroluminescent device such as efficiency or operating voltage at least remain equally good. In other variants, compared with the prior art, the compounds of the present invention and the organic electroluminescent device of the present invention especially have the characteristics of improved efficiency and / or operating voltage and longer lifespan.

[0326] Compared with the prior art, the electronic device of the present invention, especially the organic electroluminescent device, has one or more of the following surprising advantages:

[0327] 1. An electronic device, especially an organic electroluminescent device, comprising a compound of formula (I) or the preferred embodiments described above and below, especially as a matrix material or as an electron conducting material, has excellent efficiency. In this context, the inventive compound having the structure of formula (I) or the preferred embodiments described above and below can produce a lower operating voltage when used in an electronic device.

[0328] 2. Electronic devices, in particular organic electroluminescent devices, comprising compounds of formula (I) or the preferred embodiments described above and below, especially as matrix materials or as electron-conducting materials, have very good lifetimes. In this context, these compounds bring about in particular low roll-off, i.e. the power efficiency of the device at high luminous densities decreases only slightly.

[0329] 3. The compounds of formula (I) according to the invention or the preferred embodiments described above and below show very high stability and longevity.

[0330] 4. An electronic device, especially an organic electroluminescent device, comprising a compound of the formula (I) or the preferred embodiments described above and below, especially as matrix material or as electron-conducting material, has a very low refractive index.

[0331] 5. By using the compounds of formula (I) or the preferred embodiments described above and below, the formation of light loss channels in electronic devices, especially organic electroluminescent devices, can be avoided. Therefore, these devices are characterized by high PL efficiency and thus high EL efficiency of the emitter, as well as excellent energy transfer of the matrix to the dopant.

[0332] 6. The compounds of formula (I) or the preferred embodiments described above and below have excellent glass film forming properties.

[0333] 7. The compounds of formula (I) or the preferred embodiments described above and below form very good films from solution.

[0334] These aforementioned advantages are not accompanied by excessive degradation of other electronic properties.

[0335] It should be noted that variations of the embodiments described in the present invention are included within the scope of the present invention. Unless explicitly excluded, any feature disclosed in the present invention can be replaced by an alternative feature having the same purpose or an equivalent or similar purpose. Therefore, unless otherwise specified, any feature disclosed in the present invention should be regarded as an example of a general series or as an equivalent or similar feature.

[0336] Unless specific features and / or steps are mutually exclusive, all features of the present invention can be combined with each other in any way. This is particularly applicable to the preferred features of the present invention. Similarly, features of non-essential combinations can be used separately (not in combination).

[0337] It should also be noted that many features, especially those of the preferred embodiments of the invention, should be considered inventive in themselves, rather than just as some embodiments of the invention. For these features, independent protection may be sought to supplement or replace any currently claimed invention.

[0338] The technical teachings disclosed in the present invention can be refined and combined with other examples.

[0339] The present invention is illustrated in detail by the following examples, but it is not intended to limit the present invention thereby. Those skilled in the art will be able to use the information provided to implement the present invention within the entire disclosed range, and to prepare other compounds of the present invention without inventive effort, and use them in electronic devices or adopt the methods of the present invention. Example

[0340] Unless otherwise noted, the following synthesis is carried out in a dry solvent under a protective gas atmosphere. The metal complex also needs to be handled under light protection or yellow light. The solvents and reagents can be purchased from, for example, Sigma-ALDRICH or ABCR. The corresponding numbers in square brackets or the numbers quoted for individual compounds are related to the CAS numbers of the compounds known in the literature. In the case where a compound can have multiple enantiomers, diastereomers or tautomeric forms, one form is shown in a representative manner.

[0341] Synthon LS known from literature:

[0342]

[0343] A) Synthesis of Synthon S of Inventive Compound B:

[0344] Embodiment B1:

[0345]

[0346] Follow the procedure in M. Oi et al., Chem. Sci., 2019, 10, 6107, Example 36.

[0347] Starting material: 34.9 g (100 mmol) of LS1, 39.5 g (110 mmol) of 2-iodo-4,6-diphenyl-1,3,5-triazine [83819-97-0] instead of methyl 4-iodobenzoate, in a stirred autoclave, 120° C., 24 h. Further purification was carried out in each case by chromatography and / or repeated hot extractive crystallization (common organic solvents or combinations thereof, preferably acetonitrile-dichloromethane (DCM), 1:3 to 3:1, volume ratio) and fractional sublimation or high vacuum heat treatment. Yield: 31.7 g (63 mmol), 63%; purity: about 99.9% as determined by HPLC.

[0348] The following compounds can be prepared similarly: The yields depend firstly on the steric requirements of LS1 to LS8, and are generally observed in the following decreasing sequence: LS1~LS2~LS3>LS4>LS5~LS6~LS7~LS8. Secondly, for the heteroaryl-halogen coupling pairs mentioned below, they are generally in the range of 25% to 50% for chlorides, 40% to 60% for bromides, and 50% to 70% for iodides.

[0349]

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368]

[0369]

[0370]

[0371]

[0372]

[0373]

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396]

[0397]

[0398]

[0399]

[0400]

[0401]

[0402]

[0403] Example: Fabrication of OLEDs

[0404] 1) Vacuum treated devices:

[0405] The OLEDs according to the invention and the OLEDs serving as reference were produced by the general method according to WO 2004 / 058911, which was adapted to the circumstances described there (variation of layer thicknesses, materials used).

[0406] In the following examples, the results of various OLEDs are given. Clean glass plates coated with 50 nm thick structured ITO (indium tin oxide) (cleaned in a Miele laboratory glass washer, Merck Extran detergent) were pretreated with UV ozone for 25 minutes (UVP PR-100 UV ozone generator). These coated glass plates formed the substrate for the application of the OLED.

[0407] 1a) Blue fluorescent OLED component - BF:

[0408] The compounds of the invention can be used in hole injection layers (HIL), hole transport layers (HTL) and electron blocking layers (EBL). All materials are applied by thermal vapor deposition in a vacuum chamber. The emitting layer (EML) here is always composed of at least one matrix material (host material) SMB (see Table 1) and a luminescent dopant (dopant, luminophore) D, which is added to one or more matrix materials in a specific volume ratio by co-evaporation. Detailed information provided in a form such as SMB: D (97:3%) means here that the material SMB is present in the layer in a volume ratio of 97% and the dopant D is present in the layer in a 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 produce OLEDs are shown in Table 5 or are related to the synthesis examples detailed above.

[0409] The OLEDs were characterized in a standard manner. 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 %) as a function of the luminous density, calculated from the current-voltage-luminous density characteristic (IUL characteristic) assuming Lambertian luminescence characteristics, and the lifetime were determined. At a luminous density of 1000 cd / m 2 The EQE (in %) and voltage (in V) are reported at the initial luminous density of 10000 cd / m 2 The lifetime is determined when the brightness of the reference decreases to 80% of the initial brightness. The measurement period in which the brightness of the reference decreases to 80% of the initial brightness is set as 100%. The lifetime of the OLED components containing the compounds of the invention is reported as a percentage relative to the reference.

[0410] OLED has the following layer structure:

[0411] Base

[0412] Hole injection layer 1 (HIL1) consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0413] Hole transport layer (HTL), composed of HTM1, 180 nm

[0414] Electron blocking layer (EBL), see Table 1

[0415] Emission layer (EML), see Table 1

[0416] Hole blocking layer (HBL), see Table 1

[0417] Electron transport layer (ETL), see Table 1

[0418] Electron injection layer (EIL) composed of ETM2, 1 nm

[0419] Cathode made of aluminum, 100 nm

[0420] Table 1: Structure of blue fluorescent OLED components

[0421]

[0422] Table 2: Results of blue fluorescent OLED components

[0423]

[0424] 1b) Phosphorescent OLED components:

[0425] The inventive compound A can be used in a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL) and as a matrix material (host material) M (see Table 5) or A (see the materials of the present invention) in an emitting layer (EML). For this purpose, all materials are applied by thermal vapor deposition in a vacuum chamber. The emitting layer here is always composed of at least one or more matrix materials M and a phosphorescent dopant Ir, which is added to one or more matrix materials in a specific volume ratio by co-evaporation. The details given in the form of, for example, M1:M2:Ir (55%:35%:10%) refer here to the presence of material M1 in the layer at a volume ratio of 55%, M2 in the layer at a volume ratio of 35%, and Ir in the layer at a volume ratio of 10%. Similarly, the electron transport layer can also be composed of a mixture of two materials. The exact structure of the OLED can be found in Table 3. The materials used to make the OLED are shown in Table 5 or are related to the synthesis examples detailed above.

[0426] The OLEDs were characterized in a standard manner. 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 %) as a function of the luminous density, calculated from the current-voltage-luminous density characteristic (IUL characteristic) assuming Lambertian luminescence characteristics, and the lifetime were determined. At a luminous density of 1000 cd / m2 EQE (in %) and voltage (in V) are reported for blue and red emission at an initial luminous density of 1000 cd / m 2 The lifetime is determined when the green and yellow luminescence is at an initial luminous density of 10000 cd / m 2 The lifetime is determined when the brightness of the reference decreases to 80% of the initial brightness. The measurement period in which the brightness of the reference drops to 80% of the initial brightness is set to 100%. The lifetime of the OLED components containing the compounds of the invention is reported as a percentage relative to the corresponding reference of similar structure, or in the case of using the compounds of the invention as matrix material, as a percentage relative to the component containing Ref-ETM2 in the ETL and HBM2 in the HBL.

[0427] OLED has the following layer structure:

[0428] Base

[0429] Hole injection layer (HIL) consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0430] Hole transport layer (HTL) composed of HTM1, 180 nm for blue, 50 nm for green, yellow and red

[0431] Electron blocking layer (EBL), see Table 3

[0432] Emission layer (EML), see Table 3

[0433] Hole blocking layer (HBL), see Table 3

[0434] Electron transport layer (ETL), see Table 3

[0435] Electron injection layer (EIL) composed of ETM2, 1 nm

[0436] Cathode made of aluminum, 100 nm

[0437] Table 3: Structure of phosphorescent OLED components

[0438]

[0439]

[0440]

[0441]

[0442]

[0443] Table 4: Results for phosphorescent OLED components

[0444]

[0445]

[0446] Table 5: Structural formula of the materials used

[0447]

[0448]

[0449]

Claims

1. A compound comprising at least one structure of formula (I), Formula (I) The symbols are as follows: Z a are the same or different in each case and are Ar, R c , L 1 -Q or L 1 -N(Ar)2; Q is identical or different in each case and is an electron transport group; L 1 are identical or different in each case and are a bond or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups; R a are identical or different in each case and are: a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10 carbon atoms, each of which may be replaced by one or more R 2 or have 5 to 20 aromatic ring atoms and may be substituted by one or more R 2 Aromatic or heteroaromatic ring system substituted with a radical, wherein two or more substituents R a Can form a ring system together; R b are in each case identical or different and are: H, D, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10 carbon atoms, each of which may be replaced by one or more R 2 or have 5 to 20 aromatic ring atoms and may be substituted by one or more R 2 Aromatic or heteroaromatic ring system substituted with radicals, wherein the two substituents R b Can form a ring system together; Ar is identical or different in each case and is: an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups, wherein two Ar groups bonded to the same nitrogen atom may also be bridged to one another by a single bond or a bridging group selected from B(R), C(R)2, Si(R)2, C=O, C=NR, C=C(R)2, RC=CR, O, S, S=O, SO2, N(R), P(R), P(=O)R and an ortho-attached benzylidene group which may be substituted by one or more R groups; R, R c , R d are in each case identical or different and are: 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 may be replaced by one or more R 1 groups, 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 has 5 to 60 aromatic ring atoms and can be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and which may be replaced by one or more R 1 A substituted aryloxy or heteroaryloxy group, wherein two R, R d The groups together or one R, R d The groups and other groups, especially R c The groups together may also form a ring system; Ar' is identical or different in each case and is an aromatic ring having 5 to 60 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group, wherein two Ar' groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom can also be connected by a single bond or 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 bridging groups in the bridge each other; R 1 are in each case identical or different and are: 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, 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 may be substituted by one or more R 2 group, 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 hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or have 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and which may be replaced by one or more R 2 substituted aryloxy or heteroaryloxy groups, or having 5 to 60 aromatic ring atoms and which may be replaced by one or more R 2 substituted aralkyl or heteroaralkyl groups, or combinations of these systems, wherein two or more R 1 The groups may together form a ring system in which one or more R 1 The group may form a ring system with other parts of the compound; Ar'' is identical or different in each case and is a cyclic aromatic ring having 5 to 30 atoms and may be replaced by one or more R 2 Aromatic or heteroaromatic ring system substituted with a group, wherein two Ar'' groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom can also be connected by a single bond or 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 bridging groups in the bridge each other; R 2 are identical or different in each case and are selected from: H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl radicals each having 1 to 4 carbon atoms, in which two or more substituents R 2 Can form a ring system together.

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 Having the definition given in claim 1.

3. The compound according to claim 1 or 2, characterized in that The Q group is a pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and / or benzimidazole group, which may be replaced by one or more R d Group substitution.

4. Compounds according to one or more of claims 1 to 3, characterized in that The Q group is a nitrogen-containing heteroaryl group having 6 to 12 ring atoms and at least two nitrogen atoms in the ring, which may be replaced by one or more R d The radical is substituted wherein the carbon atoms adjacent to at least two nitrogen atoms in the ring are not bonded to hydrogen atoms.

5. The compound according to at least one of the preceding claims 1 to 4, characterized in that The Ar groups are identical or different at each occurrence and are selected 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 terphenylidene, each of which may be substituted by one or more R groups.

6. Compounds according to one or more of claims 1 to 5, characterized in that L 1 The groups are the same or different and are bonds or selected from the formula (L 1 -1) to (L 1 -22) structure, The symbols used are as follows: Y is CR 2 , 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 above-mentioned definition, in particular the definition given for claim 1, and the dashed key marks the connection point.

7. Compounds according to one or more of claims 1 to 6, characterized in that The Q groups are identical or different in each case and are selected from the structures of formulae (Q-1) to (Q-16), Where R d With the above definitions, especially for claim 1, the dashed key represents the connection position, and the other symbols are defined as follows: Y 1 O, S, NR d or C(R d )2; n is independently at each occurrence 0, 1, 2 or 3; and m is independently 0, 1, 2, 3 or 4 at each occurrence.

8. A compound according to one or more of claims 1 to 7, comprising at least one structure of formula (II-1) to (II-44), The symbols R and R a , R b , R c and R d The definitions given in claim 1 are as follows, and the other symbols are as follows: X is identical or different at each occurrence and is N, CR, or, if the group is bonded to the structure, C; X 1 Same or different in each case and N or CR d ; X 2 Same or different in each case and N or CR d ; Y is O, S, NR or C(R)2, preferably O, NR or C(R)2; and Y 1 O, S, NR d or C(R d )2.

9. A compound according to one or more of claims 1 to 8, comprising at least one structure of formula (III-1) to (III-48), The symbols R and R a , R b , R c and R d The definitions given in claim 1 are as follows, and the symbols used are as follows: Y is O, S, NR or C(R)2; Y 1 O, S, NR d 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.

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

11. The compound according to at least one of the preceding claims 1 to 10, characterized in that R, R a , R c , R d None of the radicals contain an aromatic or heteroaromatic ring system having three aromatic 6-membered rings which are fused to one another.

12. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 11, wherein instead of a hydrogen atom or a substituent there are one or more bonds of said compound to said polymer, oligomer or dendrimer.

13. A preparation comprising at least one compound according to one or more of claims 1 to 11 or an oligomer, polymer or dendrimer according to claim 12 and at least one further compound, wherein the further compound is preferably selected from one or more solvents.

14. A composition comprising at least one compound according to one or more of claims 1 to 11 or an oligomer, polymer or dendrimer according to claim 12 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 conducting materials, hole injection materials, electron blocking materials and hole blocking materials.

15. A process for preparing a compound according to one or more of claims 1 to 11, characterized in that A phenyl compound fused with a cyclopentyl group is synthesized and at least one aromatic or heteroaromatic group is introduced, preferably by a nucleophilic aromatic substitution reaction or a coupling reaction.

16. Use of a compound according to one or more of claims 1 to 11 or an oligomer, polymer or dendrimer according to claim 12 in an electronic device, preferably as host material, electron injection material, electron transport material or hole blocking material. 17 . An electronic device comprising at least one compound according to one or more of claims 1 to 11 or an oligomer, polymer or dendrimer according to claim 12 .

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