Materials for electronic devices

Abstract

The present invention relates to compounds suitable for use in electronic devices, and to electronic devices, more particularly organic electroluminescent devices, containing these compounds.

Description

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

[0002] Electronic devices containing organic, organometallic and / or polymer semiconductors are becoming increasingly important and are being used in many commercial products for reasons of cost and their performance. Examples here include organic charge transport materials (e.g. triarylamine-based hole transporters) in copiers, organic or polymer light emitting diodes (OLEDs or PLEDs) in readout and display devices, or organic photoreceptors in copiers. Organic solar cells (O-SCs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic integrated circuits (O-ICs), organic photoamplifiers and organic laser diodes (O-lasers) are at an advanced stage of development and may have great future significance.

[0003] An electronic device in the context of the present invention is understood to mean an organic electronic device which contains an organic semiconductor material as functional material. In particular, the electronic device represents an electroluminescent device such as an OLED.

[0004] The construction of OLEDs in which organic compounds are used as functional materials is known to the person skilled in the art from the prior art. In general, an OLED is understood to mean an electronic device which has one or more layers comprising organic compounds and which emits light when a voltage is applied.

[0005] In electronic devices, especially OLEDs, there is a great need to improve the performance data, especially lifetime, efficiency and operating voltage. For these aspects, no satisfactory solutions have been found so far.

[0006] Electronic devices generally comprise a cathode, an anode and at least one functional layer, preferably a light-emitting layer. In addition to these layers, they may also comprise further layers, for example in each case 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.

[0007] The performance data of electronic devices are mainly affected by the hole transport layer and the electron transport layer.

[0008] It was an object of the present invention to provide compounds which are suitable for use in electronic devices, especially OLEDs, especially as materials for hole-transport layers or materials for electron-transport layers, wherein they lead to good properties.

[0009] Surprisingly, it has been found that this object is achieved by specific triptycenes described in detail below, which are well suited for use in electronic devices, especially OLEDs. These OLEDs have in particular a long lifetime, high efficiency and a relatively low operating voltage. Therefore, the present invention provides these compounds and electronic devices, especially organic electroluminescent devices, comprising these compounds.

[0010] The present invention provides a compound of formula (1) and formula (2),

[0011]

[0012] The symbols used are as follows:

[0013] X is identical or different in each occurrence and is CR or N, provided that not more than two X groups in each ring are N;

[0014] Z is a group of formula (2), wherein the dotted bond in formula (2) represents a bond connected to the quaternary carbon;

[0015] Y is identical or different in each case and is CR' or N, provided that in each ring 2 or 3 Y groups are N, or 1, 2 or 3 Y groups are N and two or more Y groups which are CR' together form an aromatic or heteroaromatic ring system; preferably, in each case 2 or 3 Y groups are N;

[0016] Q is a divalent alkylene group having 1 to 4 carbon atoms, a divalent alkenylene group having 2 to 4 carbon atoms, or a divalent aryl or heteroaryl group having 5 to 60 ring atoms, wherein the alkylene, alkenylene, aryl and heteroaryl groups may be substituted with one or more R groups;

[0017] R is identical or different in each case and is H; D; F; Cl; Br; I; OAr'; SAr'; B(OR 1 )2;CHO;C(=O)R 1 CR 1 =C(R 1 )2;CN;C(=O)OR 1 ; C(=O)NR 1 ;Si(R 1 )3; NO2; P(=O)(R 1 )2;OSO2R 1 ;OR 1 ;S(=O)R 1 ; S(=O)2R 1 SR 1a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl 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 alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 1 C=CR 1 -、-C≡C-、Si(R 1 2. CONR 1 ,C=O,C=S,-C(=O)O-,P(=O)(R 1 ), -O-, -S-, SO or SO2; or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and in each case may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with R groups, wherein two or more R groups, preferably bonded to the same ring, can together form a substituted R group which can be substituted with one or more R groups. 1 radically substituted aliphatic, heteroaliphatic, aromatic or heteroaromatic ring systems, wherein, if R and the associative groups comprise at least one heteroaromatic ring system which comprises at least one nitrogen atom with three single bonds, for each of these heteroaromatic ring systems there are always at least two radicals which are bonded to the corresponding nitrogen atom via single bonds to the corresponding nitrogen atom and which are independently bonded to the base skeleton;

[0018] R' is identical or different in each case and is H; D; F; Cl; Br; I; OAr'; SAr'; B(OR 1 )2;CHO;C(=O)R 1 CR 1 =C(R 1 )2;CN;C(=O)OR 1 ; C(=O)NR 1 ;Si(R 1 )3; NO2; P(=O)(R 1 )2;OSO2R 1 ;OR 1 ;S(=O)R 1 ; S(=O)2R 1 SR 1 a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl 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 alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 1 C=CR 1-、-C≡C-、Si(R 1 2. CONR 1 ,C=O,C=S,-C(=O)O-,P(=O)(R 1 ), -O-, -S-, SO or SO2; or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and in each case may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with R groups, wherein two or more R groups, preferably bonded to the same ring, can together form a substituted R group which can be substituted with one or more R groups. 1 radically substituted aliphatic, heteroaliphatic, aromatic or heteroaromatic ring systems, wherein, if R' and the associative groups comprise at least one heteroaromatic ring system which comprises at least one nitrogen atom with three single bonds, for each of these heteroaromatic ring systems there are always at least two radicals which are bonded to the corresponding nitrogen atom via single bonds to the corresponding nitrogen atom and which are independently bonded to the base skeleton;

[0019] Ar' is identical or different in each case and is a cyclic aromatic ring having 5 to 40 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a radical, wherein two or more R 1 together can form an aromatic or heteroaromatic ring system;

[0020] R 1 are the same or different in each case and are H; D; F; I; B (OR 2 )2;CHO;C(=O)R 2 CR 2 =C(R 2 )2;CN;C(=O)OR 2 ;Si(R 2 )3; NO2; P(=O)(R 2 )2;OSO2R 2 SR 2 ;OR 2 ;S(=O)R 2 ; S(=O)2R 2 a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl 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 alkynyl group may in each case be replaced by one or more R 2 group, and one or more CH2 groups in the above groups may be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2. C=O, C=S, -C(=O)O-, CONR2 、P(=O)(R 2 ), -O-, -S-, SO or SO2, and one or more hydrogen atoms in the above groups can be replaced by D, F, Cl, Br, I, CN or NO2; or having 5 to 30 aromatic ring atoms and in each case by one or more R 2 Aromatic or heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups together may form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system;

[0021] R 2 are identical or different in each case and are H; D; F; CN; or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by D or F; at the same time, two or more R 2 The substituents may be connected to each other and form a ring.

[0022] In the context of the present invention, an aryl group contains 6 to 40 carbon atoms; in the context of the present invention, a heteroaryl group contains 5 to 40 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. Here, an aryl group or a heteroaryl group is understood to mean: a simple aromatic ring, i.e. benzene; or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc.; or a fused (annulated) aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatic compounds which are linked to one another by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0023] In the context of the present invention, the aromatic ring system contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms in the ring system. In the context of the present invention, the heteroaromatic ring system contains 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms and at least one heteroatom in the ring system, provided that the sum of carbon atoms and heteroatoms is at least 5. Heteroatoms are preferably selected from N, O and / or S. In the context of the present invention, an aromatic or heteroaromatic ring system is understood to refer to a system in which it does not necessarily only contain an aryl or heteroaryl group, but wherein two or more aryl or heteroaryl groups can also be connected by non-aromatic units (preferably less than 10% of non-H atoms) such as carbon, nitrogen or oxygen atoms or carbonyl groups. These are also understood to refer to systems in which two or more aryl or heteroaryl groups are directly connected to each other, such as biphenyl, terphenyl, bipyridine or phenylpyridine. For example, in the context of the present invention, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene etc. should also be regarded as aromatic ring systems, and the same applies to systems in which two or more aryl groups are linked, for example, via linear or cyclic alkyl groups or via silyl groups. Preferred aromatic or heteroaromatic ring systems are: simple aryl or heteroaryl groups; and groups in which two or more aryl or heteroaryl groups are directly linked to one another, for example biphenyl, terphenyl, quaterphenyl or bipyridine; and further fluorene or spirobifluorene.

[0024] The electron-rich heteroaromatic ring system is characterized in that it is a heteroaromatic ring system that does not contain an electron-deficient heteroaryl group. An electron-deficient heteroaryl group is a six-membered heteroaryl group with at least one nitrogen atom or a five-membered heteroaryl group with at least two heteroatoms, one of which is a nitrogen atom and the other is an oxygen, sulfur or substituted nitrogen atom, wherein other aryl or heteroaryl groups can also be fused to these groups in each case. In contrast, an electron-rich heteroaryl group is a five-membered heteroaryl group with just one heteroatom selected from oxygen, sulfur and substituted nitrogen, to which other aryl groups and / or other electron-rich five-membered heteroaryl groups can be fused. Thus, examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene or indenocarbazole. Electron-rich heteroaryl groups are also referred to as electron-rich heteroaromatic groups.

[0025] An electron-deficient heteroaromatic ring system is characterized in that it comprises at least one electron-deficient heteroaryl group and particularly preferably no electron-rich heteroaryl groups.

[0026] In the context of the present invention, the term "alkyl group" is used as a general term for straight-chain and branched alkyl groups and cyclic alkyl groups. Similarly, the terms "alkenyl group" and "alkynyl group" are used as a general term for straight-chain or branched alkenyl or alkynyl groups and cyclic alkenyl or alkynyl groups.

[0027] In the context of the present invention, cyclic alkyl, alkoxy or thioalkoxy groups are understood to mean monocyclic, bicyclic or polycyclic groups.

[0028] In the context of the present invention, aliphatic hydrocarbon radicals or alkyl radicals or alkenyl or alkynyl radicals which may contain 1 to 40 carbon atoms and in which individual hydrogen atoms or CH2 groups may also be replaced by radicals mentioned above are preferably: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, cyclooctyl, 2-ethylhexyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hexan-1-yl, 1,1-dimethyl-n-heptan-1-yl, 1,1-dimethyl-n-octan-1-yl, 1,1-dimethyl 1,1-dimethyl-n-decane-1-yl, 1,1-dimethyl-n-dodecane-1-yl, 1,1-dimethyl-n-tetradecane-1-yl, 1,1-dimethyl-n-hexadecane-1-yl, 1,1-dimethyl-n-octadecane-1-yl, 1,1-diethyl-n-hexane-1-yl, 1,1-diethyl-n-heptane-1-yl, 1,1-diethyl-n-octane-1-yl, 1,1-diethyl-n-decane-1-yl, 1,1-diethyl-n-dodecane-1-yl, 1,1-diethyl-n-tetradecane-1-yl, 1,1-diethyl-n-hexadecane-1-yl, 1,1-dimethyl-n-octadecane-1-yl, hexadecane-1-yl, 1,1-diethyl-n-octadecane-1-yl, 1-(n-propyl)-cyclohex-1-yl, 1-(n-butyl)cyclohex-1-yl, 1-(n-hexyl)cyclohex-1-yl, 1-(n-octyl)cyclohex-1-yl and 1-(n-decyl)cyclohex-1-yl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, cyclooctadienyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl radicals. Alkoxy radicals having 1 to 40 carbon atoms OR 1 Preferably, these are to be understood as meaning methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. Thioalkyl radicals SR having 1 to 40 carbon atoms 1It is to be understood as meaning in particular methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. Generally, the alkyl, alkoxy or thioalkyl group according to the present invention may be linear, branched or cyclic, wherein one or more non-adjacent CH2 groups may be replaced by the above groups; in addition, one or more hydrogen atoms may also be replaced by D, F, Cl, Br, I, CN or NO2, preferably by F, Cl or CN, more preferably by F or CN.

[0029] Aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which in each case may also be substituted by the abovementioned radicals or hydrocarbyl radicals and which may be bonded to the aromatic or heteroaromatic system via any desired position are understood to mean in particular radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, lettuce, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylylidene, terphenyl, biphenylylidene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene or radicals derived from combinations of these systems , cis- or trans-indenocarbazole, cis- or trans-indolecarbazole, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, trimerized indene, isotrimerized indene, spirotrimerized indene, spiroisotrimerized indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenazine, pyrazole, indazole, imidazole, benzimidazole, naphthyimidazole, Phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalineimidazole, oxadiazole, benzooxadiazole, naphthooxadiazole, anthraoxadiazole, phenanthroxiazole, isoxadiazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazaterphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, ruthenium ring, naphthyridine, azacarbazole , benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0030] In the context of this specification, the expression that two or more radicals together can form a ring system is understood to mean in particular that, in the case of formal elimination of two hydrogen atoms, the two radicals are connected to one another via a chemical bond. This is illustrated by the following scheme:

[0031] .

[0032] However, in addition, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group is bound to the position to which the hydrogen atom is bonded, thereby forming a ring. This will be illustrated by the following scheme:

[0033] .

[0034] Other preferred embodiments are shown in the following formulas (3) to (6):

[0035]

[0036] The symbols used therein have the definitions given above for formula (1).

[0037] In a preferred embodiment of the present invention, no more than two symbols X are N, more preferably no more than one symbol X is N in each ring.

[0038] In a preferred embodiment of the present invention, X is CR.

[0039] In a preferred embodiment, all X are CR, wherein R is H, D, F or CN.

[0040] In a preferred embodiment of the invention, Y is identical or different in each case and is CR' or N, provided that when two or more mutually adjacent Y's which are CR' together form a fused aromatic or heteroaromatic ring system, 2 or 3 Y groups in each ring are N; 1, 2 or 3 Y groups are N. For example, two CR's form a fused five-membered ring, wherein the system may also contain further aromatic or heteroaromatic rings.

[0041] Preferred embodiments of the compounds of formula (3), formula (4), formula (5) and formula (6) are the following compounds of formula (3-1) to formula (6-1):

[0042]

[0043] Where the symbol , if present, has the definitions given for equations (3) to (6).

[0044] The compounds of formula (1), formula (3), formula (4), formula (5) and formula (6) or their preferred embodiments may form a pair of enantiomers depending on the substitution. The compounds of the present invention are preferably in the form of racemates, but may also be in the form of pure enantiomers.

[0045] In a preferred embodiment, the group of formula (2) is selected from one of formula (2-1) to formula (2-9):

[0046]

[0047]

[0048]

[0049] where the symbols, if any, have the definitions given for formula (2), and Y 1 in each case the same or different and BR 1 , C(R 1 )2. NR 1 , O or S, preferably O or S, most preferably O.

[0050] In a preferred embodiment, the group of formula (2) is one of formula (2-1), formula (2-2), formula (2-3), formula (2-4) and formula (2-5).

[0051] In a preferred embodiment, the compound of the present invention is selected from one of the following compounds:

[0052]

[0053]

[0054] In a preferred embodiment, the compound of the present invention is selected from the compounds in the above table, wherein Z is one of formula (2-1), formula (2-2), formula (2-3), formula (2-4) or formula (2-5).

[0055] Preferred substituents R, Ar', R', R 1 and R 2 In a particularly preferred embodiment of the present invention, hereinafter, for R, Ar', R', R 1 and R 2 The stated preferences occur simultaneously and apply to the structure of formula (1) and all preferred embodiments detailed above.

[0056] In addition, in the case of R and R', if R or R' and the associative group contain at least one heteroaromatic ring system, the heteroaromatic ring system contains at least one nitrogen atom with three single bonds, then for each of these heteroaromatic ring systems, there are always at least two groups bonded to the corresponding nitrogen atom via single bonds and independently bonded to the basic skeleton, the single bonds being bonded to the corresponding nitrogen atom. This means that in the case where the heteroaromatic ring system has a nitrogen atom of the formula N(R'')3, wherein the R'' groups can also form a ring together and one R'' contains the basic skeleton, there are always at least two R'' groups bonded to the basic skeleton via one or more covalent bonds independent of the nitrogen atom. For example, in the case of carbazole, the two R'' groups are bonded to each other via single bonds. If the basic skeleton is part of a third group R'', the other two groups bonded to each other do not have a bond connected to the basic skeleton independently of nitrogen. If the basic skeleton is part of one of the bonded groups, each of these groups has a bond connected to nitrogen and an independent bond connected to the basic skeleton. The bond connected to the basic skeleton is a covalent bond. An independent bond means that the corresponding nitrogen is not part of a bond to the base skeleton.

[0057] Thus, from the perspective of the basic skeleton, the R or R' groups and the related groups thereon do not have nitrogen atoms, in particular as part of a heteroaromatic ring system which is bonded to the basic skeleton via only one single bond. These are in particular carbazole and its derivatives which are linked via a nitrogen atom. "Basic skeleton" refers to the fused structures in formula (1) and formula (2), for example triptycene, without R and R' groups. Thus, from the perspective of the basic skeleton, no heteroatoms are bonded to the basic skeleton via only nitrogen atoms.

[0058] In a preferred embodiment of the invention, R or R' is in each case identical or different and is selected from: H; D; F; CN; OR 1 ; a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group may be each replaced by one or more R 1 substituted with, but preferably unsubstituted with, groups and in which one or more non-adjacent CH2 groups may be replaced by O; or having 6 to 30 aromatic ring atoms and in each case by one or more R 1 At the same time, the two R or R' groups together can also form an aliphatic, aromatic or heteroaromatic ring system. More preferably, R or R' are in each case identical or different and are selected from: H; F; CN; a linear alkyl group having 1 to 6 carbon atoms, in particular 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 can be replaced by one or more R in each case. 1or having 6 to 24 aromatic ring atoms and in each case being substituted by one or more R 1 Group, preferably non-aromatic R 1 Most preferably, R or R' are in each case identical or different and are selected from: H; or a substituted aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms and in each case being substituted by one or more R 2 Group, preferably non-aromatic R 2 Aromatic or heteroaromatic ring systems substituted with radicals.

[0059] Suitable aromatic or heteroaromatic ring systems R or R' are selected from: phenyl; biphenyl, in particular o-, m- or p-biphenyl; terphenyl, in particular o-, m- or p-terphenyl or a branched terphenyl; quaterphenyl, in particular o-, m- or p-quaterphenyl or a branched quaterphenyl; fluorene, which may be attached via the 1-, 2-, 3- or 4-position; spirobifluorene, which may be attached via the 1-, 2-, 3- or 4-position; 1-, 2-, 3- or 4-position-attached naphthalene; indole; benzofuran; benzothiophene that may be attached via the 1-, 2-, 3- or 4-position; dibenzofuran; carbazole that may be attached via the 1-, 2-, 3- or 4-position; dibenzothiophene that may be attached via the 1-, 2-, 3- or 4-position; indenocarbazole; indolocarbazole; pyridine; pyrimidine; pyrazine; pyridazine; triazine; quinoline; quinazoline; benzimidazole; phenanthrene; terphenylidene; or a combination of two or three of these groups, each of which may be substituted by one or more R 1 When R is a heteroaryl group, especially triazine, pyrimidine or quinazoline, it is also preferred that the aromatic or heteroaromatic R on the heteroaryl group 1 Group.

[0060] Here, when the R or R' radicals are aromatic or heteroaromatic ring systems, they are preferably selected from the radicals of the following formulae R-1 to R-147,

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072] Where R 1 With the definitions given above, dashed bonds represent bonds to formula (1), and additionally the following definitions apply:

[0073] Ar 3 are identical or different in each case and are aromatic rings having 6 to 18 atoms and may be replaced by one or more R 1 a divalent aromatic or heteroaromatic ring system substituted with a radical;

[0074] A 1 in each case the same or different and BR 1 , C(R 1 )2. NR 1 , O or S, preferably C(R 1 )2. O or S;

[0075] A 2 are identical or different in each case and are C(R 1 )2. NR 1 , O or S;

[0076] p is 0 or 1, where p=0 means that there is no Ar 3 groups, and the corresponding aromatic or heteroaromatic groups are directly bonded to the associated atoms, such as carbon atoms, or directly bonded to heteroatoms such as nitrogen;

[0077] r is 0 or 1, where r=0 means there is no A 1 The group is bonded at this position, but R 1 The groups are bonded to the corresponding carbon atoms.

[0078] In a preferred embodiment, Ar 3 A divalent aromatic or heteroaromatic ring system comprising a group based on R-1 to R-147, wherein p=0, and the dotted bond and R 1 represents a bond to the aromatic or heteroaromatic group according to R-1 to R-147.

[0079] When the above R-1 to R-147 groups with respect to R have two or more A 1 Groups, possible options for these groups include those from A 1 In this case, the preferred embodiment is one of A1 The group is C(R 1 )2. NR 1 , O or S and the other A 1 The group is C(R 1 )2, or two A 1 The groups are all S or O, or two of them are A 1 The groups are all O or S.

[0080] When A 1 NR 1 When the substituent R bonded to the nitrogen atom 1 Preferably, the aromatic ring has 5 to 24 atoms and may be replaced by one or more R 2 In a particularly preferred embodiment, the R 1 The substituents are identical or different in each case and are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, and which do not have any fused aryl or heteroaryl groups in which two or more aromatic or heteroaromatic 6-membered ring groups are fused directly to one another and which may in each case also be replaced by one or more R 2 Particularly preferred are phenyl, biphenyl, terphenyl and quaterphenyl having bonding modes as listed above for R-1 to R-35, wherein these structures may be substituted by one or more R 1 The group is substituted, but is preferably unsubstituted.

[0081] When A 1 C(R 1 )2, the substituent R bonded to the carbon atom 1 are preferably identical or different in each case and are a straight-chain alkyl radical having 1 to 10 carbon atoms or a branched or cyclic alkyl radical having 3 to 10 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which radical or ring system may also be replaced by one or more R 2 Most preferably, R 1 is a methyl group or a phenyl group. In this case, R 1 The groups together may also form a ring system, thereby giving rise to a spiro ring system.

[0082] In a preferred embodiment of the invention, R' is identical or different in each case and is selected from: D; F; CN; OR 1 ; and having 6 to 30 aromatic ring atoms and in each case may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0083] Most preferably, R' is identical or different in each occurrence and is selected from: D; F; CN; or a cyclopentane radical having 6 to 24 aromatic ring atoms, more preferably 6 to 12 aromatic ring atoms and which may be replaced in each occurrence by one or more R 1 Group, preferably non-aromatic R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0084] Suitable aromatic or heteroaromatic ring systems R' are selected from: phenyl; biphenyl, in particular o-, m- or p-biphenyl; terphenyl, in particular o-, m- or p-terphenyl or a branched terphenyl; quaterphenyl, in particular o-, m- or p-quaterphenyl or a branched quaterphenyl; fluorene, which may be attached via the 1-, 2-, 3- or 4-position; spirobifluorene, which may be attached via the 1-, 2-, 3- or 4-position; pyrofluorene, which may be attached via the 1-, 2-, 3- or 4-position; naphthalene; indole; benzofuran; benzothiophene which may be attached via the 1, 2, 3 or 4 position; dibenzofuran; carbazole which may be attached via the 1, 2, 3 or 4 position; dibenzothiophene which may be attached via the 1, 2, 3 or 4 position; indenocarbazole; indolocarbazole; pyridine; pyrimidine; pyrazine; pyridazine; triazine; quinoline; quinazoline; benzimidazole; phenanthrene; terphenylidene; or a combination of two or three of these groups, each of which may be substituted by one or more R 1 When R' is a heteroaryl group, especially triazine, pyrimidine or quinazoline, it is also preferred that the aromatic or heteroaromatic R on the heteroaryl group 1 Group.

[0085] In this case, when the R' groups are aromatic or heteroaromatic ring systems, they are preferably selected from the groups of formula R-1 to R-147 above, more preferably selected from the groups of formula R-1 to R-147 above, wherein A 1 C(R 1 )2. O or S.

[0086] In another preferred embodiment of the present invention, R which is not bonded to a quaternary carbon atom of the basic skeleton 1 are identical or different in each case and are selected from H; D; F; CN; OR 2 a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group may in each case be replaced by one or more R 2 or having 6 to 30 aromatic ring atoms and in each case being replaced by one or more R 2 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two or more R 1The groups together can form an aliphatic ring system. In a particularly preferred embodiment of the present invention, R 1 are in each case identical or different and are selected from: H; a linear alkyl group having 1 to 6 carbon atoms, in particular 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl group may be replaced by one or more R 2 or having 6 to 24 aromatic ring atoms and in each case being substituted by one or more R 2 The aromatic or heteroaromatic ring system may be substituted with R, but is preferably unsubstituted.

[0087] In another preferred embodiment of the present invention, R 2 are in each case identical or different and are H; F; an alkyl radical having 1 to 4 carbon atoms or an aryl radical having 6 to 10 carbon atoms, which may be substituted by an alkyl radical having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0088] In another preferred embodiment of the present invention, if R 1 If the group is an aromatic or heteroaromatic ring system, 2 If the group is an aromatic or heteroaromatic group, all R 1 Group or R 2 The groups are selected from the groups R-1 to R-147, however, in this case, these groups are correspondingly replaced by R 2 Replaced by, or replaced by 2 The mentioned groups are substituted.

[0089] In a preferred embodiment of the present invention, R, R', R 1 or R 2 All aromatic or heteroaromatic groups of the group are selected from the corresponding R-1 to R-147 groups, preferably selected from R-1 to R-147 groups, wherein A 1 O, S or C (R 1 )2, or the corresponding C(R 2 )2 or C(R 3 )2 group.

[0090] In a preferred embodiment, the R groups do not form any further aromatic or heteroaromatic groups which are fused to the basic skeleton of formula (1).

[0091] In a preferred embodiment of the invention, R is identical or different in each case and is H; D; F; CN; or a group selected from the group consisting of R-1 to R-147, and R of these groups 1 is H, D, F or CN; preferably R-1 to R-47 and R-104 to R-110 groups.

[0092] In a preferred embodiment, R is in each case identical or different in all rings of the compounds of the formula (1) and is H, D, F or CN, preferably H or D.

[0093] In a preferred embodiment, the ring together with Y and optionally together with the R' group forms a group selected from the following: R-70, R-71, R-72, R-73, R-74, R-75, R-76, R-80, R-81, R-113, R-133, R-134, R-135, R-136, R-145, R-146, R-147 groups, wherein p is 0.

[0094] In another embodiment of the present invention, R bonded to the quaternary carbon atom of the basic skeleton 1 The group is H; D; F; CN; OR 2 a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group may in each case be replaced by one or more R 2 or having 5 to 30 aromatic ring atoms and in each case being replaced by one or more R 2 A heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups together can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system.

[0095] The R 1 Preferably on a bridging group selected from the groups R-1 to R-147, provided that they are R 2 substituted, more preferably on a bridging group selected from the group consisting of R-1 to R-147, provided that they are replaced by R 2 Replace and A 1 C(R 2 )2. O or S.

[0096] In a preferred embodiment, R′ in the radicals of formula (2-1) to formula (2-9) is in each case identical or different and is a radical having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms and which can be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with R groups, wherein two or more R groups, preferably bonded to the same ring, can together form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which can be substituted with one or more R groups. 1 The radicals are preferably identical or different in each case and are selected from R-1 to R-147. Preferably, in this case, R 1The radical is H; D; F; CN; or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be replaced by D or F; at the same time, two or more R 1 The substituents may be connected to each other and may form a ring.

[0097] In one embodiment of the invention, R' in formula (2) or R' in one of formula (2-1) to formula (2-9) is identical or different in each case and is a group selected from R-1, R-2, R-3, R-44, R-45, R-46, R-47, R-112, R-114. In a preferred embodiment, in the case of multiple R' groups, at least one group is R-1, and at least another R' group is selected from R-2, R-3, R-44, R-45, R-46, R-47, R-112, R-114. In the case of three R' groups, one group can also be CN.

[0098] At the same time, the alkyl groups in the compounds of the invention processed by vacuum evaporation preferably have no more than five carbon atoms, more preferably no more than 4 carbon atoms, and most preferably no more than 1 carbon atom. With regard to compounds processed from solution, suitable compounds are also compounds substituted with alkyl groups having up to 10 carbon atoms, especially branched alkyl groups, or with oligomeric arylene groups such as o-terphenyl, m-terphenyl, p-terphenyl or branched terphenyl or quaterphenyl groups.

[0099] The above preferred embodiments can be combined with each other as needed within the limits defined in claim 1. In a particularly preferred embodiment of the present invention, the above preferred items appear simultaneously.

[0100] Examples of preferred compounds according to the above detailed embodiments are the compounds detailed in the following table:

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] The compounds of the present invention can be prepared by synthetic procedures known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Heck reaction, Hartwig-Buchwald coupling, and the like.

[0113] Therefore, the present invention also provides a method for preparing the compound of the present invention, characterized by the following steps:

[0114] (A) synthesizing a fused basic skeleton of formula (1);

[0115] (B) Introduction of aromatic or heteroaromatic groups at the bridge atoms by coupling reactions.

[0116] Therefore, the compounds of the present invention can be prepared starting from bicyclic systems known in the literature, which are brominated or iodinated at the bridgehead carbon atom according to M. Oi et al., Chem. Sci., 2019, 10, 6107. This is shown in Schemes 1 and 2, taking triptycene as an example. In step 1, the bridgehead carbon atom is first lithiated by reaction of bromide with n-butyllithium, followed by transmetallation with copper(I) halide, preferably CuCl, and then palladium-catalyzed CC coupling with, for example, halogenated heteroaromatic compounds such as 2-chlorotriazine, 2-chloropyrimidine or 4-chloropyrimidine, 2-chloropyrazine, 2-quinazoline, 2-quinoxaline, 2-chloro-benzofurano[2,3-d]pyrimidine, 2-chlorobenzofurano[3,2-d]pyrimidine, 2-chloro[1]benzothieno[2,3-d]pyrimidine, 2-chloro[1]benzothieno-[3,2-d]pyrimidine, etc. The heteroaromatic compound here corresponds to the group containing Y in formula (1). Similarly, the corresponding brominated or iodinated heteroaromatic compounds can be used. The phosphine compound used is preferably an electron-rich phosphine compound, such as tri(o-tolyl)phosphine, tri(o-methoxyphenyl)phosphine, tricyclohexylphosphine, tri-tert-butylphosphine or S-Phos, X-Phos, RuPhos, Amphos, etc. When a relatively unreactive chlorinated heteroaromatic compound is used, activation can be performed by adding a stoichiometric amount of anhydrous lithium bromide or lithium iodide.

[0117] Scenario 1:

[0118]

[0119] 9,10-Dibromotriptycene can be selectively monolithiated (see G. Märkl et al., Tetrahedron Lett., 1974, 20, 1817) and then coupled with the first Hal-HetAr as described above. HetAr here corresponds to the group containing Y in formula (1). In a second step, the remaining Br function can be coupled with another halogenated aromatic compound Hal-Ar or a halogenated heteroaromatic compound Hal-HetAr, so that symmetrical and asymmetrical 9,10-substituted triptycenes can be obtained; see Scheme 2.

[0120] Scenario 2:

[0121] In order to process the compounds of the present invention from the liquid phase, for example by spin coating or by printing methods, preparations of the compounds of the present invention are required. These preparations can be, for example, solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents can preferably be used. Suitable and preferred solvents are, for example: toluene; anisole; o-, m- or p-xylene; methyl benzoate; mesitylene; tetralin; o-dimethoxybenzene; THF; methyl-THF; THP; chlorobenzene; dioxane; phenoxytoluene, especially 3-phenoxytoluene; (-)-fennel; 1,2,3,5-tetramethylbenzene; 1,2,4,5-tetramethylbenzene; 1-methylnaphthalene; 2-methylbenzothiazole; 2-phenoxyethanol; 2-pyrrolidone; 3-methylanisole; 4-methylanisole; 3,4-dimethylanisole; 3,5-dimethylanisole; acetophenone; α-terpineol; benzothiazole; butyl benzoate; isopropylbenzene; cyclohexanol ; cyclohexanone; cyclohexylbenzene; decalin; dodecylbenzene; ethyl benzoate; indane; NMP; p-cymene; phenethyl ether; 1,4-diisopropylbenzene; dibenzyl ether; diethylene glycol butyl methyl ether; triethylene glycol butyl methyl ether; diethylene glycol dibutyl ether; triethylene glycol dimethyl ether; diethylene glycol monobutyl ether; tripropylene glycol dimethyl ether; tetraethylene glycol dimethyl ether; 2-isopropylnaphthalene; pentylbenzene; hexylbenzene; heptylbenzene; octylbenzene; 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl; 3-methylbiphenyl; 1-methylnaphthalene; 1-ethylnaphthalene; ethyl octanoate; diethyl sebacate; octyl octanoate; heptylbenzene; menthyl isovalerate; cyclohexyl hexanoate; or a mixture of these solvents.

[0122] Therefore, the present invention also provides a kind of preparation, especially solution, dispersion or emulsion, described preparation comprises at least one compound of the present invention and at least one other compound.Described other compound can be for example solvent, especially one or the mixture of these solvents in the above-mentioned solvent.The manufacture of this solution is known to those skilled in the art and is described for example in WO2002 / 072714, WO 2003 / 019694 and the document cited therein.Described other compound can also be at least one other organic or inorganic compound used in electronic device equally, for example luminescent compound and / or matrix material.This other compound can also be polymer.

[0123] The compounds according to the invention are suitable for use in electronic devices, in particular in organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds can be used in different functions and layers.

[0124] Therefore, the present invention also provides the use of the compounds according to the invention in electronic devices.

[0125] The present invention also provides an electronic device comprising at least one compound according to the present invention.

[0126] The compounds according to the invention can be used in particular in the form of racemates or in the form of the pure enantiomers.

[0127] An electronic device in the context of the present invention is a device comprising at least one layer comprising at least one organic compound. The component may also comprise further layers of inorganic materials or be formed completely from inorganic materials.

[0128] The electronic device is preferably selected from: organic electroluminescent device (OLED), organic integrated circuit (O-IC), organic field effect transistor (O-FET), organic thin film transistor (O-TFT), organic light emitting transistor (O-LET), organic solar cell (O-SC), dye-sensitized organic solar cell (DSSC), organic optical detector, organic photoreceptor, organic field quenching device (O-FQD), light emitting electrochemical cell (LEC), organic laser diode (O-laser) and organic plasma light emitting device, but preferably an organic electroluminescent device (OLED).

[0129] The device is more preferably an organic electroluminescent device comprising an anode, a cathode and at least one emitting layer, wherein at least one organic layer which may be a emitting layer, a hole transport layer, an electron transport layer, a hole blocking layer, an electron blocking layer or other functional layer comprises at least one compound of the invention. The layers depend on the substitution of the compound.

[0130] In addition to these layers, the organic electroluminescent device may also comprise further layers, for example, in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers and / or organic or inorganic p / n junctions. It is also feasible to introduce an interlayer, for example, having an exciton blocking function, between two emitting layers. However, it should be noted that each of these layers does not necessarily have to be present.

[0131] In this case, the organic electroluminescent device may comprise one luminescent layer, or it may contain a plurality of luminescent layers. If a plurality of luminescent layers are present, these luminescent layers preferably have a plurality of luminescent maxima between 380 nm and 750 nm, so that the overall result is white luminescence; in other words, a variety of luminescent compounds that can emit fluorescence or phosphorescence are used in the luminescent layer. Particularly preferred is a system with three luminescent layers, wherein the three layers show blue, green and orange or red luminescence (for example, the basic structure is described in WO 2005 / 011013). The organic electroluminescent device of the present invention may also be a tandem OLED, in particular an OLED for emitting white light.

[0132] The compounds of the formula (1) are preferably employed in organic electroluminescent devices which comprise one or more phosphorescent emitters.The compounds according to the invention according to the above-mentioned embodiments can be employed in different layers, depending on the exact structure.

[0133] In this case, the organic electroluminescent device may contain one emitting layer, or it may contain a plurality of emitting layers, wherein at least one layer contains at least one compound of the present invention. In addition, the compounds of the present invention may also be used in electron transport layers and / or hole blocking layers and / or hole transport layers and / or exciton blocking layers.

[0134] The expression "phosphorescent compound" generally refers to a compound which emits light via a spin-forbidden transition, for example a transition from an excited triplet state or a state with a higher spin quantum number, such as a quintet state.

[0135] Suitable phosphorescent compounds (=triplet emitters) are especially compounds which emit light, preferably in the visible region, when suitably excited, and further comprise 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. Preferred phosphorescent compounds are all luminescent complexes with transition metals or lanthanides, especially when they comprise copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds comprising iridium, platinum or copper. In the context of the present invention, all luminescent iridium, platinum or copper complexes are regarded as phosphorescent emitting compounds.

[0136] Examples of such emitters can be found in the following applications: WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626、WO 2011 / 066898、WO 2011 / 157339、WO 2012 / 007086、WO 2014 / 008982、WO 2014 / 023377、WO 2014 / 094961、WO 2014 / 094960、WO 2015 / 036074、WO 2015 / 104045、WO 2015 / 117718、WO 2016 / 015815、WO 2016 / 124304、WO 2017 / 032439、WO 2018 / 011186、WO 2018 / 041769、WO 2019 / 020538、WO 2018 / 178001, WO 2019 / 115423 and WO 2019 / 158453. In general, all phosphorescent complexes for phosphorescent OLEDs known to those skilled in the art in the field of organic electroluminescence are suitable, and those skilled in the art can use other phosphorescent complexes without creative work. Those skilled in the art can combine other phosphorescent complexes with compounds of formula (1) for use in organic electroluminescent devices without creativity. Other examples are listed in the following table.

[0137] According to the present invention, the compounds of formula (1) can also be used in electronic devices containing one or more fluorescent light-emitting compounds.

[0138] In a preferred embodiment of the present invention, the compound of formula (1) is used as an electron transport material. In this case, the compound is preferably present in an electron transport layer or a hole blocking layer, or in an electron conductive or bipolar host material. It is particularly preferably used in an electron transport layer.

[0139] In the context of the present application, an electron transport layer is a layer having an electron transport function between the cathode and the light emitting layer.

[0140] In the context of the present application, electron injection layer and hole blocking layer are understood to refer to specific embodiments of electron transport layers. In the case of multiple electron transport layers between the cathode and the light-emitting layer, the electron injection layer is an electron transport layer, which is directly adjacent to the cathode or is separated from it only by a single coating of the cathode. In the case of multiple electron transport layers between the cathode and the light-emitting layer, the hole blocking layer is an electron transport layer, which is directly adjacent to the light-emitting layer on the cathode side. The OLED of the present invention preferably comprises two, three or four electron transport layers between the cathode and the light-emitting layer, wherein preferably at least one, more preferably exactly one or two, contain a compound of formula (1).

[0141] If the compound of formula (1) is used as an electron transport material in an electron transport layer, electron injection layer or hole blocking layer, the compound may be used as a pure material in the electron transport layer, i.e., in a proportion of 100%, or may be used in combination with one or more other compounds.

[0142] The hole transport layer or electron blocking layer of the electronic device of the invention may additionally comprise one or more p-type dopants. The p-type dopants used according to the invention are preferably those organic electron acceptor compounds which are able to oxidize one or more other compounds in the mixture.

[0143] Particularly preferred embodiments of p-dopants are the compounds disclosed in WO 2011 / 073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE102007031220, US 8044390, US 8057712, WO 2009 / 003455, WO 2010 / 094378, WO 2011 / 120709, US 2010 / 0096600, WO 2012 / 095143 and DE 102012209523.

[0144] Particularly preferred p-type dopants are the following substances: quinone dimethane compounds; azaindenofluorenediones; azaperibenzonaphthalene; azaterphenylidene; I2; metal halides, preferably transition metal halides; metal oxides, preferably metal oxides containing at least one transition metal or a metal of the third main group; and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd and Pt with ligands containing at least one oxygen atom as a bonding site. As dopants, transition metal oxides are also preferred, preferably oxides of rhenium, molybdenum and tungsten, more preferably Re2O7, MoO3, WO3 and ReO3.

[0145] The p-type dopant is preferably substantially uniformly dispersed in the p-doped layer. This can be achieved, for example, by co-evaporation of the p-type dopant and the hole transport material matrix.

[0146] Preferred p-type dopants are in particular the following compounds:

[0147]

[0148] The hole-transport materials used can be used in combination with hexaazaterphenylidene derivatives as described in US 2007 / 0092755. Particular preference is given here to hexaazaterphenylidene derivatives used in a separate layer.

[0149] In a further embodiment of the invention, the compounds of the formula (1) are employed in an emitting layer as matrix material in combination with one or more emitting compounds, preferably phosphorescent compounds.

[0150] In this case, the proportion of the matrix material in the light-emitting layer is between 50.0% and 99.9% by volume, preferably between 80.0% and 99.5% by volume, more preferably between 92.0% and 99.5% by volume for the fluorescent light-emitting layer, and between 85.0% and 97.0% by volume for the phosphorescent light-emitting layer.

[0151] Accordingly, the proportion of the luminescent compound is between 0.1% and 50.0% by volume, preferably between 0.5% and 20.0% by volume, more preferably between 0.5% and 8.0% by volume for the fluorescent luminescent layer, and between 3.0% and 15.0% by volume for the phosphorescent luminescent layer.

[0152] The light-emitting layer of the organic electroluminescent device can also include a system containing multiple host materials (mixed host system) and / or multiple luminescent compounds. In this case, usually, the luminescent compound is also a compound with a smaller ratio in the system, and the host material is a compound with a larger ratio in the system. However, in individual cases, the ratio of a single host material in the system can be less than the ratio of a single luminescent compound.

[0153] The compound of formula (1) is preferably used as a component of a mixed matrix system. The mixed matrix system is preferably composed of two or three different matrix materials, more preferably composed of two different matrix materials. Preferably, in this case, one of the two materials is a material with hole transport properties, and the other material is a material with electron transport properties. The compound of formula (1) is preferably a matrix material with electron transport properties. However, the required electron transport and hole transport properties of the mixed matrix component can also be mainly or completely combined in a single mixed matrix component, in which case the additional mixed matrix component performs other functions. Two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, most preferably 1:4 to 1:1. Preferably, a mixed matrix system is used in a phosphorescent organic electroluminescent device. More detailed information about the mixed matrix system comes from the application WO 2010 / 108579.

[0154] Mixed-matrix systems can comprise one or more emitting compounds, preferably one or more phosphorescent compounds.In general, preference is given to using mixed-matrix systems in phosphorescent organic electroluminescent devices.

[0155] Particularly suitable matrix materials which can be used in combination with the compounds according to the invention as matrix components of mixed-matrix systems are selected, depending on the type of emitting compound used in the mixed-matrix system, from the preferred matrix materials specified below for phosphorescent compounds or for fluorescent compounds.

[0156] Preferred phosphorescent compounds for use in mixed-matrix systems are the same as the generally preferred phosphorescent emitter materials described above.

[0157] Preferred embodiments of different functional materials in electronic devices are listed below.

[0158] Examples of phosphorescent compounds are listed below.

[0159]

[0160]

[0161]

[0162]

[0163] Preferred fluorescent luminescent compounds are selected from arylamines. In the context of the present invention, arylamines or aromatic amines are understood to be compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic leucine or aromatic leucine diamines. Aromatic anthracene amines are understood to refer to compounds in which one diarylamino group is directly bonded to an anthracene group, preferably a compound bonded at the 9 position. Aromatic anthracene diamines are understood to refer to compounds in which two diarylamino groups are directly bonded to anthracene groups, preferably compounds bonded at the 9 position and the 10 position. Aromatic pyrene amines, pyrene diamines, leucine and leucine diamines are similarly defined, wherein the diarylamino groups are preferably bonded to pyrene at the 1 position or at the 1 position and the 6 position. Further preferred emitting compounds are the following substances: indenofluorenamine or fluorenediamine, for example according to WO 2006 / 108497 or WO 2006 / 122630; benzindenofluorenamine or benzindenofluorenediamine, for example according to WO 2008 / 006449; and dibenzoindenofluorenamine or dibenzoindenofluorenediamine, for example according to WO 2007 / 140847; and indenofluorene derivatives with fused aryl groups disclosed in WO 2010 / 012328. Also preferred are the pyrenarylamines disclosed in WO 2012 / 048780 and WO 2013 / 185871. Likewise preferred are the benzindenofluoreneamines disclosed in WO 2014 / 037077, the benzofluoreneamines disclosed in WO 2014 / 106522, the extended benzindenofluorenes disclosed in WO 2014 / 111269 and in WO 2017 / 036574, the phenoxazine disclosed in WO 2017 / 028940 and WO 2017 / 028941 and the fluorene derivatives bonded to furan units or thiophene units disclosed in WO 2016 / 150544. In addition, boron compounds according to WO2020208051, WO2015102118, WO2016152418, WO2018095397, WO2019004248, WO2019132040, US20200161552, WO2021089450 may also be used.

[0164] Useful matrix materials preferably for fluorescent compounds include materials from different classes of substances. Preferred matrix materials are selected from the following classes of substances: oligomeric aromatic compounds (e.g. 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461, or dinaphthyl anthracene), in particular oligomeric aromatic compounds with fused aromatic groups; oligomeric arylidene vinylidene compounds (e.g. DPVBi or spiro-DPVBi according to EP 676461); polypodal metal complexes (e.g. according to WO 2004 / 081017); hole-conducting compounds (e.g. according to WO 2004 / 058911); electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides and the like (e.g. according to WO 2005 / 084081 and WO 2005 / 084082); atropisomers (e.g. according to WO 2006 / 048268); boronic acid derivatives (e.g. according to WO 2006 / 117052); or benzanthracene (for example according to WO 2008 / 145239). Particularly preferred matrix materials are selected from the classes of oligoarylidenes with naphthalene, anthracene, benzanthracene and / or pyrene, or atropisomers of these compounds; oligoarylidene vinylidene compounds; ketones; phosphine oxides; and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylidenes with anthracene, benzanthracene, terphenylidene and / or pyrene, or atropisomers of these compounds. An oligoaryl in the context of the present invention is to be taken to mean a compound in which at least three aryl or arylidene groups are bonded to one another. Also preferred are the following: anthracene derivatives disclosed in WO 2006 / 097208, WO 2006 / 131192, WO 2007 / 065550, WO 2007 / 110129, WO 2007 / 065678, WO 2008 / 145239, WO 2009 / 100925, WO 2011 / 054442 and EP 1553154; pyrene compounds disclosed in EP1749809, EP 1905754 and US 2012 / 0187826; benzanthrylanthracene compounds disclosed in WO 2015 / 158409; indenobenzofuran compounds disclosed in WO 2017 / 025165; and phenanthracene compounds disclosed in WO 2017 / 036573.

[0165] Preferred matrix materials for phosphorescent compounds such as compounds of formula (1) are: aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or aromatic sulfones, for example according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680; triarylamines, carbazole derivatives, for example CBP (N,N-dicarbazolylbiphenyl) or those of WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176; indolocarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 056746; indolocarbazole derivatives, for example according to WO 2010 / 136109, WO2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160; bipolar matrix materials, for example according to WO 2007 / 137725; silanes, for example according to WO 2005 / 111172; borazolidines or boric acid esters, for example according to WO 2006 / 117052; for example according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO triazine derivatives according to WO 2011 / 060859 or WO 2011 / 060877; zinc complexes according to EP 652273 or WO 2009 / 062578; siladiazolidine or siladiazolidine derivatives according to WO 2010 / 054729; phosphodiazolidine derivatives according to WO 2010 / 054730; bridged carbazole derivatives according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080; terphenylidene derivatives according to WO 2012 / 048781; lactams according to WO 2011 / 116865 or WO 2011 / 137951; or Dibenzofuran derivatives of WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565.Other phosphorescent emitters having a shorter emission wavelength than the actual emitter may likewise be present as cohosts in the mixture, or compounds which participate in charge transport but not to a significant extent, as described, for example, in WO 2010 / 108579.

[0166] Suitable charge transport materials that can be used in the hole injection layer or hole transport layer or electron blocking layer or electron transport layer of the electronic component of the present invention include, in addition to the compounds of formula (1), for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010 or other materials used in these layers according to the prior art.

[0167] The material used for the hole transport layer may be any material used as a hole transport material in the hole transport layer according to the prior art. An aromatic amine compound may be used. Other compounds which are preferably used in the hole-transporting layer of the OLED according to the invention are, in particular: indenofluoreneamine derivatives (for example according to WO 06 / 122630 or WO 06 / 100896), amine derivatives disclosed in EP 1661888, hexaazaterphenylidene derivatives (for example according to WO 01 / 049806), amine derivatives with condensed aromatics (for example according to US Pat. No. 5,061,569), amine derivatives disclosed in WO 95 / 09147, monobenzoindenofluoreneamine (for example according to WO 08 / 006449), dibenzoindenofluoreneamine (for example according to WO 07 / 140847), spirobifluoreneamine (for example according to WO 2012 / 034627 and WO 2013 / 120577), fluoreneamine (for example according to WO 2004 / 015937, WO 2014 / 015938, WO 2014 / 015935 and WO 2015 / 082056), spirodibenzopyranamines (for example according to WO 2013 / 083216), dihydroacridine derivatives (for example according to WO 2012 / 150001), spirodibenzofurans and spirodibenzothiophenes (for example according to WO 2015 / 022051, WO 2016 / 102048 and WO 2016 / 131521), phenanthrenyl diarylamines (for example according to WO 2015 / 131976), spirotribenzophenones (for example according to WO 2016 / 087017), spirobifluorenes with meta-phenylenediamine groups (for example according to WO2016 / 078738), spirobiacridines (for example according to WO2015 / 158411), xanthene diarylamines (for example according to WO2014 / 072017) and 9,10-dihydroanthracenspiro compounds with diarylamino groups according to WO2015 / 086108.

[0168] Very particular preference is given to using spirobifluorenes substituted in the 4-position by a diarylamino group as hole-transport compounds, in particular those compounds claimed and disclosed in WO 2013 / 120577, and spirobifluorenes substituted in the 2-position by a diarylamino group as hole-transport compounds, in particular those compounds claimed and disclosed in WO 2012 / 034627.

[0169] The OLED of the present invention preferably comprises two or more different electron transport layers. The compound of formula (1) can be used in one or more or all of the electron transport layers here. In a preferred embodiment, the compound of formula (1) is used in exactly one or exactly two electron transport layers, and other compounds are used in other electron transport layers present. Other compounds that can be used with the compound of formula (1) are any materials used as electron transport materials in the electron transport layer according to the prior art. Particularly suitable are aluminum complexes such as Alq3, zirconium complexes such as Zrq4, lithium complexes such as Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, phosphodiazocyclopentane derivatives and phosphine oxide derivatives. Further suitable materials are derivatives of the above compounds, as disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975 and WO 2010 / 072300.

[0170] The preferred cathode of the electronic component is a metal with a low work function, a metal alloy or a multilayer structure comprising various metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (such as Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). In addition, it is suitable to be an alloy consisting of an alkali metal or alkaline earth metal and silver, such as an alloy consisting of magnesium and silver. In the case of a multilayer structure, in addition to the metals mentioned, other metals such as Ag or Al with a relatively high work function can also be used, wherein a combination of the metals is generally used, such as Ca / Ag, Mg / Ag or Ba / Ag. It is also advantageous to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of suitable materials are alkali metal fluorides or alkaline earth metal fluorides, and corresponding oxides or carbonates (such as LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). For this purpose, lithium quinoline (LiQ) can also be used. The layer thickness of this layer is preferably between 0.5 nm and 5 nm.

[0171] Preferred anodes are materials with a high work function. The anode preferably has a work function greater than 4.5 eV relative to vacuum. Firstly, for this purpose, metals with a high redox potential are suitable, such as Ag, Pt or Au. Secondly, metal / metal oxide electrodes (such as Al / Ni / NiO x 、Al / PtO x ). For some applications, at least one of the electrodes must be transparent or partially transparent in order to be able to illuminate the organic material (organic solar cells) or emit light (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of two or more layers, for example of an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0172] The device is appropriately structured (depending on the application), contact-connected and finally sealed to eliminate the harmful effects of water and air.

[0173] In 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 use any known material for organic electroluminescent devices in combination with the compound of formula (1) of the present invention or the above preferred embodiments without creative work.

[0174] Furthermore, an organic electroluminescent device is preferred, characterized in that one or more layers are applied by a sublimation process. In this case, the organic electroluminescent device is applied by sublimation in a vacuum sublimation system at a temperature of less than 10 -5 mbar, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of 10 mbar. However, even lower pressures, such as less than 10 -7 Initial pressures of millibars are also possible.

[0175] Likewise preferred is an organic electroluminescent device, characterized in that one or more layers are applied by OVPD (organic vapor phase deposition) or by means of carrier gas sublimation. -5 The material is applied at a pressure of mbar to 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and is thereby structured.

[0176] Additionally preferred is an organic electroluminescent device, characterized in that one or more layers are produced from solution, for example by spin coating, or by any printing method such as screen printing, flexographic printing, lithographic printing, LITI (light-induced thermography, thermal transfer), inkjet printing or nozzle printing. For this purpose, soluble compounds, obtained for example by appropriate substitution, are required.

[0177] Furthermore, hybrid processes are possible in which, for example, one or more layers are applied from solution and one or more other layers are applied by vapor deposition.

[0178] The person skilled in the art is generally aware of these processes and is able to apply them without inventive step to organic electroluminescent devices comprising the compounds according to the invention.

[0179] According to the invention, electronic devices containing one or more compounds of the formula (1) can be used in displays, as light sources in lighting applications and as light sources in medical and / or cosmetic applications (eg phototherapy).

[0180] The compounds according to the invention and the organic electroluminescent devices according to the invention are notable for one or more of the following surprising properties:

[0181] 1. The compounds of the present invention induce longevity.

[0182] 2. The compounds according to the invention lead to high efficiencies, especially high EQEs.

[0183] 3. The compounds of the present invention cause low operating voltage.

[0184] The present invention is illustrated in detail by the following examples, but it is not intended to limit the present invention thereby. Those skilled in the art will be able to use the information provided to implement the present invention within the entire disclosed range, and to prepare more compounds of the present invention without inventive effort, and use them in electronic devices or adopt the methods of the present invention. Example

[0185] Unless otherwise indicated, the following syntheses were carried out in dry solvents under a protective gas atmosphere. Metal complexes were additionally protected from light or handled under yellow light. Solvents and reagents can be derived from, for example, Sigma-ALDRICH or ABCR. The corresponding numbers in square brackets or the numbers quoted for individual compounds are related to the CAS numbers of compounds known in the literature. In the case of compounds that can have multiple enantiomers, diastereomers or tautomeric forms, one form is shown in a representative manner.

[0186] Synthon LS known from the literature:

[0187]

[0188]

[0189] A) Synthesis of Compound B and Synthon S of the Invention:

[0190] Embodiment B1:

[0191]

[0192] Variant A: via organolithium compounds

[0193] To a solution of 3.3 g (10 mmol) LS1 in a mixture of 100 ml THF and 150 ml toluene cooled to -78 ° C, 4.0 ml (10.5 mmol) n-BuLi (2.6 mol in n-hexane) were added dropwise over 30 minutes and the mixture was stirred for a further 1.5 hours. A solution of 2.8 g (10.5 mmol) 2-chloro-4,6-diphenyl-1,3,5-triazine [3842-55-5] in 100 ml THF was added dropwise, the reaction mixture was stirred for a further 30 minutes, then gradually warmed to room temperature and stirred for a further 2 hours. 2 ml of water were added with thorough stirring, the reaction mixture was concentrated to dryness, the residue was extracted with 30 ml of methanol with stirring and chromatographed (Torrent, automated column system from A. Semrau). Further purification was achieved in each case by repeated hot extractive crystallization (common organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1, volume:volume) and fractional sublimation or thermal treatment under high vacuum. Yield: 1.7 g (3.4 mmol), 34%; purity: about 99.9% according to HPLC.

[0194] Variant B: Via organocopper compounds

[0195] The process was carried out according to M. Oi et al., Chem. Sci., 2019, 10, 6107, Example 16.

[0196] Starting material: 33.3 g (100 mmol) LS1, 39.5 g (110 mmol) 2-iodo-4,6-diphenyl-1,3,5-triazine [83819-97-0], in a stirred autoclave at 140° C. for 35 h. Further purification is achieved in each case by chromatography and / or repeated hot extractive crystallization (common organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1, volume:volume) and fractional sublimation or thermal treatment under high vacuum. Yield: 34.3 g (71 mmol), 71%; purity: about 99.9% according to HPLC.

[0197] The following compounds can be prepared analogously: Unless otherwise stated, variant B is used hereinafter. The yields of chlorides are generally in the range of 30% to 70%, the yields of bromides are generally in the range of 50% to 80%, and the yields of iodides are generally in the range of 60% to 90%.

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[0248] Example: Fabrication of OLEDs

[0249] 1) Vacuum treated devices:

[0250] The OLEDs according to the invention and the OLEDs according to the prior art are produced by the general process according to WO 2004 / 058911, adapted to the circumstances described here (variation of layer thicknesses, materials used).

[0251] In the following examples, the results of various OLEDs are presented. Clean glass plates coated with structured ITO (indium tin oxide) with a thickness of 50 nm (cleaned in a Miele laboratory glass washer, Merck Extran detergent) were pretreated with UV ozone for 25 minutes (UVP PR-100 UV ozone generator). These coated glass plates formed the substrate for the application of the OLEDs.

[0252] 1a) Blue Fluorescent OLED Component - BF:

[0253] Compound B of the present invention can be used in electron transport layer (ETL) and hole blocking layer (HBL). All materials are applied by thermal vapor deposition in a vacuum chamber. The light-emitting layer (EML) here is always composed of at least one matrix material (host material) SMB (see Table 1) and a light-emitting dopant (dopant, luminophore) D, which is added to the matrix material by co-evaporation in a specific volume ratio. The detailed information given in the form of SMB: D (97: 3%) means that the material SMB is present in the layer at a volume ratio of 97%, and the dopant D is present in the layer at a volume ratio of 3%. Similarly, the electron transport layer is also composed of a mixture of two materials; see Table 1. The materials used to manufacture OLEDs are shown in Table 5.

[0254] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum was determined, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in %) were calculated as a function of the luminous density from the current-voltage-luminous density characteristic (IUL characteristic) assuming Lambertian luminescence behavior, and the lifetime was also determined. 2 The EQE in % and the voltage in V are reported at a luminous density of 1000 cd / m 2The lifetime is determined at an initial luminous density of . The measurement period in which the reference brightness drops to 90% of the initial brightness is set as 100%. The lifetime of the OLED component containing compound B according to the invention is reported as a percentage relative to the reference.

[0255] OLEDs have the following layer structure:

[0256] Base

[0257] Hole injection layer (HIL) consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0258] Hole transport layer (HTL) composed of HTM1, 160 nm

[0259] Electron blocking layer (EBL) composed of EBM1, 10 nm

[0260] Emission layer (EML), see Table 1

[0261] Hole blocking layer (HBL), see Table 1

[0262] Electron transport layer (ETL), see Table 1

[0263] Electron injection layer (EIL) composed of ETM2, 1 nm

[0264] Cathode made of aluminum, 100 nm

[0265] Table 1: Structure of blue fluorescent OLED components

[0266]

[0267] Table 2: Results of blue fluorescent OLED components

[0268]

[0269] 1b) Phosphorescent OLED components:

[0270] Compound B of the present invention can be used as a matrix material (host material) in an electron transport layer (ETL), a hole blocking layer (HBL) and an emitting layer (EML). For this purpose, all materials are applied by thermal vapor deposition in a vacuum chamber. The emitting layer here is always composed of at least one or more than one matrix material M and a phosphorescent dopant Ir, which is added to the matrix material in a specific volume ratio by co-evaporation. Details given in the form of, for example, M1:M2:Ir (55%:35%:10%) refer here to: material M1 is present in the layer at a volume ratio of 55%, M2 is present in the layer at a volume ratio of 35%, and Ir is present in the layer at a volume ratio of 10%. Similarly, the electron transport layer can also be composed of a mixture of two materials. The exact structure of OLED can be found in Table 3. The materials used to manufacture OLED are shown in Table 5.

[0271] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum was determined, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in %) were calculated as a function of the luminous density from the current-voltage-luminous density characteristic (IUL characteristic) assuming Lambertian luminescence behavior, and the lifetime was also determined. 2 The EQE in % and the voltage in V are reported at a luminous density of 1000 cd / m 2 (blue and red devices) or 10000 cd / m 2 The lifetime is determined at the initial luminous density of the reference luminance (green and yellow devices). The measurement period in which the reference brightness drops to 80% of the initial brightness is set to 100%. The lifetime of the OLED assembly containing compound B of the invention is reported as a percentage relative to the reference.

[0272] OLEDs have the following layer structure:

[0273] Base

[0274] Hole injection layer (HIL) consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0275] Hole transport layer (HTL) composed of HTM1, 180 nm for blue, 50 nm for green, 40 nm for yellow, and 90 nm for red

[0276] Electron blocking layer (EBL), 20 nm EBM2 for blue, 20 nm EBM1 for green and yellow, 10 nm for red

[0277] Emission layer (EML), see Table 3

[0278] Hole blocking layer (HBL), see Table 3

[0279] Electron transport layer (ETL), see Table 3

[0280] Electron injection layer (EIL) composed of ETM2, 1 nm

[0281] Cathode made of aluminum, 100 nm

[0282] Table 3: Structure of phosphorescent OLED components

[0283]

[0284]

[0285]

[0286]

[0287]

[0288] Table 4: Results for phosphorescent OLED components

[0289]

[0290]

[0291]

[0292] Table 5: Structural formula of materials used

[0293]

[0294]

[0295]

[0296]

Claims

1. A compound of formula (1) and formula (2), The symbols used are as follows: X is identical or different in each occurrence and is CR or N, provided that not more than two X groups in each ring are N; Z is a group of formula (2), wherein the dotted bond in formula (2) represents a bond connected to the quaternary carbon; Y is identical or different in each case and is CR' or N, provided that in each ring 2 or 3 Y groups are N, or 1, 2 or 3 Y groups are N and two or more Y groups which are CR' together form an aromatic or heteroaromatic ring system; preferably, in each case 2 or 3 Y groups are N; Q is a divalent alkylene group having 1 to 4 carbon atoms, a divalent alkenylene group having 2 to 4 carbon atoms, or a divalent aryl or heteroaryl group having 5 to 60 ring atoms, wherein the alkylene, alkenylene, aryl and heteroaryl groups may be substituted with one or more R groups; R is identical or different in each case and is H; D; F; Cl; Br; I; OAr'; SAr'; B(OR 1 )2;CHO;C(=O)R 1 CR 1 =C(R 1 )2;CN;C(=O)OR 1 ; C(=O)NR 1 ;Si(R 1 )3; NO2; P(=O)(R 1 )2;OSO2R 1 ;OR 1 ;S(=O)R 1 ; S(=O)2R 1 SR 1 a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl 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 alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 1 C=CR 1 -、-C≡C-、Si(R 1 2. CONR 1 ,C=O,C=S,-C(=O)O-,P(=O)(R 1 ), -O-, -S-, SO or SO2; or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and in each case may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with R groups, wherein two or more R groups, preferably bonded to the same ring, can together form a substituted R group which can be substituted with one or more R groups. 1 A radical-substituted aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system wherein: If R and the associative groups comprise at least one heteroaromatic ring system which comprises at least one nitrogen atom having three single bonds, for each of these heteroaromatic ring systems there are always at least two radicals which are bonded to the corresponding nitrogen atom via single bonds to the corresponding nitrogen atom and which are independently bonded to the base skeleton; R' is identical or different in each case and is H; D; F; Cl; Br; I; OAr'; SAr'; B(OR 1 )2;CHO;C(=O)R 1 CR 1 =C(R 1 )2;CN;C(=O)OR 1 ; C(=O)NR 1 ;Si(R 1 )3; NO2; P(=O)(R 1 )2;OSO2R 1 ;OR 1 ;S(=O)R 1 ; S(=O)2R 1 SR 1 a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl 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 alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 1 C=CR 1 -、-C≡C-、Si(R 1 2. CONR 1 ,C=O,C=S,-C(=O)O-,P(=O)(R 1 ), -O-, -S-, SO or SO2; or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and in each case may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with R groups, wherein two or more R groups, preferably bonded to the same ring, can together form a substituted R group which can be substituted with one or more R groups. 1 radically substituted aliphatic, heteroaliphatic, aromatic or heteroaromatic ring systems, wherein, if R' and the associative groups comprise at least one heteroaromatic ring system which comprises at least one nitrogen atom with three single bonds, for each of these heteroaromatic ring systems there are always at least two radicals which are bonded to the corresponding nitrogen atom via single bonds to the corresponding nitrogen atom and which are independently bonded to the base skeleton; Ar' is identical or different in each case and is a cyclic aromatic ring having 5 to 40 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a radical, wherein two or more R 1 together can form an aromatic or heteroaromatic ring system; R 1 are the same or different in each case and are H; D; F; I; B (OR 2 )2;CHO;C(=O)R 2 CR 2 =C(R 2 )2;CN;C(=O)OR 2 ;Si(R 2 )3; NO2; P(=O)(R 2 )2;OSO2R 2 SR 2 ;OR 2 ;S(=O)R 2 ; S(=O)2R 2 a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl 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 alkynyl group may in each case be replaced by one or more R 2 group, and one or more CH2 groups in the above groups may be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2. C=O, C=S, -C(=O)O-, CONR 2 、P(=O)(R 2 ), -O-, -S-, SO or SO2, and one or more hydrogen atoms in the above groups can be replaced by D, F, Cl, Br, I, CN or NO2; or having 5 to 30 aromatic ring atoms and in each case by one or more R 2 Aromatic or heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups together may form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R 2 are identical or different in each case and are H; D; F; CN; or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by D or F; at the same time, two or more R 2 The substituents may be connected to each other and form a ring.

2. The compound according to claim 1, wherein the compound is selected from the group consisting of compounds of formula (3), formula (4), formula (5) and formula (6), The symbols used herein have the definitions given in claim 1.

3. The compound according to one or more of claims 1 and 2, which is selected from the compounds of formula (3-1), formula (4-1), formula (5-1) and formula (6-1), The symbols used herein have the definitions given in claim 2.

4. The compound according to one or more of claims 1 and 3, wherein the group of formula (2) is selected from one of formula (2-1) to formula (2-9): ， The symbols used herein have the definitions given in claim 1. In addition, Y 1 in each case the same or different and BR 1 , C(R 1 )2. NR 1 , O or S.

5. A process for the preparation of a compound according to one or more of claims 1 to 4, characterized by the following steps: (A) synthesizing a fused basic skeleton of formula (1); (B) Introduction of aromatic or heteroaromatic groups at the bridge atoms by coupling reactions.

6. An oligomer, polymer or dendrimer comprising one or more compounds of formula (1) according to one or more of claims 1 to 4, wherein the one or more bonds to the polymer, oligomer or dendrimer may be at any desired position in formula (1).

7. A preparation comprising at least one compound according to one or more of claims 1 to 4 and at least one further compound and / or at least one solvent.

8. Use of compounds according to one or more of claims 1 to 4 or preparations according to claim 7 in electronic devices.

9. An electronic device comprising at least one compound according to one or more of claims 1 to 4 and / or at least one oligomer, polymer or dendrimer according to claim 6.

10. The electronic device according to claim 9, wherein the electronic device is an organic electroluminescent device, characterized in that The device comprises an anode, a cathode and at least one light-emitting layer, wherein at least one organic layer which may be a light-emitting layer, a hole transport layer, an electron transport layer, a hole blocking layer, an electron blocking layer or other functional layer comprises at least one compound of formula (1).

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