Materials for organic electroluminescent devices

Abstract

The present application relates to compounds suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, comprising said compounds.

Description

[0001] This invention relates to materials for use in electronic devices, particularly organic electroluminescent devices, and to electronic devices comprising said materials, particularly organic electroluminescent devices.

[0002] The luminescent materials used in organic electroluminescent devices are often phosphorescent organometallic complexes. Due to quantum mechanical reasons, using organometallic compounds as phosphorescent emitters can achieve up to four times the energy efficiency and power efficiency. In electroluminescent devices, especially those exhibiting triplet emission (phosphorescence), there is still a need for improvement. The properties of phosphorescent electroluminescent devices are not solely determined by the triplet emitter used. More specifically, other materials used, such as the matrix material, also have particular significance. Therefore, improvements in these materials can lead to significant improvements in the properties of the electroluminescent device.

[0003] WO 2010 / 136109 discloses indobenzocarbazole derivatives as matrix materials for phosphorescent emitters. The compounds of this invention are not disclosed.

[0004] Generally speaking, improvements are still needed when these materials are used as matrix materials, particularly in terms of device lifespan, efficiency, and operating voltage.

[0005] Therefore, the problem solved by the present invention is to provide compounds suitable for use in organic electronic devices, especially organic electroluminescent devices, and which result in good device properties when used in such devices, and to provide corresponding electronic devices.

[0006] More specifically, the problem addressed by this invention is to provide compounds that result in long lifetimes, good efficiency, and low operating voltages. In particular, the properties of the matrix material also have a significant impact on the lifetime and efficiency of organic electroluminescent devices.

[0007] Another problem addressed by this invention can be considered as providing compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, particularly as matrix materials. A specific problem addressed by this invention is providing matrix materials suitable for electroluminescent devices emitting red and yellow phosphorescence, especially red phosphorescence, and, if appropriate, also suitable for electroluminescent devices emitting blue phosphorescence.

[0008] In addition, the compounds result in devices with excellent color purity, especially when they are used as matrix materials, hole blocking materials or electron transport materials in organic electroluminescent devices.

[0009] Another objective can be considered as providing electronic devices with excellent performance at the lowest cost and with consistent quality.

[0010] Furthermore, the electronic device should be usable or employable in a variety of applications. More specifically, the performance of the electronic device should be maintained over a wide temperature range.

[0011] It was unexpectedly discovered that the specific compounds described in detail below solve this problem and are well-suited for use in electroluminescent devices, leading to improvements in organic electroluminescent devices, particularly in lifetime, color purity, efficiency, and operating voltage. The present invention therefore provides the said compounds and electronic devices, especially organic electroluminescent devices, comprising such compounds.

[0012] This invention provides compounds of formula (1).

[0013]

[0014] The symbols and markings used are as follows:

[0015] X is N or CR, provided that no more than two X groups in a ring are N; preferably, X is CR.

[0016] The two adjacent Y's are groups of the following formula (2), and the other two Y's are X's.

[0017]

[0018] The two dashed bonds represent the bonds between the groups;

[0019] X 1 It is N or CR, provided that there are no more than two X's in the ring. 1 The group is N; preferably, X 1 It is CR;

[0020] HetAr is an aromatic ring atom with 6 to 18 atoms and can be converted by one or more R atoms. 3 Electron-deficient heteroaryl groups substituted by a group; simultaneously, the HetAr group and the naphthyl subunit bound to the HetAr group can form an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system; preferably, the HetAr group and the naphthyl subunit bound to the HetAr group do not form any such ring system;

[0021] R is the same or different in each case and is: H, D, F, Cl, Br, I, N (R) 4 )2, N(Ar')2, CN, NO2, OR 4 SR 4 COOR 4 C(=O)N(R) 4 )2,Si(R 4 )3, B(OR 4 )2, C(=O)R4 , P(=O)(R 4 )2, S(=O)R 4 S(=O)2R 4 OSO2R 4 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 4 The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 4 2. C=O, NR 4 O, S or CONR 4 Instead, or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case may be one or more R 4 Aromatic or heteroaromatic ring systems with substituted groups;

[0022] R 1 In each case, the same or different alkyl group is a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the straight-chain, branched, or cyclic alkyl group in each case may be one or more R 4 The group is substituted and one or more non-adjacent CH2 groups can be replaced by O, or it has 5 to 40 aromatic ring atoms and in each case can be replaced by one or more R groups. 4 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two R groups... 1 The groups together can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; preferably, the R... 1 The group does not form any such ring system;

[0023] R 2 The same or different in each case are: H, D, F, Cl, Br, I, N(R) 4 )2, N(Ar')2, CN, NO2, OR 4 SR 4 COOR 4 C(=O)N(R) 4 )2,Si(R 4 )3, B(OR 4 )2, C(=O)R 4 , P(=O)(R 4 )2, S(=O)R 4 S(=O)2R 4 OSO2R 4A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 4 The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 4 2. C=O, NR 4 O, S or CONR 4 Instead, or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case may be one or more R 4 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two R groups... 2 Groups together or one R 2 Group and an R 3 The groups together can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; preferably, the R... 2 The group does not form any such ring system;

[0024] R 3 The same or different in each case are: H, D, F, Cl, Br, I, N(R) 4 )2, N(Ar')2, CN, NO2, OR 4 SR 4 COOR 4 C(=O)N(R) 4 )2,Si(R 4 )3, B(OR 4 )2, C(=O)R 4 , P(=O)(R 4 )2, S(=O)R 4 S(=O)2R 4 OSO2R 4 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 4 The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 4 2. C=O, NR 4 O, S or CONR 4 Instead, or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case may be one or more R 4 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two R groups... 3 Groups together or one R 3 Group and an R2 The groups together can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; preferably, the R... 3 The group does not form any such ring system;

[0025] Ar' may be the same or different in each case and is a ring with 5 to 40 aromatic atoms and can be denoted by one or more R. 4 Aromatic or heteroaromatic ring systems with substituted groups;

[0026] R 4 The same or different in each case are: H, D, F, Cl, Br, I, N(R) 5 )2, CN, NO2, OR 5 SR 5 ,Si(R 5 3, B(OR) 5 )2, C(=O)R 5 , P(=O)(R 5 )2, S(=O)R 5 S(=O)2R 5 OSO2R 5 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 5 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 5 2. C=O, NR 5 O, S or CONR 5 Instead, or having 5 to 40 aromatic ring atoms and in each case being one or more R 5 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 4 The groups together can form an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system; preferably, the R... 4 The group does not form any such ring system;

[0027] R 5 In each case, the same or different are: H, D, F, or an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 carbon atoms, especially a hydrocarbon group, wherein one or more hydrogen atoms in the organic group may also be replaced by F;

[0028] o may be the same or different in each case and is 0, 1, 2, 3, 4, 5 or 6, preferably 0 or 1, very preferably 0.

[0029] In the context of this invention, an aryl group contains 6 to 40 carbon atoms; a heteroaryl group contains 2 to 40 carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. Here, aryl group or heteroaryl group should be understood to refer to a simple aromatic ring, i.e., benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a condensed (fused) aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatic systems linked together by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but rather as aromatic ring systems.

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

[0031] In the context of this invention, aromatic ring systems contain 6 to 60 carbon atoms. Heteroaromatic ring systems in the context of this invention contain 2 to 60 carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. In the context of this invention, aromatic or heteroaromatic ring systems should be understood to refer to systems that do not necessarily contain only aryl or heteroaromatic groups, but in which two or more aryl or heteroaromatic groups can also be linked by non-aromatic units such as carbon, nitrogen, or oxygen atoms. For example, systems such as fluorene, 9,9'-spirodifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, piracene, etc., should also be considered aromatic ring systems in the context of this invention, as should systems in which two or more aryl groups are linked by, for example, short alkyl groups. Preferably, the aromatic ring system is selected from fluorene, 9,9'-spirodifluorene, 9,9-diarylamine, or a group in which two or more aryl and / or heteroaryl groups are linked to each other by single bonds.

[0032] In the context of this invention, an aliphatic hydrocarbon group, alkyl group, alkenyl group, or alkynyl group containing 1 to 20 carbon atoms, wherein some hydrogen atoms or CH2 groups may also be replaced by the aforementioned groups, is preferably understood to refer to 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, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptenyl, or ocynyl groups. Alkoxy groups having 1 to 40 carbon atoms are preferably understood to be methyl methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexyloxy, pentafluoroethoxy, and 2,2,2-trifluoroethoxy. Thioalkyl groups having 1 to 40 carbon atoms should be understood, in particular, to be thioyl, ethyl thioyl, n-propyl thioyl, isopropyl thioyl, n-butyl thioyl, isobutyl thioyl, sec-butyl thioyl, tert-butyl thioyl, n-pentyl thioyl, sec-pentyl thioyl, n-hexyl thioyl, cyclohexyl thioyl, n-heptyl thioyl, cycloheptyl thioyl, n-octyl thioyl, cyclooctyl thioyl, 2-ethylhexyl thioyl, trifluoromethyl thioyl, pentafluoroethyl thioyl, 2,2,2-trifluoroethyl thioyl, ethylene thioyl, propylene thioyl, butene thioyl, pentene thioyl, cyclopentene thioyl, hexene thioyl, hepten thioyl, cycloheptene thioyl, octenene thioyl, cyclooctenene thioyl, ethynyl thioyl, propynyl thioyl, butynyl thioyl, pentynyl thioyl, hexynyl thioyl, heptenyl thioyl, or octyynyl thioyl. Generally, the alkyl, alkoxy, or thioalkyl groups according to the present invention can be straight-chain, branched, or cyclic, wherein one or more non-adjacent CH2 groups can be replaced by the above groups; in addition, one or more hydrogen atoms can also be replaced by D, F, Cl, Br, I, CN, or NO2, preferably by F, Cl, or CN, more preferably by F or CN, and especially preferably by CN.

[0033] Aromatic or heteroaromatic ring systems having 5-60 or 5-40 aromatic ring atoms, and in each case potentially substituted by the aforementioned groups, and linked to the aromatic or heteroaromatic system via any desired position, should be understood to specifically refer to groups derived from the following substances: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, pyrene, celestene, perylene, fluoranthene, tetraphenylbenzene, pentaphenylbenzene, benzo[a]pyrene, biphenyl, diphenylidene, terphenyl, diphenylidene, fluorene, spirofluorene, dihydrophenanthrene, dihydropyrene, tetrahydro[a]pyrene, etc. Pyrene, cis or trans indofluorene, cis or trans benzocarbazole, cis or trans indole-carbazole, terpinene, isoterpinene, spiroterpinene, spiroisoterpinene, 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, phenanthrene Azides, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthiazoles, phenanthreneimidazoles, pyridiniumimidazoles, pyraziniumimidazoles, quinoxalineimazoles azole, benzo[ azole, naphtho azole, anthraquinone azole, phenanthrene azole, isotonic Azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylide, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenazine Azides, phenothiazines, fluorescent rings, naphthidine, azacarbazole, benzo[a]carbline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzo[a]triazole, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- Diazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indazine, and benzothiadiazole, or groups derived from combinations of said systems.

[0034] In the context of this specification, the phrase "two or more groups together can form a ring" should be understood to mean, in particular, that the two groups are connected to each other by chemical bonds and formally eliminate two hydrogen atoms. This is illustrated by the following scheme:

[0035]

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

[0037]

[0038] In a preferred embodiment, the compounds of the present invention may be selected from compounds of formulas (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l) and (1m).

[0039]

[0040]

[0041]

[0042] Where o, Y, X, HetAr, R, R 1 and R 2 The compounds have the definitions given above, especially for formula (1). Here, compounds of formula (1a), (1b), and (1c) are preferred, and compounds of formula (1c) are particularly preferred.

[0043] Preferably, in the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l) and (1m), no more than four, preferably no more than two, X groups are N; more preferably, all X groups are CR, wherein no more than four, more preferably no more than three, and especially preferably no more than two of the CR groups represented by X are not CH groups.

[0044] It can also be the following case: in the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l), and (1m), there is no more than one X. 1 The group is N; more preferably, all X 1 All groups are CR, where X 1 The CR groups represented preferably have no more than 3, and more preferably no more than 2, that are not CH groups.

[0045] Based on the position of fusion of the groups in formula (2), the present invention covers compounds of formulas (3), (4) and (5):

[0046]

[0047] Among them, o, HetAr, R, R 1 and R 2 With the definitions given above, especially for formula (1), and the denoting r being the same or different in each case and being 0, 1, 2, 3, 4, 5 or 6, preferably 0 or 1 and very preferably 0, the denoting n being 0, 1, 2, 3 or 4, preferably 0 or 1 and very preferably 0, and the denoting m being 0, 1 or 2, preferably 0 or 1 and very preferably 0. Herein, the compound of formula (3) is preferred.

[0048] The sum of the markers m, n, o and r in the compounds of formulas (3), (4) and (5) is preferably not greater than 6, especially preferably not greater than 4, and more preferably not greater than 2.

[0049] In a preferred embodiment of the invention, the compounds of formulas (3), (4) and (5) are selected from the compounds of formulas (3a-1), (3a-2), (4a-1), (4a-2), (5a-1) and (5a-2):

[0050]

[0051] Among them, o, HetAr, R and R 1 The compounds having the definitions given above, especially for formula (1), are preferred here.

[0052] More preferably, the compounds of formulas (3), (4) and (5) are selected from the compounds of formulas (3b), (4b) and (5b):

[0053]

[0054] Among them, o, HetAr, R and R 1 It has the definition given above, especially for formula (1). Here, the compound of formula (3b) is preferred.

[0055] It can also be the following cases: the substituents R and R in the above formula 1 R 2 and R 3 It does not form a fused aromatic or heteroaromatic ring system with the ring atoms of the ring system, preferably any fused ring system. This includes rings that can bond to R, R 1 R 2 R 3 Possible substituents R of the group 4 R 5 A fused ring system is formed.

[0056] When two are particularly selectable from R 1 R 2R 3 R 4 R 5 R 6 and / or R 7 When groups form a ring system with each other, the ring system can be a monocyclic or polycyclic aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring. In this case, the groups forming the ring system together can be adjacent, meaning that the groups are bonded to the same carbon atom or to carbon atoms directly bonded to each other, or they can be further separated from each other. Furthermore, groups with substituent R... 1 R 2 R 3 R 4 R 5 R 6 and / or R 7 The ring systems can also be linked together by bonds to form closed loops. In this case, each corresponding bonding site preferably has a substituent R. 1 R 2 R 3 R 4 R 5 R 6 and / or R 7 .

[0057] Furthermore, the preferred compounds of the present invention are characterized by their sublimability. These compounds typically have a molar mass of less than about 1200 g / mol.

[0058] As mentioned above, HetAr is an aromatic ring with 6 to 18 atoms and can be converted by one or more R atoms. 3 Electron-deficient heteroaryl groups substituted by radicals. In a preferred embodiment of the invention, HetAr has 6 to 14 aromatic ring atoms, more preferably 6 to 10 aromatic ring atoms, wherein HetAr in each case may be substituted by one or more R groups. 3 Group substitution. In a preferred embodiment of the invention, the R group on the HetAr group... 3 The groups do not form ring systems with each other. In another preferred embodiment of the invention, R 3 The group, together with the naphthyl subgroup bound to HetAr, forms a ring system, more preferably a ring system having 16 to 21, preferably 16 or 17 ring atoms, wherein the number of ring atoms includes both the naphthyl subgroup and the HetAr group.

[0059] In one embodiment, the HetAr group, together with the naphthyl subunit bound to the HetAr group, forms an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system. If the HetAr group, together with the naphthyl subunit bound to the HetAr group, forms an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system, it is a ring system having 16 to 21, preferably 16 or 17, ring atoms, wherein the number of ring atoms includes both the naphthyl subunit and the HetAr group.

[0060] Preferably, the HetAr group is selected from the structures of the following formulas (HetAr-1) to (HetAr-8):

[0061]

[0062]

[0063] The dashed bond represents a bond connected to a naphthyl subunit group; other symbols are as follows:

[0064] X 2 The same or different in each case and is CR 3 Or N, provided that at least one symbol X 2 It is N, preferably with at least two symbols X. 2 It is N, and no more than three symbols X. 2 It is N, where R 3 It has the definition given above, especially for equation (1);

[0065] A is C(R) 4 2. NR 4 O or S, with O or S preferred.

[0066] Preferably, no more than two nitrogen atoms are directly bonded to each other. More preferably, no nitrogen atoms are directly bonded to each other.

[0067] It can also be the following case: The HetAr group is selected from the structure of the following formula (HetAr-9):

[0068]

[0069] Where X 2 With the definition given above, especially for the (HetAr-1) group, the dashed bond indicates a bond connected to a naphthyl subunit. Ar may be the same or different in each case and is a ring with 5 to 40 aromatic atoms and can be bonded to one or more R groups. 4 Aromatic or heteroaromatic ring systems with substituted groups, and R 4 It has the definition given above, especially for equation (1).

[0070] In a preferred embodiment of the invention, HetAr has two or three nitrogen atoms. Here, formula (HetAr-1) preferably represents a pyrimidine group or a 1,3,5-triazine group. For formulas (HetAr-2), (HetAr-3), and (HetAr-4), they preferably have two nitrogen atoms. More preferably, formulas (HetAr-2) and (HetAr-4) represent a quinazoline group.

[0071] Groups of the preferred formulas (HetAr-1), (HetAr-2), and (HetAr-3), with particular preference for groups of the formulas (HetAr-1) and (HetAr-2).

[0072] The preferred embodiments of the (HetAr-1) group are groups of formulas (HetAr-1a) to (HetAr-1d), the preferred embodiments of the (HetAr-2) group are groups of formulas (HetAr-2a) and (HetAr-2b), the preferred embodiments of the (HetAr-3) group are groups of formula (HetAr-3a), the preferred embodiments of the (HetAr-4) group are groups of formula (HetAr-4a), the preferred embodiments of the (HetAr-5) group are groups of formula (HetAr-5a), the preferred embodiments of the (HetAr-6) group are groups of formulas (HetAr-6a) to (HetAr-6c), the preferred embodiments of the (HetAr-7) group are groups of formulas (HetAr-7a) to (HetAr-7c), and the preferred embodiments of the (HetAr-8) group are groups of formulas (HetAr-8a) to (HetAr-8c).

[0073]

[0074]

[0075] Ar may be the same or different in each case and is a ring with 5 to 40 atoms and can be denoted by one or more R atoms. 4 Aromatic or heteroaromatic ring systems with substituted groups, and other symbols as defined above.

[0076] In a preferred embodiment of the invention, the compound is selected from formula (4), (4a-1), (4a-2) or (4b), wherein HetAr is selected from formulas (HetAr-1) and (HetAr-2), preferably from formulas (HetAr-1a) to (HetAr-2b), very preferably from formulas (HetAr-1a) to (HetAr-1d), most preferably from formula (HetAr-1d), and even more preferably, Ar in the given formulas (HetAr-1) to (HetAr-2) and (HetAr-1a) to (HetAr-1d) represents a ring having 6 to 40 ring atoms and can be oxidized by one or more R atoms. 4 The aromatic ring system with substituted groups, preferably Ar is phenyl, biphenyl, terphenyl, or tetraphenyl, wherein the mentioned Ar group can be replaced by one or more R groups. 4 Group substitution and R 4 It has the definition given above.

[0077] In another preferred embodiment of the invention, the compound is selected from formula (5), (5a-1), (5a-2) or (5b), wherein HetAr is selected from formulas (HetAr-1) and (HetAr-2), preferably from formulas (HetAr-1a) to (HetAr-2b), very preferably from formulas (HetAr-1a) to (HetAr-1d), most preferably from formula (HetAr-1d), and even more preferably, Ar in the given formulas (HetAr-1) to (HetAr-2) and (HetAr-1a) to (HetAr-1d) represents a ring having 6 to 40 ring atoms and can be oxidized by one or more R atoms. 4 The aromatic ring system with substituted groups, preferably Ar is phenyl, biphenyl, terphenyl, or tetraphenyl, wherein the mentioned Ar group can be replaced by one or more R groups. 4 Group substitution and R 4 It has the definition given above.

[0078] In a highly preferred embodiment of the invention, the compound is selected from formula (3), (3a-1), (3a-2), or (3b), wherein HetAr is selected from formulas (HetAr-1) and (HetAr-2), preferably from formulas (HetAr-1a) to (HetAr-2b), very preferably from formulas (HetAr-1a) to (HetAr-1d), most preferably from formula (HetAr-1d), and even more preferably, Ar in the given formulas (HetAr-1) to (HetAr-2) and (HetAr-1a) to (HetAr-1d) represents a ring having 6 to 40 ring atoms and can be oxidized by one or more R atoms. 4 The aromatic ring system with substituted groups, preferably Ar is phenyl, biphenyl, terphenyl, or tetraphenyl, wherein the mentioned Ar group can be replaced by one or more R groups.4 Group substitution and R 4 It has the definition given above.

[0079] Preferred aromatic or heteroaromatic ring systems (Ar) are selected from: phenyl, biphenyl, especially ortho, meta, or para biphenyl, terphenyl, especially ortho, meta, or para terphenyl or branched terphenyl, tetraphenyl, especially ortho, meta, or para tetraphenyl or branched tetraphenyl, fluorene linked at positions 1, 2, 3, or 4, spirobifluorene linked at positions 1, 2, 3, or 4, and naphthalene, especially those bonded at positions 1 or 2. Naphthalene, indole, benzofuran, benzothiophene, carbazole linked at positions 1, 2, 3, or 4, dibenzofuran linked at positions 1, 2, 3, or 4, dibenzothiophene linked at positions 1, 2, 3, or 4, indocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or biphenylide, each of the groups being purported to be ... 4 Group substitution.

[0080] The Ar group here is more preferably selected independently from groups of the following formulas: Ar-1 to Ar-75:

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087] Where R 4 As defined above, a dashed key represents a key connected to HetAr. Additionally:

[0088] Ar 1 In each case, they may be the same or different, and they have 6 to 18 aromatic ring atoms and in each case can be one or more R 4 Divalent aromatic or heteroaromatic ring systems with substituted groups;

[0089] A is the same or different in every case and is C(R) 4 2. NR 4 , O or S;

[0090] p is 0 or 1, where p = 0 means Ar 1The functional group is absent, and the corresponding aromatic or heteroaromatic functional group is directly bonded to HetAr;

[0091] q is 0 or 1, where q = 0 means that there is no A group bonded at the stated position, and therefore R 4 The functional group is bonded to the corresponding carbon atom.

[0092] Preferred formulas are (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), The structure of (Ar-75) is particularly preferably the structure of formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16).

[0093] When the aforementioned groups of Ar have two or more A groups, the possible options for the groups include all combinations from the definition of A. In this case, a preferred embodiment is that one of the A groups is NR. 4 And the other A group is C(R) 4 )2 or both of the A groups are NR 4 Or those in which both A groups are O.

[0094] When A is NR 4 At that time, the substituent R bonded to the nitrogen atom 4 Preferably, it has 5 to 24 aromatic ring atoms and may also be composed of one or more R atoms. 5 Aromatic or heteroaromatic ring systems with substituted groups. In a particularly preferred embodiment, the R... 4 The substituents may be the same or different in each case and are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, particularly 6 to 18 aromatic ring atoms, and do not have fused aryl groups or any fused heteroaromatic groups in which two or more of the aromatic or heteroaromatic 6-membered ring groups are directly fused to each other, and in each case may also be replaced by one or more R 5 Group substitution. Phenyl, biphenyl, terphenyl, and tetraphenyl groups having the bonding modes listed above for Ar-1 to Ar-11 are preferred, wherein the structure can be substituted with one or more R groups. 5 Group substitution, rather than being R 4 The structure can be replaced, but preferably not replaced. Also preferred are triazines, pyrimidines, and quinazolines as listed above for Ar-47 to Ar-50, Ar-57, and Ar-58, wherein the structure can be replaced by one or more R... 5 Group substitution, rather than being R 4 replace.

[0095] When A is C(R) 4 At time 2, the substituent R bonded to the carbon atom 4 Preferably, the same or different in each case, and is a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be composed of one or more R 5 Group substitution. Most preferably, R 4 It is a methyl group or a phenyl group. In this case, R 4 Groups together can also form ring systems, thus producing spirocyclic systems.

[0096] The following are the preferred substituents R, R 1 R 2 and R 3 The description.

[0097] In a preferred embodiment of the present invention, R, R 2 and R 3 In each case, they may be the same or different and are selected from: H, D, F, CN, NO2, Si(R) 4 )3, B(OR 4 )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 in each case may be one or more R 4 Group substitution, or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case being substituted with one or more R groups. 4 Aromatic or heteroaromatic ring systems with substituted groups.

[0098] In another preferred embodiment of the present invention, R, R 2 and R 3 In each case, the same or different and 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 in each case may be one or more R 4 Group substitution, or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case being substituted with one or more R groups. 4 Aromatic or heteroaromatic ring systems with substituted groups.

[0099] In another preferred embodiment of the present invention, R, R 2 and R 3 In each case, they may be the same or different and are selected from: H, D, having 6 to 30 aromatic ring atoms and being able to be produced by one or more R... 4Aromatic or heteroaromatic ring systems substituted with groups, and N(Ar')2 groups. More preferably, R, R 2 and R 3 In each case, the same or different and selected from: H, 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 one or more R 4 Aromatic or heteroaromatic ring systems with substituted groups.

[0100] Preferred aromatic or heteroaromatic ring systems R, R 2 R 3 Ar' is selected from: phenyl, biphenyl, especially ortho, meta, or para biphenyl, terphenyl, especially ortho, meta, or para terphenyl or branched terphenyl, tetraphenyl, especially ortho, meta, or para tetraphenyl or branched tetraphenyl, fluorene linked at positions 1, 2, 3, or 4, spirobifluorene linked at positions 1, 2, 3, or 4, naphthalene, especially naphthalene bonded at positions 1 or 2, indole Benzofuran, benzothiophene, carbazole linked at positions 1, 2, 3, or 4, dibenzofuran linked at positions 1, 2, 3, or 4, dibenzothiophene linked at positions 1, 2, 3, or 4, indocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or biphenylide; each of the groups may be expressed by one or more R 4 Group substitution. The structures Ar-1 to Ar-75 listed above are particularly preferred, with preferred structures being (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), and (Ar-75), and especially preferred structures being (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16).

[0101] Other suitable R, R 2 and R 3 The group is of formula -Ar 4 -N(Ar 2 (Ar) 3 ) groups, wherein Ar 2 Ar 3 and Ar 4 In each case, they may be the same or different, and they have 5 to 24 aromatic ring atoms and in each case can be one or more R 4 Aromatic or heteroaromatic ring systems with substituted groups. 2 Ar 3 and Ar 4The total number of aromatic ring atoms shall not exceed 60, preferably not more than 40.

[0102] Here, through C(R) 4 2. NR 4 O and S groups, Ar 4 and Ar 2 They can also bond with each other and / or Ar 2 and Ar 3 They are bonded to each other. Preferably, Ar atoms are bonded to each other at the corresponding adjacent positions to the nitrogen atom. 4 and Ar 2 Mutual bonding and Ar 2 and Ar 3 They are bonded to each other. In another embodiment of the invention, Ar 2 Ar 3 and Ar 4 The groups are not bonded to each other.

[0103] Preferably, Ar 4 It has 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms, and in each case can be denoted by one or more R atoms. 4 Aromatic or heteroaromatic ring systems with substituted groups. More preferably, Ar 4 Selected from ortho, meta, or para-phenylene groups or ortho, meta, or para-biphenyl groups, each of which can be derived from one or more R... 4 Group substitution is preferred, but unsubstituted groups are also preferred. Most preferably, Ar... 4 It is an unsubstituted benzene group.

[0104] Preferably, Ar 2 and Ar 3 In each case, they may be the same or different, and they have 6 to 24 aromatic ring atoms and in each case can be one or more R 4 Aromatic or heteroaromatic ring systems with substituted groups. Particularly preferred is Ar. 2 and Ar 3The functional groups may be the same or different in each case and are selected from: phenyl, ortho, meta, or para biphenyl, ortho, meta, or para terphenyl or branched terphenyl, ortho, meta, or para tetraphenyl or branched tetraphenyl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, or 4-fluorenyl, 1-spirodifluorenyl, 2-spirodifluorenyl, 3-spirodifluorenyl, or 4-spirodifluorenyl, 1-naphthyl or 2-naphthyl, indole, benzofuran, benzothiophene, 1-carbazole, 2- Carbazole, 3-carbazole or 4-carbazole, 1-dibenzofuran, 2-dibenzofuran, 3-dibenzofuran or 4-dibenzofuran, 1-dibenzothiophene, 2-dibenzothiophene, 3-dibenzothiophene or 4-dibenzothiophene, indobenzocarbazole, indolocarbazole, 2-pyridine, 3-pyridine or 4-pyridine, 2-pyrimidine, 4-pyrimidine or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene, or biphenylide, each of the groups may be expressed by one or more R 1 Group substitution. Most preferably, Ar 2 and Ar 3 In each case, the same or different and selected from: phenyl, biphenyl, especially ortho, meta or para biphenyl, terphenyl, especially ortho, meta or para terphenyl or branched terphenyl, tetraphenyl, especially ortho, meta or para tetraphenyl or branched tetraphenyl, fluorenyl, especially 1-fluorenyl, 2-fluorenyl, 3-fluorenyl or 4-fluorenyl, or spirodifluorenyl, especially 1-spirodifluorenyl, 2-spirodifluorenyl, 3-spirodifluorenyl or 4-spirodifluorenyl.

[0105] In a preferred embodiment of the present invention, R 1 In each case, the groups may be the same or different 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 one or more R 4 Group substitution, or having 6 to 24 aromatic ring atoms and in each case being substituted with one or more R groups. 4 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two R groups... 1 The groups can also form a ring system together. More preferably, R 1 In each case, the same or different and 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 group in each case may be one or more R 4 The aromatic ring system is substituted with a group, but preferably unsubstituted, or has 6 to 12 aromatic ring atoms, especially 6 aromatic ring atoms, wherein in each case the aromatic ring system may be substituted with one or more preferably non-aromatic R groups. 4 Group substitution, but preferably unsubstituted; simultaneously, both R groups... 1 The groups can also form a ring system together. Most preferably, R 1In each case, the groups may be the same or different and are selected from straight-chain alkyl groups having 1, 2, 3, or 4 carbon atoms, or branched alkyl groups having 3 to 6 carbon atoms. Most preferably, R 1 It is either a methyl group or a phenyl group, wherein two phenyl groups together can form a ring system, and a methyl group is preferred over a phenyl group.

[0106] In another preferred embodiment of the invention, R 4 In each case, the same or different and selected from: H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group in each case may be one or more R 2 Group substitution, or having 6 to 24 aromatic ring atoms and in each case being substituted with one or more R groups. 5 Aromatic or heteroaromatic ring systems with substituted groups. In a particularly preferred embodiment of the invention, R 4 In each case, the same or different and selected from: H, a straight-chain alkyl group having 1 to 6 carbon atoms, especially 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 in each case may be one or more R 5 The group is substituted, but preferably unsubstituted, or has 6 to 13 aromatic ring atoms and in each case can be substituted by one or more R groups. 5 Aromatic or heteroaromatic ring systems that are substituted with groups, but preferably unsubstituted.

[0107] In another preferred embodiment of the invention, R 5 In each case, the same or different are: H, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, wherein the aryl group may be substituted with an alkyl group having 1 to 4 carbon atoms, but preferably not substituted.

[0108] Furthermore, in the compounds of the present invention processed by vacuum evaporation, the alkyl group preferably has no more than five carbon atoms, more preferably no more than four carbon atoms, and most preferably no more than one carbon atom. For compounds processed from solution, suitable compounds are those substituted with alkyl groups having up to 10 carbon atoms, especially branched alkyl groups, or those substituted with oligomeric aromatic subunit groups such as ortho, meta, or para-terphenyl or branched terphenyl or tetraphenyl groups.

[0109] When the compound of formula (1) or a preferred embodiment is used as a matrix material for a phosphorescent emitter or in a layer directly adjacent to a phosphorescent layer, it is also preferred that the compound does not contain any fused aryl or heteroaryl groups in which more than two six-membered rings are directly fused together. Phenanthrene and biphenylene constitute exceptions to this case because of their high triplet energy, and therefore they can still be preferred despite the presence of fused aromatic six-membered rings.

[0110] Within the limitations defined in claim 1, the above-described preferred embodiments can be freely combined with each other. In a particularly preferred embodiment of the invention, the above-described preferences occur simultaneously.

[0111] Examples of preferred compounds according to the embodiments described above are detailed in the table below:

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124] The basic structure of the compounds of the present invention can be prepared by the routes outlined in the following schemes. The various synthetic steps, such as the CC coupling reaction according to Suzuki, the CN coupling reaction according to Hartwig-Buchwald, or the cyclization reaction, are known in principle to those skilled in the art. More information on the synthesis of the compounds of the present invention can be found in the synthetic examples. The synthesis of the basic structure is shown in Scheme 1. The basic structure can be synthesized by coupling benzo[a]fluorene, substituted with an optionally substituted 2-nitrophenylboronic acid, to an optionally substituted leaving group (e.g., bromine), followed by a ring-closing reaction. Alternatively, coupling with an optionally substituted amino group of 2-aminochlorobenzene can be performed, followed by a ring-closing reaction. Schemes 2 and 3 show various options for introducing a naphthyl-HetAr group onto the nitrogen atom in the basic skeleton. Here, a naphthyl-HetAr group substituted with a suitable leaving group (e.g., bromine) can be introduced in an aromatic nucleophilic substitution reaction or a palladium-catalyzed coupling reaction, as shown in Scheme 2. Alternatively, in an aromatic nucleophilic substitution reaction, a naphthyl subunit still bearing a suitable leaving group (e.g., bromine) is introduced into the basic skeleton, and in a further coupling reaction, optionally after conversion to a boric acid derivative, a HetAr group can be introduced, as shown in Scheme 3.

[0125] Option 1

[0126]

[0127] Option 2

[0128]

[0129]

[0130] Option 3

[0131]

[0132] The symbol definitions used in schemes 1 to 3 basically correspond to the definitions specified in equation (1). For clarity, the numbering and full representation of all symbols have been omitted.

[0133] Therefore, the present invention also provides a method for preparing the compounds of the present invention, wherein a basic skeleton that does not yet contain a naphthyl-HetAr group is first synthesized, and wherein a naphthyl-HetAr group is introduced by an aromatic nucleophilic substitution reaction or a coupling reaction.

[0134] In order to process the compounds according to the invention from the liquid phase, for example by spin coating or printing, formulations of the compounds according to the invention are necessary. These formulations can be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents are preferred. Suitable and preferred solvents are, for example, toluene, anisole, ortho-, meta-, or para-xylene, methyl benzoate, mesitylene, naphthol, veratrine, THF, methyl-THF, THP, chlorobenzene, dichlorobenzene, etc. Alkane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenazine, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indene, 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 mixtures of these solvents.

[0135] Therefore, the present invention also provides formulations comprising at least one compound of the present invention and at least one other compound. The other compound may be, for example, a solvent, particularly one of the solvents described above or a mixture of these solvents. If the other compound contains a solvent, the mixture is referred to herein as a formulation. The other compound may be, or at least one other organic or inorganic compound also used in electronic devices, such as a luminescent compound and / or other matrix material. Suitable luminescent compounds and other matrix materials are listed below in conjunction with organic electroluminescent devices. The other compound may also be polymerized.

[0136] This invention also provides the use of the compounds of this invention in electronic devices, particularly organic electroluminescent devices.

[0137] The present invention also provides electronic devices comprising at least one compound of the present invention. In the context of the present invention, an electronic device is a device comprising at least one layer containing at least one organic compound. The element may also comprise a layer of inorganic material or a layer formed entirely of inorganic material.

[0138] The electronic devices are preferably selected from: 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), light-emitting electrochemical cells (LEC), organic laser diodes (O-lasers), organic plasma light-emitting devices (DMKoller 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 photosensors, 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 OLEDs.

[0139] The organic electroluminescent device comprises a cathode, an anode, and at least one emitting layer. In addition to these layers, it may also comprise other layers, such as one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers in each case. Similarly, an intermediate layer having, for example, exciton blocking functionality can be introduced between two emitting layers. However, it should be noted that each of these layers is not necessarily required. In this case, the organic electroluminescent device may contain one emitting layer, or it may contain multiple emitting layers. If multiple emitting layers are present, these preferably have a total of multiple emission maximum values ​​between 380 nm and 750 nm, thereby producing white light overall; in other words, various luminescent compounds capable of fluorescence or phosphorescence are used in the emitting layers. A system with three emitting layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red light emission. The organic electroluminescent device of the present invention can also be a tandem electroluminescent device, especially a white-emitting OLED.

[0140] It is not difficult for those skilled in the art to select suitable materials for the other layers of an organic electroluminescent device by considering the variety of materials known in the prior art. Those skilled in the art will consider the chemical and physical properties of the materials in a conventional manner, as it is known that materials interact with each other in organic electroluminescent devices. This is related, for example, to the energy levels of orbitals (HOMO, LUMO) or triplet and singlet energy levels, as well as other material properties.

[0141] The following examples list selected electron transport materials particularly suitable for use in electron blocking or electron transport layers, either in combination with or without the compounds of the present invention, as electron transport or electron blocking materials in electron blocking or electron transport layers. These are preferably triazines, very preferably 1,3,5-triazines, which are most preferably aromatic and / or heteroaromatic substitutions. Specific examples of preferred electron transport materials having a 1,3,5-triazine structure and their synthesis are disclosed, for example, in WO2010 / 072300 A1, WO2014 / 023388 A1, and Prior Art Journal 2017#03, 188-260. Some selected compounds are shown below.

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148] The compounds of the present invention can be used in different layers depending on the specific structure. Preferably, organic electroluminescent devices contain compounds of formula (1) or those described in the preferred embodiments above as matrix materials for phosphorescent emitters or emitters exhibiting TADF (thermally excited delayed fluorescence), especially phosphorescent emitters, in the emitting layer. Additionally, the compounds of the present invention can also be used in electron transport layers and / or hole transport layers and / or exciton blocking layers and / or hole blocking layers. Particularly preferred are the use of the compounds of the present invention as matrix materials for red, orange, or yellow phosphorescent emitters, especially red phosphorescent emitters, in the emitting layer, or as electron transport materials or hole blocking materials in the electron transport layer or hole blocking layer.

[0149] When the compounds of the present invention are used as matrix materials for phosphorescent compounds in the luminescent layer, they are preferably used in combination with one or more phosphorescent materials (triple-state emitters). In the context of this invention, phosphorescence should be understood as emission from excited states with high spin multiplicity, i.e., spin > 1, particularly from excited triplet states. In the context of this application, all luminescent complexes containing transition metals or lanthanides, particularly all iridium, platinum, and copper complexes, should be considered phosphorescent compounds.

[0150] Based on the total mixture of the luminescent material and the matrix material, the mixture of the compound of the present invention and the luminescent compound contains between 99 vol% and 1 vol%, preferably between 98 vol% and 10 vol%, more preferably between 97 vol% and 60 vol%, and especially between 95 vol% and 80 vol%. Accordingly, based on the total mixture of the luminescent material and the matrix material, the mixture contains between 1 vol% and 99 vol%, preferably between 2 vol% and 90 vol%, more preferably between 3 vol% and 40 vol%, and especially between 5 vol% and 20 vol%.

[0151] In one embodiment of the invention, the compound of the invention is used herein as the sole matrix material (“single host”) for the phosphorescent emitter.

[0152] Another embodiment of the present invention is the use of the compound of the present invention in combination with other matrix materials as a matrix material for phosphorescent emitters. Suitable matrix materials that can be used in combination with the compounds of the present invention are, for example, aromatic ketones, aromatic phosphine oxides, or aromatic sulfoxides or sulfones disclosed in WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680; triarylamines, carbazole derivatives, such as CBP (N,N-biscarbazole biphenyl), or carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP1205527, WO 2008 / 086851 or WO 2013 / 041176; indolecarbazole derivatives, for example, according to WO 2007 / 063754 or WO 2008 / 056746; for example, according to WO Indobenzocarbazole derivatives according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azirazole derivatives according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160; bipolar matrix materials according to WO 2007 / 137725; silanes according to WO 2005 / 111172; borazocyclopentanes or borate esters according to WO 2006 / 117052; and WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO Triazine derivatives according to 2011 / 060859 or WO 2011 / 060877; zinc complexes according to EP 652273 or WO 2009 / 062578; silylated diazacyclopentane or silicotetrazacyclopentane derivatives according to WO 2010 / 054729; phosphorodiazacyclopentane derivatives according to WO 2010 / 054730; bridged carbazole derivatives according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080; triphenylide derivatives according to WO 2012 / 048781; and derivatives according to WO 2015 / 169412, WO 2016 / 015810, WO Dibenzofuran derivatives of 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565; or, for example, biscarbazole according to JP 3139321 B2.

[0153] Similarly, another phosphorescent emitter with a shorter emission wavelength than the actual emitter can also be used as a co-body in the mixture. Particularly good results can be achieved when the emitter used is a red phosphorescent emitter and the co-body used in combination with the compound of the present invention is a yellow phosphorescent emitter.

[0154] Furthermore, the co-matrix used can be a compound that does not participate in charge transport to a significant extent (even if it does participate), for example, as described in WO 2010 / 108579. Compounds with large band gaps and that themselves do not participate in the charge transport of the luminescent layer to a significant extent (even if they do participate) are particularly suitable as co-matrix materials in combination with the compounds of the present invention. Such materials are preferably pure hydrocarbons. Examples of such materials can be found, for example, in WO 2009 / 124627 or WO 2010 / 006680.

[0155] Particularly preferred co-host materials that can be used in combination with the compounds of the present invention are compounds of one of formulas (6), (7), (8), (9), and (10), preferably biscarbazole derivatives of one of formulas (6), (7), (8), (9), and (10).

[0156]

[0157] The symbols and markings used are as follows:

[0158] R 6 The same or different in each case are: H, D, F, Cl, Br, I, N(R) 7 )2, N(Ar”)2, CN, NO2, OR 7 SR 7 COOR 7 C(=O)N(R) 7 )2,Si(R 7 )3, B(OR 7 )2, C(=O)R 7 , P(=O)(R 7 )2, S(=O)R 7 S(=O)2R 7 OSO2R 7 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 7 The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 7 2. C=O, NR 7 O, S or CONR 7Instead, or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case may be one or more R 7 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two R groups... 6 The groups together can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; preferably, the R... 6 The group does not form any such ring system;

[0159] Ar" may be the same or different in each case and is a ring with 5 to 40 aromatic atoms and can be denoted by one or more R 7 Aromatic or heteroaromatic ring systems with substituted groups;

[0160] A 1 It is C(R) 7 2. NR 7 , O or S;

[0161] Ar 5 In each case, they may be the same or different and have 5 to 40 aromatic ring atoms and can be generated by one or more R... 7 Aromatic or heteroaromatic ring systems with substituted groups;

[0162] R 7 The same or different in each case are: H, D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 )3, B(OR 8 )2, C(=O)R 8 , P(=O)(R 8 )2, S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 8 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Instead, or having 5 to 40 aromatic ring atoms and in each case being one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 7 The groups together can form an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system; preferably, the R... 7The group does not form any such ring system;

[0163] R 8 In each case, the same or different are: H, D, F, or an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 carbon atoms, especially a hydrocarbon group, wherein one or more hydrogen atoms in the organic group may also be replaced by F;

[0164] s may be the same or different in each case and is 0, 1, 2, 3 or 4, preferably 0 or 1, and very preferably 0;

[0165] t may be the same or different in each case and is 0, 1, 2 or 3, preferably 0 or 1, and very preferably 0;

[0166] u is the same or different in each case and is 0, 1 or 2, preferably 0 or 1, and very preferably 0.

[0167] The sum of the labels s, t and u in the compounds of formulas (6), (7), (8), (9) and (10) is preferably not greater than 6, especially preferably not greater than 4 and more preferably not greater than 2.

[0168] In a preferred embodiment of the present invention, R 6 The same or different in each case and: H, D, F, CN, NO2, Si(R) 7 )3, B(OR 7 )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 in each case may be one or more R 7 Group substitution, or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case being substituted with one or more R groups. 7 Aromatic or heteroaromatic ring systems with substituted groups.

[0169] In another preferred embodiment of the invention, R 6 In each case, the same or different and 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 in each case may be one or more R 7 Group substitution, or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case being substituted with one or more R groups. 7 Aromatic or heteroaromatic ring systems with substituted groups.

[0170] In another preferred embodiment of the invention, R 6In each case, they may be the same or different and are selected from: H, D, having 6 to 30 aromatic ring atoms and being able to be produced by one or more R... 7 Aromatic or heteroaromatic ring systems substituted with groups, and N(Ar”)2 groups. More preferably, R 6 In each case, the same or different and selected from: H, 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 one or more R 7 Aromatic or heteroaromatic ring systems with substituted groups.

[0171] Preferred aromatic or heteroaromatic ring systems R 6 "Ar" is selected from: phenyl, biphenyl, especially ortho, meta, or para biphenyl, terphenyl, especially ortho, meta, or para terphenyl or branched terphenyl, tetraphenyl, especially ortho, meta, or para tetraphenyl or branched tetraphenyl, fluorene that may be linked at positions 1, 2, 3, or 4, spirobifluorene that may be linked at positions 1, 2, 3, or 4, naphthalene, especially naphthalene bonded at positions 1 or 2, indole Indoles, benzofurans, benzothiophenes, carbazoles linked at positions 1, 2, 3, or 4, dibenzofurans linked at positions 1, 2, 3, or 4, dibenzothiophenes linked at positions 1, 2, 3, or 4, indoxacarbazoles, indolecarbazoles, pyridines, pyrimidines, pyrazines, pyridazines, triazines, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or biphenylene oxides; each of these groups may be expressed by one or more R... 7 Group substitution. The structures Ar-1 to Ar-75 listed above are particularly preferred, with preferred structures being (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), and (Ar-75), and particularly preferred structures being (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16). In the above structures Ar-1 to Ar-75, regarding R... 6 and Ar" group, substituent R 4 Should be subject to the corresponding R 7 Group substitution. The above applies to R. 2 and R 3 The preferred option for the group applies accordingly to R. 6 Group.

[0172] Other suitable R 6 The group is of formula -Ar 4 -N(Ar 2 (Ar) 3 ) groups, wherein Ar 2Ar 3 and Ar 4 In each case, they may be the same or different, and they have 5 to 24 aromatic ring atoms and in each case can be one or more R 4 Aromatic or heteroaromatic ring systems with substituted groups. 2 Ar 3 and Ar 4 The total number of aromatic ring atoms in Ar is no more than 60, and preferably no more than 40. 2 Ar 3 and Ar 4 Other preferred options for the group have been stated above and apply accordingly.

[0173] It can also be the following case: the substituent R in the above formula 6 An aromatic or heteroaromatic ring system that does not form fused rings with the ring atoms of the ring system, preferably any fused ring system. This includes rings that can bond to R 6 Possible substituents R of the group 7 R 8 A fused ring system is formed.

[0174] When A 1 It is NR 7 At that time, the substituent R bonded to the nitrogen atom 7 Preferably, it has 5 to 24 aromatic ring atoms and may also be composed of one or more R atoms. 8 Aromatic or heteroaromatic ring systems with substituted groups. In a particularly preferred embodiment, the R... 7 The substituents may be the same or different in each case and are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, particularly 6 to 18 aromatic ring atoms, and without any fused aryl or heteroaromatic groups in which two or more of the aromatic or heteroaromatic 6-membered ring groups are directly fused to each other, and may also be replaced by one or more R in each case. 8 Group substitution. Phenyl, biphenyl, terphenyl, and tetraphenyl groups having the bonding modes listed above for Ar-1 to Ar-11 are preferred, wherein these structures can be substituted by one or more R groups. 8 Groups instead of R 4 Substitution is preferred, but not substituted. Triazines, pyrimidines, and quinazolines as listed above for Ar-47 to Ar-50, Ar-57, and Ar-58 are also preferred, wherein these structures can be replaced by one or more R... 8 Group substitution, rather than being R 4 replace.

[0175] When A 1 It is C(R) 7 At time 2, the substituent R bonded to the carbon atom 7Preferably, the same or different in each case, and is a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be composed of one or more R 8 Group substitution. Most preferably, R 7 It is a methyl group or a phenyl group. In this case, R 7 Groups together can also form ring systems, thus producing spirocyclic systems.

[0176] Preferred aromatic or heteroaromatic ring systems Ar 5 Selected from: phenyl, biphenyl, especially ortho, meta, or para biphenyl, terphenyl, especially ortho, meta, or para terphenyl or branched terphenyl, tetraphenyl, especially ortho, meta, or para tetraphenyl or branched tetraphenyl, fluorene linked at positions 1, 2, 3, or 4, spirodifluorene linked at positions 1, 2, 3, or 4, naphthalene, especially naphthalene bonded at positions 1 or 2, indole, benzofuran, benzothiophene, carbazole linked at positions 1, 2, 3, or 4, dibenzofuran linked at positions 1, 2, 3, or 4, dibenzothiophene linked at positions 1, 2, 3, or 4, indocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or biphenylide; each of the groups may be derived from one or more R 7 Group substitution.

[0177] Ar 5 The groups are more preferably independently selected from the above-described Ar-1 to Ar-75 formulas, with preferred structures being (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), and (Ar-75), and particularly preferred structures being (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16). In the above-described Ar-1 to Ar-75 structures, regarding Ar... 5 Group, substituent R 4 Should be subject to the corresponding R 7 Group substitution.

[0178] In another preferred embodiment of the invention, R 7 In each case, the same or different and selected from: H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group in each case may be one or more R 2Group substitution, or having 6 to 24 aromatic ring atoms and in each case being substituted with one or more R groups. 8 Aromatic or heteroaromatic ring systems with substituted groups. In a particularly preferred embodiment of the invention, R 7 In each case, the same or different and selected from: H, a straight-chain alkyl group having 1 to 6 carbon atoms, especially 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 in each case may be one or more R 5 The group is substituted, but preferably unsubstituted, or has 6 to 13 aromatic ring atoms and in each case can be substituted by one or more R groups. 8 Aromatic or heteroaromatic ring systems that are substituted with groups, but preferably unsubstituted.

[0179] In another preferred embodiment of the invention, R 8 In each case, the same or different are: H, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, wherein the aryl group may be substituted with an alkyl group having 1 to 4 carbon atoms, but preferably not substituted.

[0180] Preferred embodiments of the compounds of formulas (6) and (7) are the compounds of formulas (6a) and (7a):

[0181]

[0182] Where R 6 Ar 5 and A 1 With the definitions given above, especially for equations (6) or (7). In a preferred embodiment of the invention, A in equation (7a) 1 It is C(R) 7 )2.

[0183] Preferred embodiments of the compounds of formulas (6) and (7) are the compounds of formulas (6b) and (7b):

[0184]

[0185] Where R 6 Ar 5 and A 1 With the definitions given above, especially for equations (6) or (7). In a preferred embodiment of the invention, A in equation (7b) 1 It is C(R) 7 )2.

[0186] Examples of suitable compounds of formulas (6), (7), (8), (9) and (10) are the compounds described below:

[0187]

[0188]

[0189]

[0190]

[0191]

[0192] Combining at least one compound of formula (1) or the preferred embodiments thereof described above with a compound of one of formulas (6), (7), (8), (9), and (10) can achieve surprising advantages. Therefore, the present invention also provides a composition comprising at least one compound of formula (1) or the preferred embodiments thereof described above and at least one other matrix material, wherein the other matrix material is selected from a compound of one of formulas (6), (7), (8), (9), and (10).

[0193] Preferably, the composition consists of at least one compound of formula (1) or the preferred embodiments thereof and at least one compound of formula (6), (7), (8), (9) and (10). These compositions are particularly suitable as so-called premixes that can be evaporated together.

[0194] Based on the total mass of the composition, the compound of formula (1) or the preferred embodiment thereof is preferably in the composition in the range of 10% to 95% by weight, more preferably in the range of 15% to 90% by weight, and very preferably in the range of 40% to 70% by weight.

[0195] It can also be the case that, based on the whole composition, the mass proportion of one of the compounds of formulas (6), (7), (8), (9) and (10) in the composition is in the range of 5% to 90% by weight, preferably in the range of 10% to 85% by weight, more preferably in the range of 20% to 85% by weight, even more preferably in the range of 30% to 80% by weight, very particularly preferably in the range of 20% to 60% by weight, and most preferably in the range of 30% to 50% by weight.

[0196] Alternatively, the other matrix material may be a hole transport matrix material of at least one of formulas (6), (7), (8), (9), and (10), and the mass proportion of the hole transport matrix material based on the whole composition is in the range of 10% to 95% by weight, preferably in the range of 15% to 90% by weight, more preferably in the range of 15% to 80% by weight, even more preferably in the range of 20% to 70% by weight, very particularly preferably in the range of 40% to 80% by weight, and most preferably in the range of 50% to 70% by weight.

[0197] It can also be the case that the composition consists of at least one compound of formula (1) or one of the above preferred embodiments and other matrix materials mentioned, preferably formulas (6), (7), (8), (9) and (10).

[0198] Suitable phosphorescent compounds (= triplet emitters) are especially compounds that, when properly excited, preferably emit light in the visible light region and further contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, particularly a metal having said atomic number. Preferred phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, especially compounds containing iridium or platinum.

[0199] Examples of the aforementioned luminescent materials can be found in the following applications: WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626, WO2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 023377, WO2014 / 094961, WO 2014 / 094960, WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO2016 / 015815, WO 2016 / 124304, WO 2017 / 032439, and WO 2018 / 011186. Generally speaking, all phosphorescent complexes known to those skilled in the art in the field of organic electroluminescence and used in phosphorescent electroluminescence devices according to existing technology are suitable, and those skilled in the art can use other phosphorescent complexes without inventive effort.

[0200] Examples of phosphorescent dopants are listed in the table below:

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209] The compounds of this invention are also particularly suitable as matrix materials for phosphorescent emitters in organic electroluminescent devices, as described in, for example, WO 98 / 24271, US 2011 / 0248247, and US 2012 / 0223633. In these multicolor display elements, an additional blue emitting layer is applied to all pixels, including pixels having colors other than blue, by vapor deposition over the entire area.

[0210] In another embodiment of the invention, the organic electroluminescent device of the present invention does not contain any separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer. This means that the light-emitting layer is directly adjacent to the hole injection layer or anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode, as described, for example, in WO2005 / 053051. Alternatively, a metal complex that is the same as or similar to the metal complex in the light-emitting layer can be used as the hole transport or hole injection material directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0211] In the other layers of the organic electroluminescent device of the present invention, any material commonly used according to the prior art can be used. Therefore, those skilled in the art can combine any material known for use in organic electroluminescent devices with the compound of the present invention of formula (1) or the preferred embodiments described above without inventive effort.

[0212] Another preferred embodiment is an organic electroluminescent device, characterized by coating one or more layers via a sublimation process. In this case, within a vacuum sublimation system, at less than 10... -5 millibars, preferably less than 10 -6 The material is applied via vapor deposition at an initial pressure of millibars. However, the initial pressure can also be even lower, for example, less than 10. -7 millibar.

[0213] Also preferred is an organic electroluminescent device, characterized by coating one or more layers by an OVPD (organic vapor deposition) method or by means of carrier gas sublimation. In this case, at 10 -5 The material is applied at a pressure between millibar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and thereby structured.

[0214] Another preferred embodiment is an organic electroluminescent device, characterized in that one or more layers are manufactured from a solution, for example by spin coating, or by any printing method such as screen printing, flexographic printing, offset printing, LITI (photoinduced thermal imaging, thermal transfer printing), inkjet printing, or nozzle printing. For this purpose, a soluble compound is required, which is obtained, for example, through appropriate substitution.

[0215] Formulations using the compound of formula (1) or the preferred embodiments thereof described above are novel. Therefore, the present invention also provides a formulation comprising at least one solvent and a compound of formula (1) or the preferred embodiments thereof described above. A formulation comprising at least one solvent and a compound of formula (1) or the preferred embodiments thereof described above, and at least one compound of formulas (6), (7), (8), (9), and (10).

[0216] Alternatively, a hybrid process can be used, for example, in which one or more layers are applied from a solution while one or more other layers are applied via vapor deposition.

[0217] These methods are generally known to those skilled in the art, and can be applied to organic electroluminescent devices containing the compounds of the present invention without inventive effort.

[0218] The compounds of the present invention and the organic electroluminescent devices of the present invention possess a particular characteristic of improved lifetime compared to the prior art. This is especially true compared to similar compounds having an indene-carbazole backbone instead of a benzo[a]indene-carbazole backbone. Meanwhile, other electronic properties of the electroluminescent devices, such as efficiency or operating voltage, are at least as good. In another variant, the compounds of the present invention and the organic electroluminescent devices of the present invention are particularly characterized by improved efficiency and / or operating voltage and a longer lifetime compared to the prior art. This is especially true compared to similar compounds having an indene-carbazole backbone instead of a benzo[a]indene-carbazole backbone.

[0219] The electronic devices of the present invention, particularly organic electroluminescent devices, are remarkable for one or more of the following advantages that surprisingly surpass the prior art:

[0220] 1. Compounds comprising formula (1) or the preferred embodiments listed in the context, particularly for electronic devices, especially organic electroluminescent devices, as matrix materials or electronically conductive materials, exhibit excellent lifetimes. In this case, these compounds particularly produce low roll-off, i.e., minimal decrease in power efficiency of the device at high brightness.

[0221] 2. Compounds comprising formula (1) or the preferred embodiments listed in the context, as electronic devices, especially organic electroluminescent devices, exhibit excellent efficiency as electronic conductive materials and / or matrix materials. In this case, when the compounds of the present invention comprising formula (1) or the preferred embodiments listed above and below are used in electronic devices, a low operating voltage is generated.

[0222] 3. The compounds of the present invention according to formula (1) or the preferred embodiments listed above and below exhibit high stability and longevity.

[0223] 4. Compounds of the preferred embodiments of formula (1) or listed in the context can avoid the formation of light loss channels in electronic devices, especially organic electroluminescent devices. As a result, the device is characterized by high PL efficiency of the light emitter and the resulting high EL efficiency, as well as excellent energy transfer from the matrix to the dopant.

[0224] 5. The use of compounds of formula (1) or the preferred embodiments listed in the context in the layers of electronic devices, especially organic electroluminescent devices, results in high mobility of the electron conduction structure.

[0225] 6. The compounds of the preferred embodiments of formula (1) or listed in the context have excellent glass film forming properties.

[0226] 7. The compound of the preferred embodiment of formula (1) or listed in the context forms a good film from solution.

[0227] 8. The compounds of the preferred embodiments listed in formula (1) or in the context have, for example, a low triplet energy level T1 in the range of 2.22 eV to 2.42 eV.

[0228] These advantages are not accompanied by an unusually high degree of degradation in other electronic properties.

[0229] It should be noted that the scope of this invention covers variations of the embodiments described herein. Unless expressly excluded, any feature disclosed herein may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Therefore, unless otherwise stated, any feature disclosed herein should be considered as an example of a class series or as an equivalent or similar feature.

[0230] All features of this invention may be combined with each other in any way, unless specific features and / or steps are mutually exclusive. This is especially true for preferred features of the invention. Similarly, features that are not necessarily combined may be used separately (without being combined).

[0231] It should also be noted that many features, especially those of the preferred embodiments of the invention, should be considered inventive in themselves, and not merely as embodiments of the invention. Independent protection may be sought for these features, supplementing any currently claimed invention or as an alternative to it.

[0232] The technical teachings disclosed in this invention can be extracted and combined with other examples.

[0233] The following examples illustrate the invention in more detail, but are not intended to limit the invention. Those skilled in the art will be able to use the information given to practice the invention and prepare other compounds of the invention throughout the entire scope of the disclosure without any inventive effort. Example:

[0234] Unless otherwise specified, the following synthesis was carried out in a dry solvent under a protective gas atmosphere. Solvents and reagents are available from ALDRICH or ABCR. The numbers given for reactants are their respective CAS numbers.

[0235] a)(2-chlorophenyl)(11,11-dimethyl-11H-benzo[a]fluorene-9-yl)amine

[0236]

[0237] 47 g (145 mmol) of 9-bromo-11,11-dimethyl-11H-benzo[a]fluorene, 16.8 g (159 mmol) of 2-chloroaniline, 41.9 g (436.2 mmol) of sodium tert-butoxide, and 1.06 g (1.45 mmol) of Pd(dppf)Cl₂ were dissolved in 500 mL of toluene and stirred under reflux for 5 hours. The reaction mixture was cooled to room temperature, expanded with toluene, and filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure, and the residue was crystallized from toluene / n-heptane. The product was isolated as a colorless solid. Yield: 33 g (89 mmol); 70% of theoretical value.

[0238] The following compounds can be prepared in a similar manner:

[0239]

[0240]

[0241] b) Cycloning

[0242]

[0243] 48 g (129 mmol) of (2-chlorophenyl)(11,11-dimethyl-11H-benzo[a]fluorene-9-yl)amine, 53 g (389 mmol) of potassium carbonate, 4.5 g (12 mmol) of tricyclohexylphosphine tetrafluoroborate, 1.38 g (6 mmol) of palladium(II) acetate, and 3.3 g (32 mmol) of neopentanoic acid were suspended in 500 mL of dimethylacetamide and stirred under reflux for 6 hours. After cooling, the reaction mixture was mixed with 300 mL of water and 400 mL of CH2Cl2. The mixture was stirred for another 30 minutes, the organic phase was separated, filtered through a short diatomaceous earth bed, and the solvent was removed under reduced pressure. The crude product was thermally extracted with toluene and recrystallized from toluene. The product was separated as a beige solid. Yield: 34 g (102 mmol); 78% of the theoretical value.

[0244] The following compounds can be prepared in a similar manner:

[0245]

[0246]

[0247] c) 11,11-Dimethyl-3-(2-nitrophenyl)-11H-benzo[b]fluorene

[0248]

[0249] 1.7 g (1.49 mmol) of Pd(PPh3)4 was added to a degassed suspension of 59 g (183.8 mmol) of 2-nitrophenylboronic acid, 54 g (184 mmol) of 3-bromo-11,11-dimethyl-11H-benzo[b]fluorene, and 66.5 g (212.7 mmol) of potassium carbonate in a mixture of 250 mL of water and 250 mL of THF, and the mixture was heated under reflux for 17 hours. After cooling, the organic phase was separated, washed three times with 200 mL of water each time, washed once with 200 mL of saturated sodium chloride aqueous solution, dried over magnesium sulfate, and concentrated to dryness by rotary evaporation. The gray residue was recrystallized from hexane. The precipitated crystals were filtered off, washed with a small amount of MeOH, and dried under reduced pressure. Yield: 53 g (146 mmol); 80% of theoretical value.

[0250] The following compounds can be prepared in a similar manner:

[0251]

[0252] d) Carbazole synthesis

[0253]

[0254] A mixture of 87 g (240 mmol) of 11,11-dimethyl-3-(2-nitrophenyl)-11H-benzo[b]fluorene and 290.3 mL (1669 mmol) of triethyl phosphite was heated under reflux for 12 hours. The remaining triethyl phosphite was then distilled off (72-76 °C / 9 mm Hg). Water / MeOH (1:1) was added to the residue, the solid was filtered off, and recrystallized. Yield: 58 g (176 mmol); 74% of theoretical value.

[0255] The following compounds can be prepared in a similar manner:

[0256]

[0257]

[0258] e) Nucleophilic substitution

[0259]

[0260] Under a protective atmosphere, 4.2 g of 60% NaH (106 mmol) in mineral oil was dissolved in 300 ml of dimethylformamide. 34 g (106 mmol) of 7,9-dihydro-7,7-dimethylbenzo[6,7]indo[2,1-b]carbazole was dissolved in 250 ml of DMF and added dropwise to the reaction mixture. After 1 hour at room temperature, a solution of 48 g (122 mmol) of 2-(4-bromo-1-naphthyl)-4,6-diphenyl[1,3,5]triazine in 200 ml of THF was added dropwise. The reaction mixture was stirred at room temperature for 12 hours. After this time, the reaction mixture was poured onto ice. After warming to room temperature, the precipitated solid was filtered and washed with ethanol and heptane. The residue was thermally extracted with toluene and recrystallized from toluene / n-heptane, finally sublimated under high vacuum; the purity was 99.9%. The yield was 50g (72mmol); 68% of the theoretical value.

[0261] The following compounds can be prepared in a similar manner:

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271] f) Bromination

[0272]

[0273] 158 g (230 mmol) of compound e was initially fed into 1000 mL of THF. Then, a solution of 41.7 g (234.6 mmol) of NBS in 500 mL of THF was added dropwise at -15 °C in the dark, allowing the mixture to reach room temperature and stirring at that temperature for 4 hours. Subsequently, 150 mL of water was added to the mixture, and extraction was performed with CH2Cl2. The organic phase was dried over MgSO4, and the solvent was removed under reduced pressure. The product was extracted with hot hexane with stirring and filtered. Yield: 104 g (135 mmol), 59% of the theoretical value, by… 1 The purity was determined to be approximately 98% by ¹H NMR.

[0274] The following compounds can be prepared in a similar manner:

[0275]

[0276]

[0277] g) Suzuki reaction

[0278]

[0279] 33.5 g (44 mmol) of the product of Example f, 13.4 g (47 mmol) of 9-phenylcarbazole-3-boric acid, and 29.2 g of Rb₂CO₃ were suspended in 250 mL of p-xylene. 0.95 g (4.2 mmol) of Pd(OAc)₂ and 12.6 mL of 1 M tri-tert-butylphosphine solution were added to the suspension. The reaction mixture was heated under reflux for 16 hours. After cooling, the organic phase was separated, washed three times with 200 mL of water, and then concentrated to dryness. The residue was thermally extracted with toluene, recrystallized from toluene, and finally sublimated under high vacuum; purity was 99.9%. Yield: 28 g (30 mmol), 70% of theoretical value.

[0280] The following compounds can be prepared in a similar manner:

[0281]

[0282]

[0283] Manufacturing of electroluminescent devices

[0284] The following examples V1 to E9 (see Table 1) illustrate the use of the materials of the present invention in electroluminescent devices.

[0285] Pretreatment of Examples V1-E9: A glass plate coated with a 50 nm thick structured ITO (indium tin oxide) was first treated with oxygen plasma, and then with argon plasma, before coating. These plasma-treated glass plates formed the substrate for applying electroluminescent devices.

[0286] The electroluminescent device essentially has the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emitting layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally a cathode. The cathode is formed of an aluminum layer with a thickness of 100 nm. The exact structure of the OLED can be found in Table 1. The materials required to manufacture the electroluminescent device are shown in Table 2. The data for the electroluminescent device are listed in Table 3.

[0287] All materials are applied via thermal vapor deposition in a vacuum chamber. In this case, the luminescent layer always consists of at least one matrix material (host material) and a luminescent dopant (emitter) added to the matrix material by co-evaporation in a specific volume ratio. Details given in the form 1e:IC2:TER5 (57%:40%:3%) mean that material 1e is present in the layer at a volume ratio of 57%, IC2 at 40%, and TER5 at 3%. Similarly, the electron transport layer can also consist of a mixture of the two materials.

[0288] The OLED was characterized in a standard manner. For this purpose, the electroluminescence spectrum was measured, and the current efficiency (SE, measured in cd / A) and external quantum efficiency (EQE, measured in %) as a function of luminescence density, as well as lifetime, were calculated from the current-voltage-luminescence density characteristic line exhibiting Lambertian emission properties. The electroluminescence spectrum at 1000 cd / m²... 2 The luminous density was determined, and the CIE 1931 x and y color coordinates were calculated accordingly. The parameter U1000 in Table 3 refers to 1000 cd / m². 2 The voltage required to achieve a luminous density. SE1000 and EQE1000 represent the voltage required at 1000 cd / m². 2 The achieved current efficiency and external quantum efficiency.

[0289] Lifetime (LD) is defined as the time it takes for the luminous density to decrease from its initial value to a specific proportion (L1) during operation at a constant current density (j0). The figure L1 = 95% in Table 3 refers to the lifetime reported in the LD column corresponding to the time after the luminous density decreases to 95% of its initial value.

[0290] Use of the mixture of the present invention in the light-emitting layer of a phosphorescent photoluminescent device

[0291] The material of the present invention is used as a matrix material in the light-emitting layer of an electroluminescent device emitting red phosphorescence in Examples E1 to E9. Compared with the prior art (V1 to V5), a significant improvement in lifetime can be achieved while keeping other parameters comparable.

[0292] Table 1: Structure of electroluminescent devices

[0293]

[0294]

[0295] Table 2: Structural Formulas of OLED Materials

[0296]

[0297]

[0298]

[0299]

[0300] Table 3: OLED Performance Data

[0301]

[0302] The data above demonstrate that compounds possessing all the features of claim 1 result in unexpected improvements. Compared to compounds having the same electron-deficient heteroaryl group but without a naphthyl group instead having a phenyl group as a linking group (see Comparative Experiments V2 and V3 with Experiments E1, E2 and E5 of the present invention), or compared to compounds having the same electron-deficient heteroaryl group in which the benzo[a] group is fused with a carbazole group instead of an indene group, or without a benzo[a] group fused with an indene group (see Comparative Experiments V1, V4 and V5 with Experiments E1, E2, E3 and E5 of the present invention), compounds having a naphthyl group that acts as a linking group between the nitrogen atom of the benzo[a]indene-carbazole group and the electron-deficient heteroaryl group exhibit surprisingly longer lifetimes.

[0303] Furthermore, data show that compounds in which the groups of formula (2) are fused to the compound of formula (3) have surprising advantages. Therefore, compounds of formula (3) are preferred.

[0304] In addition, as shown in Example E3, compounds in which the HetAr group and the naphthyl subunit together form a closed ring exhibit high performance.

Claims

1. A compound of formula (1), The symbols and markings used are as follows: X is CR; The two adjacent Y's are groups of the following formula (2), and the other two Y's are X's. The two dashed bonds represent the linkage of the group; X 1 It is CR; HetAr is selected from the structure of the following formula (HetAr-9): Where X 2 The same or different in each case and is CR 3 Or N, provided that at least one symbol X 2 It is N, and no more than three symbols X. 2 It is N; Dashed lines indicate bonds connected to naphthyl subunits; Ar may be the same or different in each case and is a ring with 5 to 40 aromatic atoms and can be substituted by one or more R 4 Aromatic or heteroaromatic ring systems with substituted groups; R is the same or different in each case and is: H, D, F, CN, NO2, Si(R) 4 3, B(OR) 4 )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 in each case may be one or more R 4 Group substitution, or having 5 to 40 aromatic ring atoms and in each case being substituted with one or more R groups. 4 Aromatic or heteroaromatic ring systems with substituted groups; R 1 In each case, they may be the same or different and are straight-chain alkyl groups having 1, 2, 3 or 4 carbon atoms or branched alkyl groups having 3 to 6 carbon atoms; R 2 The same or different in each case are: H, D, F, CN, NO2, Si(R) 4 3, B(OR) 4 )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 in each case may be one or more R 4 Group substitution, or having 5 to 40 aromatic ring atoms and in each case being substituted with one or more R groups. 4 Aromatic or heteroaromatic ring systems with substituted groups; R 3 The same or different in each case are: H, D, F, CN, NO2, Si(R) 4 3, B(OR) 4 )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 in each case may be one or more R 4 Group substitution, or having 5 to 40 aromatic ring atoms and in each case being substituted with one or more R groups. 4 Aromatic or heteroaromatic ring systems with substituted groups; R 4 In each case, the same or different are: H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group in each case may be one or more R 5 Group substitution, or having 6 to 24 aromatic ring atoms and in each case being substituted with one or more R groups. 5 Aromatic or heteroaromatic ring systems with substituted groups; R 5 In each case, the same or different are: H, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms; o is the same or different in each case and is 0, 1, 2, 3, 4, 5 or 6.

2. The compound according to claim 1, wherein R 5 The organic group mentioned therein is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.

3. The compound according to claim 1, wherein the compound is selected from compounds of formulas (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1h'), (1k), (1l), and (1m). Where o, Y, X, HetAr, R, R 1 and R 2 It has the definition given in claim 1.

4. The compound according to claim 3, characterized in that, The compound is selected from formula (1a), (1b) or (1c).

5. The compound according to any one of claims 1 to 4, characterized in that, In the compounds of formulas (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1h'), (1k), (1l) and (1m), no more than 4 of the CR groups represented by X are not CH groups; and / or In the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1h'), (1k), (1l), and (1m), in X 1 The CR group represents no more than 3 groups that are not CH groups.

6. The compound according to any one of claims 1 to 4, wherein the compound is selected from compounds of formulas (3), (4) and (5), Among them, o, HetAr, R, R 1 and R 2 It has the definition given in claim 1, and the denominator r is the same or different in each case and is 0, 1, 2, 3, 4, 5 or 6, the denominator n is 0, 1, 2, 3 or 4, and the denominator m is 0, 1 or 2.

7. The compound according to claim 6, characterized in that, The compound is a compound of formula (3).

8. The compound according to claim 6, characterized in that, The sum of the labels m, n, o, and r is no greater than 6.

9. The compound according to any one of claims 1 to 4, wherein the compound is selected from compounds of formula (3a-1), (3a-2), (4a-1), (4a-2), (5a-1), and (5a-2). Among them, HetAr, R and R 1 It has the definition given in claim 1.

10. The compound according to any one of claims 1 to 4, wherein the compound is selected from compounds of formulas (3b), (4b), and (5b). Among them, HetAr, R and R 1 It has the definition given in claim 1.

11. The compound according to any one of claims 1 to 4, characterized in that, HetAr is selected from groups of formulas (HetAr-1a), (HetAr-1c), and (HetAr-1d). Where Ar has the definition given in claim 1, R 4 It has the definition given in claim 1 and the dashed bond represents a bond connected to a naphthyl subunit.

12. The compound according to claim 1, characterized in that, Ar may be the same or different in each case and is selected from phenyl, biphenyl, terphenyl, tetraphenyl, fluorene, spirodifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indole-carbazole, indolo-carbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, and biphenylide, each of the above groups may be substituted by one or more R 4 Group substitution.

13. The compound according to any one of claims 1 to 4, characterized in that, R, R 2 and / or R 3 In each case, they may be the same or different and are selected from: H, D, and those having 6 to 30 aromatic ring atoms and being capable of being formed by one or more R atoms. 4 Aromatic or heteroaromatic ring systems with substituted groups.

14. The compound according to any one of claims 1 to 4, characterized in that, R, R 2 and / or R 3 In each case, the same or different aromatic or heteroaromatic ring systems selected from H, D, or groups selected from Ar-1 to Ar-75, and / or Ar groups selected from Ar-1 to Ar-75, whether the Ar group is the same or different in each case: Where R 4 As defined above, a dashed bond represents a bond attached to the corresponding group. Furthermore: Ar 1 In each case, they may be the same or different, and they have 6 to 18 aromatic ring atoms and in each case can be one or more R 4 Divalent aromatic or heteroaromatic ring systems with substituted groups; A is the same or different in every case and is C(R) 4 2. NR 4 , O or S; p is 0 or 1, where p = 0 means Ar 1 The functional group is absent, and the corresponding aromatic or heteroaromatic functional group is directly bonded to HetAr; q is 0 or 1, where q = 0 means that there is no A group bonded at the stated position, and consequently R 4 The functional group is bonded to the corresponding carbon atom.

15. A method for preparing the compound according to any one of claims 1 to 14, characterized in that, A basic skeleton that does not yet contain a naphthyl-HetAr group is synthesized, and the naphthyl-HetAr group is introduced through an aromatic nucleophilic substitution reaction or a coupling reaction.

16. A composition comprising at least one compound according to any one of claims 1 to 14 and at least one other matrix material, wherein the other matrix material is selected from compounds of formula (6), (7), (8), (9), and (10). The symbols and markings used are as follows: R 6 The same or different in each case are: H, D, F, Cl, Br, I, N(R) 7 )2, N(Ar'')2, CN, NO2, OR 7 SR 7 COOR 7 C(=O)N(R) 7 )2,Si(R 7 3, B(OR) 7 )2,C(=O)R 7 , P(=O)(R 7 )2,S(=O)R 7 S(=O)2R 7 OSO2R 7 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 7 The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 7 2. C=O, NR 7 O, S or CONR 7 Instead, or having 5 to 40 aromatic ring atoms and in each case being one or more R 7 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two R groups... 6 Groups together can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; Ar'' is the same or different in each case and has 5 to 40 aromatic ring atoms and can be denoted by one or more R''. 7 Aromatic or heteroaromatic ring systems with substituted groups; A 1 It is C(R) 7 2. NR 7 , O or S; Ar 5 In each case, they may be the same or different and have 5 to 40 aromatic ring atoms and can be generated by one or more R... 7 Aromatic or heteroaromatic ring systems with substituted groups; R 7 The same or different in each case are: H, D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 3, B(OR) 8 )2,C(=O)R 8 , P(=O)(R 8 )2,S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 8 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Instead, or having 5 to 40 aromatic ring atoms and in each case being one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 7 The groups together can form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; R 8 In each case, the same or different is: H, D, F or an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms in the organic group may also be replaced by F; s is the same or different in each case and is 0, 1, 2, 3 or 4; t is the same or different in each case and is 0, 1, 2 or 3; u is the same or different in each case and is 0, 1 or 2.

17. The composition according to claim 16, characterized in that, R 8 The organic groups mentioned are hydrocarbon groups.

18. The composition according to claim 16, characterized in that, Based on the total mass of the composition, the mass percentage of the compound according to any one of claims 1 to 14 in the composition is in the range of 10% by weight to 95% by weight.

19. The composition according to any one of claims 16 to 18, characterized in that, Based on the entire composition, the mass proportion of one of the compounds of formulas (6), (7), (8), (9) and (10) in the composition is in the range of 5% by weight to 90% by weight.

20. The composition according to any one of claims 16 to 18, characterized in that, The composition consists only of the compound according to any one of claims 1 to 14 and one of the other matrix materials mentioned.

21. A formulation comprising at least one compound according to any one of claims 1 to 14 and / or at least one composition according to any one of claims 16 to 20, and at least one other compound, wherein the other compound is selected from one or more solvents.

22. Use of the compound according to any one of claims 1 to 14 and / or the composition according to any one of claims 16 to 20 in an electronic device.

23. An electronic device comprising at least one compound according to any one of claims 1 to 14 and / or a composition according to any one of claims 16 to 20, wherein the electronic device is an electroluminescent device.

24. The electronic device according to claim 23, wherein the electronic device is an organic electroluminescent device, characterized in that, The compound according to any one of claims 1 to 14 is used as a matrix material in the luminescent layer and / or in the electron transport layer and / or in the hole blocking layer.

25. The electronic device according to claim 24, characterized in that, The compound according to any one of claims 1 to 14, combined with other matrix materials selected from compounds of formula (6), (7), (8), (9), and (10), is used as a matrix material for phosphorescent emitters. Where symbol A 1 Ar 5 and R 6 And the denotings s, t, and u have the definitions given in claim 16.

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