Compounds useful as active compounds in organic electronic devices

Abstract

The present invention relates to a compound useful as an active compound in an organic electronic device. In particular, the present invention relates to compounds that can be used as active compounds in organic electronic devices, in particular in electronic devices. The invention also relates to a method for preparing the compounds according to the invention, and to electronic devices comprising said compounds.

Description

[0001] This application is a divisional application of a Chinese invention patent application filed on September 24, 2019, with application number 201980062271.0 and invention name “Compounds that can be used as active compounds in organic electronic devices”. Technical Field

[0002] The present invention relates to a compound that can be used as an active compound in an organic electronic device. In particular, the present invention relates to compounds, especially compounds for use in electronic devices. The present invention further relates to a method for preparing the compounds of the present invention and to electronic devices comprising these compounds. Background Art

[0003] The structure of organic electroluminescent devices (OLEDs) in which organic semiconductors are used as functional materials is described, for example, in US 4539507, US 5151629, EP 0676461 and WO 98 / 27136. The luminescent materials used are often organometallic complexes that exhibit phosphorescence. Due to quantum mechanical reasons, up to four times the energy efficiency and power efficiency can be achieved by using organometallic compounds as phosphorescent emitters. In general, there is still a demand for improvements in OLEDs, especially also in OLEDs that exhibit phosphorescence, such as improvements in efficiency, operating voltage and lifetime. Organic electroluminescent devices comprising fluorescent emitters or emitters that exhibit TADF (thermally activated delayed fluorescence) are also known.

[0004] The properties of organic electroluminescent devices are not only determined by the luminophore used. In particular, the other materials used, such as host / matrix materials, hole blocking materials, electron transport materials, hole transport materials, and electron or exciton blocking materials, are also of particular significance here. Improvements in these materials can lead to significant improvements in electroluminescent devices.

[0005] According to the prior art, compounds with dicyclic or tricyclic ring systems are particularly used to prepare metal complexes showing phosphorescence. These compounds particularly act as ligands in the corresponding complexes. The prior art particularly includes documents WO 2014 / 094960 A1, WO 2014 / 094961 A1, WO 2015 / 104045A1, WO 2015 / 117718A1 and WO 2016 / 124304. Matrix materials, electron transport materials, hole transport materials, fluorescent luminophores or luminophores presenting TADF (thermally activated delayed fluorescence) are not listed in these documents.

[0006] Furthermore, document WO 2015 / 036078 discloses heterocyclic compounds which are particularly useful as matrix materials, electron transport materials or hole transport materials. Most of these compounds contain a bicyclic ring system fused to a pyridine or pyridazine structure, to which an aromatic or heteroaromatic ring system is in turn fused.

[0007] In general, when these materials are used, for example, as matrix materials, hole conductor materials or electron transport materials, there is still a need for improvement, in particular with regard to the lifetime of the device, as well as with regard to efficiency and operating voltage. Furthermore, the compounds should have a high color purity. Summary of the invention

[0008] Another object of the present invention is to provide compounds which are suitable for use as fluorescent emitters or emitters exhibiting TADF (thermally activated delayed fluorescence) in organic electronic devices, especially organic electroluminescent devices, and which lead to good device properties when used in such devices, as well as to provide corresponding electronic devices.

[0009] It was therefore an object of the present invention to provide compounds which are suitable for use in organic electronic devices, in particular in organic electroluminescent devices, and which, when used in such devices, lead to good device properties, and to corresponding electronic devices.

[0010] A particular object of the present invention is to provide compounds which lead to high lifetimes, good efficiencies and low operating voltages. In particular, the nature of the matrix material, hole conductor material or electron transport material also has a fundamental influence on the lifetime and efficiency of organic electroluminescent devices.

[0011] Another problem solved by the present invention can be regarded as providing compounds suitable for use in phosphorescent or fluorescent OLEDs, in particular as matrix materials. More particularly, the problem solved by the present invention is to provide matrix materials suitable for red, yellow and green phosphorescent OLEDs.

[0012] Furthermore, the compounds, in particular when they are used as matrix materials, as hole conductor materials or as electron-transport materials in organic electroluminescent devices, should lead to devices having good color purity.

[0013] Furthermore, the compounds should be processable in a very simple manner and exhibit in particular good solubility and film-forming properties. For example, the compounds should exhibit increased oxidation stability and an improved glass transition temperature.

[0014] Another object may be considered to be to provide electronic devices with good performance very cheaply and with constant quality.

[0015] Furthermore, it should be possible to use or employ the electronic device for a variety of applications. More particularly, the performance of the electronic device should be maintained over a wide temperature range.

[0016] Surprisingly, it has been found that specific compounds described in detail below solve these problems and eliminate the disadvantages of the prior art. The use of said compounds leads to very good properties of organic electronic devices, in particular organic electroluminescent devices, especially in terms of lifetime, efficiency and operating voltage. Therefore, the present invention provides electronic devices, in particular organic electroluminescent devices, comprising such compounds, and corresponding preferred embodiments.

[0017] The present invention therefore provides a compound which can be used as active compound for organic electronic devices, characterised in that the compound has at least one aromatic or heteroaromatic ring system having 5 to 60 carbon atoms and which is fused to an aliphatic polycyclic ring system having at least 3 rings.

[0018] Preference may be given to the case where the largest ring of the aliphatic polycyclic ring system having at least 3 rings has not more than 14, preferably not more than 12, more preferably not more than 10 and especially preferably not more than 7 atoms in the respective ring.

[0019] It may also be the case that the ring via which the aliphatic polycyclic ring system having at least 3 rings is fused to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms contains six ring atoms and at least two non-adjacent nitrogen atoms.

[0020] It may also be the case that the ring via which the aliphatic polycyclic ring system having at least 3 rings is fused to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms comprises six ring atoms and contains no nitrogen atoms.

[0021] It may also be the case that the ring via which the aliphatic polycyclic ring system having at least 3 rings is fused to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms contains six ring atoms and at least one nitrogen atom, and that no other ring system is fused to this ring.

[0022] Active compounds are generally organic or inorganic materials which are introduced between anode and cathode, for example in organic electronic devices, especially organic electroluminescent devices, such as charge injection, charge transport or charge blocking materials, but especially emitting materials and matrix materials.

[0023] Compounds that can be used as active compounds of organic electronic devices can be preferably selected from fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, exciton blocking materials, electron injection materials, hole conductor materials, hole injection materials, n-type dopants, p-type dopants, wide band gap materials, electron blocking materials and / or hole blocking materials. Preferred here are fluorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, exciton blocking materials, electron injection materials, hole conductor materials, hole injection materials, n-type dopants, p-type dopants, wide band gap materials, electron blocking materials and / or hole blocking materials.

[0024] In a preferred configuration, the compounds of the present invention may comprise at least one structure of formula (I) to (XVIII):

[0025]

[0026]

[0027]

[0028] The symbols used are as follows:

[0029] Y is the same or different in each occurrence and is O, S, C(R) 2 、CArR、C(Ar) 2 、Si(Ar) 2 , SiArR or Si(R) 2 , NR or NAr, preferably O, S, NAr, more preferably NAr;

[0030] X is the same or different at each occurrence and is N or CR, preferably CR;

[0031] R is the same or different at each occurrence and is: H, D, OH, F, Cl, Br, I, CN, NO 2 ,N(Ar) 2 ,N(R 1 ) 2 ,C(=O)N(Ar) 2 ,C(=O)N(R 1 ) 2 ,Si(Ar) 3 ,Si(R 1 ) 3 ,B(OAr) 2 , B(OR 1 ) 2 , C(=O)Ar, C(=O)R 1 , P(=O)(Ar)2 , P(=O)(R 1 ) 2 , S(=O)Ar, S(=O)R 1 ,S(=O) 2 Ar, S(=O) 2 R 1 , OSO 2 Ar, OSO 2 R 1 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R 1 group substitution, where one or more non-adjacent CH 2 The group can be R 1 C=CR 1 、C≡C、Si(R 1 ) 2 、C=O、NR 1 , O, S or CONR 1 or having 5 to 40 aromatic ring atoms and in each case being replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 40 aromatic ring atoms and which may be replaced by one or more R 1 At the same time, the two R groups together can also form a monocyclic or polycyclic aliphatic or aromatic or heteroaromatic ring system;

[0032] Ar is identical or different at each occurrence and is an aromatic ring having 5 to 60 atoms and may be replaced by one or more R 1 At the same time, the two Ar groups bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom can also be connected by a single bond or selected from B(R 1 )、C(R 1 ) 2 、Si(R 1 ) 2 、C=O、C=NR 1 , C=C(R 1 ) 2 ,O,S,S=O,SO 2 、N(R 1 )、P(R 1 ) and P(=O)R 1 The bridging groups are connected to each other;

[0033] R 1be the same or different in each occurrence and be: H, D, OH, F, Cl, Br, I, CN, NO 2 ,N(Ar 1 ) 2 ,N(R 2 ) 2 , C(=O)Ar 1 , C(=O)R 2 , P(=O)(Ar 1 ) 2 , P(Ar 1 ) 2 , B(Ar 1 ) 2 , B(OR 2 ) 2 , Si(Ar 1 ) 3 ,Si(R 2 ) 3 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 group substitution, where one or more non-adjacent CH 2 The group can be -R 2 C=CR 2 -、-C≡C-、Si(R 2 ) 2 , Ge(R 2 ) 2 Sn(R 2 ) 2 , C=O, C=S, C=Se, C=NR 2 、-C(=O)O-、-C(=O)NR 2 -、NR 2 ,P(=O)(R 2 ), -O-, -S-, SO or SO 2 and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be replaced by one or more R 2 or having 5 to 40 aromatic ring atoms and may be substituted with one or more R 2 an aryloxy or heteroaryloxy group substituted with a group, or having 5 to 40 aromatic ring atoms and which may be replaced by one or more R 2 substituted aralkyl or heteroaralkyl groups, or combinations of these systems; at the same time, two or more preferably adjacent R 1The groups together may form a monocyclic or polycyclic aliphatic or aromatic or heteroaromatic ring system;

[0034] Ar 1 is identical or different on each occurrence and is a radical having 5 to 30 aromatic ring atoms and may be replaced by one or more preferably non-aromatic R 2 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two Ar 1 The group may also be connected by a single bond or selected from B(R 2 )、C(R 2 ) 2 、Si(R 2 ) 2 、C=O、C=NR 2 , C=C(R 2 ) 2 ,O,S,S=O,SO 2 、N(R 2 )、P(R 2 ) and P(=O)R 2 The bridging groups are connected to each other;

[0035] R 2 is the same or different in each occurrence and is: H, D, F, Cl, Br, I, CN, B (OR 3 ) 2 , NO 2 , C(=O)R 3 , CR 3 =C(R 3 ) 2 , C(=O)OR 3 ,C(=O)N(R 3 ) 2 ,Si(R 3 ) 3 , P(R 3 ) 2 , B(R 3 ) 2 ,N(R 3 ) 2 , NO 2 , P(=O)(R 3 ) 2 , OSO 2 R 3 , OR 3 , S(=O)R 3 ,S(=O) 2 R 3, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be replaced by one or more R 3 group substitution, where one or more non-adjacent CH 2 The group can be -R 3 C=CR 3 -、-C≡C-、Si(R 3 ) 2 , Ge(R 3 ) 2 Sn(R 3 ) 2 、C=O、C=S、C=NR 3 、-C(=O)O-、-C(=O)NR 3 -、NR 3 ,P(=O)(R 3 ), -O-, -S-, SO or SO 2 and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 or having 5 to 40 aromatic ring atoms and in each case being replaced by one or more R 3 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 40 aromatic ring atoms and which may be replaced by one or more R 3 substituted aryloxy or heteroaryloxy groups, or combinations of these systems; at the same time, two or more preferably adjacent R 2 The substituents together may also form a monocyclic or polycyclic aliphatic or aromatic or heteroaromatic ring system;

[0036] R 3 are identical or different at each occurrence and are selected from: H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and in which the aromatic or heteroaromatic ring system may be substituted by one or more alkyl radicals each having 1 to 4 carbon atoms; at the same time, two or more preferably adjacent R 3 The substituents together may also form a monocyclic or polycyclic aliphatic or aromatic or heteroaromatic ring system;

[0037] The marker s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0038] The marker t is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0039] The label v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2.

[0040] Adjacent carbon atoms in the sense of the present invention are carbon atoms that are directly bonded to each other. In addition, in the definition of groups, "adjacent groups" means that these groups are bonded to the same carbon atom or to adjacent carbon atoms. These definitions are particularly applicable to the terms "adjacent groups" and "adjacent substituents" accordingly.

[0041] Within the scope of the present description, the expression that two or more radicals together can form a ring should be understood to mean in particular that the two radicals are chemically bonded to one another with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0042]

[0043] However, in addition, the above terms should also be understood to mean that if one of the two groups is hydrogen, the second group is bound to the position of the hydrogen atom, thereby forming a ring. This should be illustrated by the following scheme:

[0044]

[0045] Condensed aryl groups, fused aromatic ring systems or fused heteroaromatic ring systems in the sense of the present invention are groups in which two or more aromatic groups are fused to each other along a common limit, i.e., annulation, such that for example two carbon atoms belong to at least two aromatic or heteroaromatic rings, as in for example naphthalene. On the contrary, for example, fluorene is not a fused aryl group in the sense of the present invention, because the two aromatic groups in fluorene do not have a common limit. The corresponding definition is applicable to heteroaryl groups and fused ring systems, which can but need not also contain heteroatoms.

[0046] If two or more preferably adjacent R, R 1 , R 2 and / or R 3 The radicals together form a ring system, the result may be a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system.

[0047] Aryl groups in the sense of the present invention contain 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms; heteroaryl groups in the sense of the present invention contain 2 to 60 carbon atoms, preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. Aryl groups or heteroaryl groups are understood here to mean simple aromatic rings, i.e. benzene, or simple heteroaromatic rings, such as pyridine, pyrimidine, thiophene, etc., or fused aryl or heteroaryl groups, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

[0048] An aromatic ring system in the sense of the present invention contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms in the ring system. A heteroaromatic ring system in the sense of the present invention contains 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and at least one heteroatom in the ring system, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system in the sense of the present invention is understood as meaning a system which does not necessarily contain only aryl or heteroaryl groups, but rather a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of non-H atoms), for example carbon, nitrogen or oxygen atoms or carbonyl groups. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, stilbenes, etc. are also to be regarded as aromatic ring systems in the sense of the present invention, as are systems in which two or more aryl groups are interrupted, for example, by linear or cyclic alkyl groups or by silyl groups. In addition, systems in which two or more aryl or heteroaryl groups are directly bonded to one another, such as biphenyl, terphenyl, quaterphenyl or bipyridine, are likewise to be regarded as aromatic or heteroaromatic ring systems.

[0049] Cyclic alkyl, alkoxy or thioalkoxy groups in the sense of this invention are understood to mean monocyclic, bicyclic or polycyclic groups.

[0050] In the context of the present invention, individual hydrogen atoms or CH 2 The C group may also be replaced by the above groups 1 - to C 20-alkyl radicals are understood to mean, for example: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 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, 2-ethylhexyl, cyclooctyl, 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-octyl, 1,1-dimethyl-n-decyl, 1,1-dimethyl-n-dodecyl, 1,1-dimethyl-n-tetradecyl, 1,1-dimethyl-n-hexadecyl, 1,1-dimethyl-n-octadecyl, 1,1-diethyl-n-hexyl, 1,1-diethyl-n-heptyl, 1,1-diethyl-n-octyl, 1,1-diethyl The cyclohexyl radicals are 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 radicals. An alkenyl radical is understood to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. An alkynyl radical is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. 1 - to C 40 An -alkoxy group is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy.

[0051] An aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30 aromatic ring atoms, which in each case may also be substituted by the abovementioned radicals and which may be attached to the aromatic or heteroaromatic system via any desired position is understood to mean, for example, radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, pyrene, lettuce, perylene, fluoranthene, benzofluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylylidene, terphenyl, biphenylylidene, fluorene, spirobifluorene, dihydrophenanthr ... Hydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, 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, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenanthroline, azine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthimidazole, pyridimidazole, pyrazimidazole, quinoxalineimidazole, Azoles, benzo Azoles, naphtho Azoles, anthracenes Azoles, phenanthracenes Azoles, Isopropylamine azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, 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, phen Oxazine, phenothiazine, fluorescent red 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.

[0052] Also preferred are compounds having structures of formula (I) to (XVIII) wherein no more than two X groups per ring are N, preferably all X groups in a ring are CR, and preferably at least one, more preferably at least two, X groups per ring are selected from CH and CD.

[0053] In another configuration, preferred are compounds having structures of formula (I) to (XVIII) wherein two X groups on each ring are N, wherein the X groups are not adjacent.

[0054] Furthermore, preference is given to compounds having structures of the formulae (I) to (XVIII) in which not more than four, preferably not more than two, X groups are N, and more preferably all X groups are CR, wherein preferably not more than four, more preferably not more than three and especially preferably not more than two of the CR groups represented by X are not CH groups.

[0055] In another configuration, compounds having structures of formula (I) to (XVIII) are preferred, wherein two X groups are N, wherein the X groups are not adjacent.

[0056] The compounds of the present invention may preferably comprise at least one structure of formula (Ia) to (XVIIIa):

[0057]

[0058]

[0059]

[0060] wherein the symbols Y, R, v, t and s have the definitions given above, in particular for formulae (I) to (XVIII), the index o is 0, 1 or 2, preferably 0 or 1, and the index n is 0, 1, 2 or 3, preferably 0, 1 or 2, and the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the index l is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1 or 2, wherein Y is preferably O, S, NR or NAr, more preferably NAr.

[0061] Furthermore, in the structures of formulae (Ia) to (XVIIIa), it may be the case that the sum of the indices v, t, s, o, n, m and l is not greater than 6, preferably not greater than 4, and more preferably not greater than 2.

[0062] When X is CR or when the aromatic and / or heteroaromatic groups are substituted by substituents R, these substituents R are preferably selected from: H, D, F, CN, N(Ar) 2 , C(=O)Ar, P(=O)(Ar) 2, a linear alkyl or alkoxy group having 1 to 10 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, each of which may be replaced by one or more R 1 group substitution, where one or more non-adjacent CH 2 The radical may be replaced by O and in which one or more hydrogen atoms may be replaced by D or F, has 5 to 24 aromatic ring atoms and may be replaced by one or more R in each case. 1 A substituted, but preferably unsubstituted, aromatic or heteroaromatic ring system, or a substituted, but preferably unsubstituted aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms and which may be replaced by one or more R 1 At the same time, preferably two substituents R bonded to adjacent carbon atoms can optionally form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, which can be replaced by one or more R 1 wherein the Ar group has the definitions given above, in particular for formulae (I) to (XVIII).

[0063] More preferably, these substituents R are selected from: H, D, F, CN, N(Ar) 2 , a linear alkyl group having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3 or 4 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms, each of which may be substituted by one or more R 1 substituted with, but preferably unsubstituted with, 5 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 replaced by one or more non-aromatic R 1 A substituted, but preferably unsubstituted aromatic or heteroaromatic ring system; at the same time, preferably two substituents R bonded to adjacent carbon atoms 1 Optionally, a monocyclic or polycyclic aliphatic ring system may be formed, which may be replaced by one or more R 2 The group is substituted, but preferably unsubstituted, in which Ar may have the definition given above.

[0064] Most preferably, the substituents R are selected from H and aromatic or heteroaromatic ring systems having 6 to 18 aromatic ring atoms, preferably having 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic R 1The substituents R are preferably substituted with, but preferably unsubstituted with, phenyl, o-, m- or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophenyl, 1-, 2-, 3- or 4-carbazolyl and indenocarbazolyl, each of which may be substituted with one or more R 1 The group is substituted, but is preferably unsubstituted.

[0065] In addition, it may be the case that the substituents R of the heteroaromatic ring systems of the formulae (I) to (XVIII) and / or (Ia) to (XVIIIa) do not form a fused aromatic or heteroaromatic ring system with the ring atoms of the aromatic or heteroaromatic ring system, preferably do not form any fused ring system. This includes substituents R that can be bonded to R 1 Possible substituents R of the group 1 , R 2 , R 3 A fused ring system is formed.

[0066] In a further preferred embodiment, it may be the case that the compounds useful as active compounds in organic electronic devices comprise at least two, preferably at least three, aliphatic polycyclic ring systems having at least 3 rings.

[0067] It may also be the case that the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms fused to an aliphatic polycyclic ring system having at least 3 rings is selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophene, pyrenyl, triazine, imidazolyl, benzimidazolyl, benzo oxazolyl, benzothiazolyl, 1-, 2-, 3- or 4-carbazolyl, indenocarbazolyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl, and / or terphenylidene; each of which may be substituted by one or more R and / or R 1 The phenyl group is substituted with spirobifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene and terphenylidene groups.

[0068] In another preferred embodiment, the following may be the case: the aliphatic polycyclic ring system having at least 3 rings and fused to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms forms a substructure of formula (N-1) to (N-6):

[0069]

[0070]

[0071] The symbol R 1 , v, t and s have the definitions given above, in particular for formulae (I) to (XVIII), and the dotted line represents the bond of the aliphatic polycyclic ring system having at least 3 rings fused to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms. The double bonds shown in the structures of formulae (N-1) to (N-6) are considered to be part of the fusion of the structure of one of formulae (N-1) to (N-6) to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms.

[0072] It may also be the case that the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms fused to the aliphatic polycyclic ring system having at least 3 rings forms a substructure of formula (Ar-1) to (Ar-66):

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080] Where X' is N or CR 1 , preferably CR 1 , Y' is selected from O, S, C(R 1 ) 2 、Si(R 1 ) 2 NR 1 and NAr 1 , preferably O, S, NAr 1 , more preferably NAr 1 , U is selected from O, S, C(R 1 ) 2 、N(R 1 )、B(R 1 )、Si(R 1 ) 2 、C=O、S=O、SO 2 , P(R 1 ) and P(=O)R 1 , where R1 The aliphatic polycyclic ring system having at least 3 rings is combined with the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms at the corresponding positions indicated by o to form a ring. Preferred structures are those of formulae (Ar-2) to (Ar-66), and particularly preferred structures are those of formulae (Ar-4) to (Ar-15) and (Ar-23) to (Ar-44).

[0081] Also preferred are compounds having substructures of formula (Ar-1) to (Ar-66) in which no more than two X' groups per ring are N, preferably all X' groups in one ring are CR. 1 , and preferably at least one, more preferably at least two, X' groups per ring are selected from CH and CD.

[0082] In another configuration, preferred are compounds having structures of formula (I) to (XVIII) wherein two X' groups on each ring are N, wherein the X' groups are not adjacent.

[0083] Furthermore, compounds having substructures of the formulae (Ar-1) to (Ar-66) are preferred, wherein no more than four, preferably no more than two, X' groups are N, and more preferably all X' groups are CR 1 , wherein X' represents CR 1 Not more than four, more preferably not more than three and especially preferably not more than two of the radicals are not CH groups.

[0084] In another configuration, compounds having substructures of formulae (Ar-1) to (Ar-66) are preferred, wherein two X' groups are N, wherein the X groups are not adjacent.

[0085] In yet another configuration, compounds having substructures of formula (Ar-55) to (Ar-66) are preferred, wherein preferably no more than two X' groups are N.

[0086] In a preferred embodiment, the combinations according to the following table are particularly preferred:

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109] As CR 1 X' group, where CR 1 The group is not a CH group and is preferably selected from hole conductor groups and / or electron conductor groups, wherein the electron conductor group preferably contains at least 2 nitrogen atoms in one six-membered ring or two fused six-membered rings, and is more preferably selected from triazines and pyrimidines. Depending on the end use of the compound of the present invention, groups that promote TADF (thermally activated delayed fluorescence) are further preferred.

[0110] Among the compounds given above, compounds having a fused, more preferably two-dimensionally fused, aromatic or heteroaromatic ring system are particularly preferred, for example compounds having substructures of the formulae (Ar-2) to (Ar-12), (Ar-19) to (Ar-35) and (Ar-45) to (Ar-54), more preferably compounds having substructures of the formulae (Ar-4) to (Ar-9), (Ar-23) to (Ar-32) and (Ar-46) to (Ar-54), and particularly preferred compounds having substructures of the formulae (Ar-4), (Ar-5), (Ar-23) to (Ar-25), (Ar-46) and (Ar-49).

[0111] In another embodiment of the present invention, compounds containing fluorene, dibenzofuran, dibenzothiophene, carbazole, spirobifluorene and similar structures are preferred, especially compounds having substructures of formulae (Ar-10) to (Ar-15) and (Ar-33) to (Ar-44), more preferably (Ar-13) to (Ar-15) and (Ar-36) to (Ar-44).

[0112] For clarity of the above combinations, it should be emphasized that, for example, the combination of substructure N-1 with substructure Ar-1 produces a compound of formula (I). Similarly, for example, the combination of substructure N-2 with substructure Ar-45 produces a structure of formula (V). The same applies to other combinations.

[0113] It may also be the case that the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms fused to the aliphatic polycyclic ring system having at least 3 rings forms a substructure of the formula (Ar'-1) to (Ar'-65):

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122] Where R 1have the definitions given above, in particular for formulae (I) to (XVIII), and the symbols Y' and U have the definitions given above, in particular for formulae (Ar-1) to (Ar-65), the index o is 0, 1 or 2, preferably 0 or 1, the index n is 0, 1, 2 or 3, preferably 0, 1 or 2, and the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the index l is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1 or 2, and the aliphatic polycyclic ring system having at least 3 rings is combined with the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms at the corresponding positions identified by o to form a ring. Preferred structures are the structures of the formulae (Ar'-2) to (Ar'-53), and particularly preferred structures are the structures of the formulae (Ar'-4) to (Ar'-15) and (Ar'-22) to (Ar'-43).

[0123] Furthermore, in the substructures of the formulae (Ar'-1) to (Ar'-65), it may be the case that the sum of the indices o, n, m and l is not greater than 6, preferably not greater than 4, more preferably not greater than 2.

[0124] Substructures of the formulae (Ar'-54) to (Ar'-65) are further preferred.

[0125] In a preferred embodiment, the combinations according to the following table are particularly preferred:

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155] R in the above combination 1 Group, where R 1 The group is not an H group and is preferably selected from hole conductor groups and / or electron conductor groups, wherein the electron conductor groups preferably contain at least 2 nitrogen atoms in one six-membered ring or two fused six-membered rings, and are more preferably selected from triazines and pyrimidines. Depending on the end use of the compounds of the present invention, groups that promote TADF (thermally activated delayed fluorescence) are further preferred.

[0156] Among the compounds given above, compounds having a fused, more preferably two-dimensionally fused, aromatic or heteroaromatic ring system are particularly preferred, for example compounds having substructures of the formulae (Ar'-2) to (Ar'-12), (Ar'-18) to (Ar'-34) and (Ar'-44) to (Ar'-53), more preferably compounds having substructures of the formulae (Ar'-4) to (Ar'-9), (Ar'-22) to (Ar'-31) and (Ar'-45) to (Ar'-53), and particularly preferred compounds having substructures of the formulae (Ar'-4), (Ar'-5), (Ar'-22) to (Ar'-24), (Ar'-45) and (Ar'-48).

[0157] In another embodiment of the present invention, compounds containing fluorene, dibenzofuran, dibenzothiophene, carbazole, spirobifluorene and similar structures are preferred, especially compounds having substructures of the formulae (Ar'-10) to (Ar'-15) and (Ar'-32) to (Ar'-43), more preferably (Ar'-13) to (Ar'-15) and (Ar'-35) to (Ar'-43).

[0158] In a further configuration, it may be the case that the compounds useful as active compounds for organic electronic devices comprise a fused aromatic or heteroaromatic ring system having at least two, preferably three, optionally substituted fused rings.

[0159] In another embodiment, the following may be the case: the compound that can be used as an active compound for an organic electronic device comprises a hole transport group, wherein, preferably, in the structures of formulae (I) to (XVIII) and / or (Ia) to (XVIIIa), the Ar group present in the Y group or the R group comprises and preferably represents a hole transport group, or in the structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), R 1 The group comprises and preferably represents a hole transporting group. Hole transporting groups are known in the art and they preferably comprise triarylamine or carbazole groups.

[0160] The following may be preferred: the hole transport group comprises one group and is preferably a group selected from the group consisting of formulae (H-1) to (H-3),

[0161]

[0162] The dotted key marks the connection location, and

[0163] Ar 2 ,Ar 3 ,Ar 4Each is independently an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which may be replaced by one or more R 1 group substitution;

[0164] p is 0 or 1, and

[0165] Z is a bond or C(R 1 ) 2 、Si(R 1 ) 2 、C=O、NR 1 、N-Ar 1 , BR 1 , PR 1 , PO(R 1 ),

[0166] SO, SO 2 , Se, O or S, preferably a bond or C(R 1 ) 2 NR 1 , O or S, where the symbol Ar 1 and R 1 has the meanings given above, in particular for formulae (I) to (XVIII). The substituents R in the structures of the formulae (H-1) to (H-3) are 1 In the structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), the substituent R 2 In addition, it is preferred to exclude the presence of NN bonds.

[0167] Alternatively, the hole transport group may contain one group and preferably a group selected from the group consisting of formulae (H-4) to (H-26),

[0168]

[0169]

[0170]

[0171] where Y 1 O, S, C (R 1 ) 2 NR 1 or NAr 1 , dotted bonds mark the connection positions, e is 0, 1 or 2, j is 0, 1, 2 or 3, h is the same or different at each occurrence and is 0, 1, 2, 3 or 4, p is 0 or 1, Ar 1 and R 1has the definitions given above, in particular for formulae (I) to (XVIII), and Ar 2 has the definitions given above, in particular for formula (H-1) or (H-2). The substituent R in the structures of formulae (H-3) to (H-26) is 1 In the structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), the substituent R 2 In addition, it is preferred to exclude the presence of NN bonds.

[0172] The hole transport groups of formulae (H-1) to (H-26) described in detail above constitute the preferred R of formulae (I) to (XVIII) or preferred embodiments thereof. 1 A group, in which R in this case as detailed in formulae (H-1) to (H-26) 1 The group should be R 2 Group replacement.

[0173] It is clear from the above terms that if the label is p=0, then the corresponding Ar 2 The groups are not present and bonds are formed.

[0174] Preferably, Ar 2 The group may be combined with Ar of formula (H-1) to (H-26) 2 The radical may be completely conjugated with the aromatic or heteroaromatic radical or the nitrogen atom to which it is bonded.

[0175] In another preferred embodiment of the present invention, Ar 2 is an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms, and the ring system may be replaced by one or more R 1 substituted, but preferably unsubstituted, wherein R 1 may have the definitions given above, in particular for formulae (I) to (XVIII). More preferably, Ar 2 is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which may be substituted by one or more R 1 substituted, but preferably unsubstituted, wherein R 1 may have the definitions given above, in particular for formulae (I) to (XVIII).

[0176] Also preferably, the symbol Ar shown in formulas (H-1) to (H-26) 2In particular, aryl or heteroaryl groups have 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, so that the aromatic or heteroaromatic radicals of the aromatic or heteroaromatic ring system are bonded directly to the corresponding atoms of the other radical, i.e. via an atom of the aromatic or heteroaromatic radical.

[0177] The following cases are also possible: Ar shown in formulas (H-1) to (H-26) 2 The radical comprises an aromatic ring system having no more than two fused aromatic and / or heteroaromatic six-membered rings; preferably it does not comprise any fused aromatic or heteroaromatic ring system having a fused six-membered ring. Thus, a naphthyl structure is preferred over anthracene structures. In addition, a fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structure is preferred over a naphthyl structure. Particularly preferred are structures without fusion, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0178] The following case may also be true: Ar shown in formulas (H-1) to (H-26) 2 In particular, the radical has not more than 1 nitrogen atom, preferably not more than 2 heteroatoms, particularly preferably not more than 1 heteroatom and especially preferably no heteroatoms.

[0179] In another preferred embodiment of the present invention, Ar 3 and / or Ar 4 is identical or different at each occurrence and is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, and more preferably an aromatic ring system having 6 to 12 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 aromatic ring atoms, each of which may be replaced by one or more R 1 substituted, but preferably unsubstituted, wherein R 1 may have the definitions given above, in particular in formulae (I) to (XVIII).

[0180] In another preferred embodiment, the following may be the case: the compound that can be used as an active compound in an organic electronic device contains a group containing an electron transporting group, wherein, preferably, in the structures of formulae (I) to (XVIII) and / or (Ia) to (XVIIIa), the Ar group present in the Y group or the R group contains and preferably represents a group containing an electron transporting group, or in the structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), R 1 The group includes and preferably refers to a group containing an electron transporting group. Electron transporting groups are well known in the art and facilitate the ability of a compound to transport and / or conduct electrons.

[0181] In addition, compounds that can be used as active compounds in organic electronic devices show surprising advantages, the compounds comprising at least one structure selected from pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and / or benzimidazole, particularly preferably pyrimidine, triazine and quinazoline. These structures generally promote the ability of the compound to transport and / or conduct electrons.

[0182] In a preferred configuration of the present invention, the group containing an electron transporting group may be a group represented by the formula (QL),

[0183]

[0184] Where L 1 represents a bond or has 5 to 40, preferably 5 to 30 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a radical, Q is an electron transporting group, wherein R 1 has the definitions given above, in particular for formulae (I) to (XVIII), and the bonds mark the attachment sites. In this case, the substituent R in the structure of formula (QL) 1 In the structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), the substituent R 2 replace.

[0185] Preferably, L 1 The group may be combined with the Q group and the L bonded to the formula (QL) 1 The atoms of the radical, preferably the carbon or nitrogen atoms, form complete conjugation. Once a direct bond is formed between adjacent aromatic or heteroaromatic rings, complete conjugation of the aromatic or heteroaromatic system is formed. Other bonds between the aforementioned conjugated groups, for example via sulfur, nitrogen or oxygen atoms or carbonyl groups, are not detrimental to the conjugation. In the case of the fluorene system, the two aromatic rings are directly bonded, wherein the sp 3 -hybridized carbon atoms do prevent the fusion of these rings, but due to the sp 3 The -hybridized carbon atom is not necessarily located between the electron-transporting Q group and the following atom, so that conjugation is possible, via which the group of formula (QL) is bonded to other structural units of the compound of the present invention. In contrast, in the case of the second spirobifluorene structure, if the Q group is bonded to L of formula (QL) 1 If the bond between the aromatic or heteroaromatic groups to which the group is bonded is via the same phenyl group in the spirobifluorene structure or via phenyl groups in the spirobifluorene structure that are directly bonded to each other and in one plane, then complete conjugation can be formed. 1The bond between the aromatic or heteroaromatic group to which the group is bonded is via the sp 3 If different phenyl groups are bonded to the second spirobifluorene structure to which the -hybridized carbon atom is bonded, the conjugation is interrupted.

[0186] In another preferred embodiment of the present invention, L 1 is a bond or an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms, and the ring system may be substituted by one or more R 1 substituted, but preferably unsubstituted, wherein R 1 may have the definitions given above, in particular for formulae (I) to (XVIII). More preferably, L 1 is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which may be substituted by one or more R 2 substituted, but preferably unsubstituted, wherein R 2 may have the definitions given above, in particular for formulae (I) to (XVIII).

[0187] Also preferably, the symbol L shown in formula (QL) 1 In particular, it is identical or different on each occurrence and is a bond or an aryl or heteroaryl group with 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, so that the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is bonded directly to the corresponding atom of the other group, i.e. via an atom of the aromatic or heteroaromatic group.

[0188] Alternatively, the following may be true: L shown in formula (QL) 1 The group contains an aromatic ring system with no more than two fused aromatic and / or heteroaromatic six-membered rings; preferably does not contain any fused aromatic or heteroaromatic ring system. Therefore, a naphthyl structure is preferred over anthracene structure. In addition, a fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structure is preferred over a naphthyl structure.

[0189] Particularly preferred are structures without condensations, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0190] Suitable aromatic or heteroaromatic ring systems L 1 Examples of are selected from: o-, m- or p-phenylene, o-, m- or p-biphenylene, terphenylene, especially branched terphenylene, quaterphenylene, especially branched quaterphenylene, fluorene, spirobifluorene, dibenzofuranene, dibenzothiophene and carbazole; each of which may be substituted by one or more R 1 The group is substituted, but is preferably unsubstituted.

[0191] The following situation may also be true: L shown in formula (QL) 1 In particular, the radical has not more than 1 nitrogen atom, preferably not more than 2 heteroatoms, particularly preferably not more than 1 heteroatom and more preferably no heteroatoms.

[0192] Preferably, the Q group, or electron transport group, in particular as shown in formula (QL), can be selected from the structures of formula (Q-1), (Q-2), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9) and / or (Q-10):

[0193]

[0194]

[0195] The dotted key marks the connection position.

[0196] Q' is the same or different in each occurrence and is CR 1 or N, and

[0197] Q" is NR 1 , O or S;

[0198] where at least one Q' is N, and

[0199] R 1 As defined above, in particular in formulae (I) to (XVIII).

[0200] The substituent R in the structures of formula (Q-1) to (Q-10) 1 In the structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), the substituent R 2 replace.

[0201] In addition, the Q group, or electron transport group, particularly shown in formula (QL), may preferably be selected from the structures of formula (Q-11), (Q-12), (Q-13), (Q-14) and / or (Q-15):

[0202]

[0203]

[0204] The symbol R 1 Having the definitions given above, in particular for formulae (I) to (XVIII), X' is N or CR 1 The dotted bond indicates the connection position, wherein X' is preferably a nitrogen atom. The substituent R in the structures of formula (Q-11) to (Q-15)1 In the structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), the substituent R 2 replace.

[0205] In another embodiment, the Q group, or electron transport group, particularly as shown in formula (QL), can be selected from the structures of formula (Q-16), (Q-17), (Q-18), (Q-19), (Q-20), (Q-21) and / or (Q-22):

[0206]

[0207]

[0208] The symbol R 1 has the definitions detailed above, especially for formulae (I) to (XVIII), the dotted bonds mark the attachment positions, and m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, n is 0, 1, 2 or 3, preferably 0, 1 or 2, and o is 0, 1 or 2, preferably 1 or 2. Preferred structures are the formulae (Q-16), (Q-17), (Q-18) and (Q-19). Furthermore, the substituent R in the structures of formulae (Q-16) to (Q-22) is 1 In the structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), the substituent R 2 replace.

[0209] In another embodiment, the Q group, or electron transport group, particularly as shown in formula (QL), can be selected from the structures of formula (Q-23), (Q-24) and / or (Q-25):

[0210]

[0211]

[0212] The symbol R 1 have the definitions given above, especially for formulae (I) to (XVIII), and the dotted bonds mark the positions of attachment. Furthermore, the substituents R in the structures of formulae (Q-23) to (Q-25) 1 In the structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), the substituent R 2 replace.

[0213] In another embodiment, in particular the Q group, or electron transport group, shown in formula (QL) can be selected from the structures of formula (Q-26), (Q-27), (Q-28), (Q-29) and / or (Q-30):

[0214]

[0215]

[0216] The symbol Ar 1 and R 1 Having the definitions given above, in particular for formulae (I) to (XVIII), X' is N or CR 1 The dotted bond marks the connection position. Preferably, in the structures of formula (Q-26), (Q-27) and (Q-28), exactly one X' is a nitrogen atom. Moreover, the substituent R in the structures of formula (Q-26) to (Q-30) 1 In the structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), the substituent R 2 replace.

[0217] Preferably, the Q group, or electron transport group, especially as shown in formula (QL), can be selected from the structures of formula (Q-31), (Q-32), (Q-33), (Q-34), (Q-35), (Q-36), (Q-37), (Q-38), (Q-39), (Q-40), (Q-41), (Q-42), (Q-43) and / or (Q-44):

[0218]

[0219]

[0220]

[0221] The symbol Ar 1 and R 1 has the definitions given above, in particular for formulae (I) to (XVIII), the dotted bonds mark the attachment positions, and m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, n is 0, 1, 2 or 3, preferably 0 or 1, n is 0, 1, 2 or 3, preferably 0, 1 or 2, and l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2. Here, the substituent R in the structures of formulae (Q-31) to (Q-44) 1 In the structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), the substituent R 2 replace.

[0222] In another preferred embodiment of the present invention, Ar 1 is identical or different on each occurrence and is an aromatic or heteroaromatic ring system, preferably an aryl or heteroaryl group having 5 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, and more preferably an aromatic ring system, preferably an aryl group having 6 to 12 aromatic ring atoms, or a heteroaromatic ring system, preferably a heteroaryl group having 5 to 13 aromatic ring atoms, each of which may be substituted by one or more R 2 substituted, but preferably unsubstituted, wherein R 2 may have the meanings specified above, especially in formulae (I) to (XVIII).

[0223] Preferably, the symbol Ar 1 is an aryl or heteroaryl group, such that the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is bonded directly, i.e. via an atom of the aromatic or heteroaromatic group, to the corresponding atom of another group, for example a carbon or nitrogen atom of a group (H-1) to (H-26) or (Q-26) to (Q-44) shown above.

[0224] Advantageously, Ar in formula (H-1) to (H-26) or (Q-26) to (Q-44) 1 is a ring having 6 to 12 aromatic atoms and may be substituted by one or more R 2 A substituted, but preferably unsubstituted aromatic ring system, wherein R 2 may have the definitions detailed above, in particular for formulae (I) to (XVIII).

[0225] Preferably, R in formula (H-1) to (H-26) or (Q-1) to (Q-44) 1 or R 2 The group does not correspond to the R 1 or R 2 The aryl or heteroaryl group Ar to which the group is bonded 1 ,Ar 2 ,Ar 3 and / or Ar 4 This includes the ring atoms that can be bonded to R 1 or R 2 Possible substituents R of the group 2 , R 3 A fused ring system is formed.

[0226] It can also be the following situation, that is, Ar, Ar 1 ,Ar 2 ,Ar 3 and / or Ar 4The radical is selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, in particular branched terphenyl, quaterphenyl, in particular branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophenyl, pyrenyl, triazine, imidazolyl, benzimidazolyl, benzo oxazolyl, benzothiazolyl, 1-, 2-, 3- or 4-carbazolyl, indenocarbazolyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl and / or terphenylidene, each of which may be replaced by one or more R 1 and / or R 2 The moiety may be substituted, but is preferably unsubstituted, particularly preferably phenyl, spirobifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene, terphenylidene moiety.

[0227] When X or X 1 Yes CR 1 or when the aromatic and / or heteroaromatic group is substituted by a substituent R 1 When substituted, these substituents R 1 Preferably selected from: H, D, F, CN, N(Ar 1 ) 2 , C(=O)Ar 1 , P(=O)(Ar 1 ) 2 , a linear alkyl or alkoxy group having 1 to 10 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, each of which may be replaced by one or more R 2 group substitution, where one or more non-adjacent CH 2 The radical may be replaced by O and in which one or more hydrogen atoms may be replaced by D or F, has 5 to 24 aromatic ring atoms and may be replaced by one or more R in each case. 2 A substituted, but preferably unsubstituted, aromatic or heteroaromatic ring system, or a ring system having 5 to 25 aromatic ring atoms which may be replaced by one or more R 2 At the same time, preferably the two substituents R bonded to adjacent carbon atoms 1 Optionally, it may form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more R 1 Group substitution; wherein Ar 1 The radicals have the definitions given above, in particular for the formulae (I) to (XVIII).

[0228] More preferably, these substituents R 1 Selected from: H, D, F, CN, N(Ar 1 )2 , a linear alkyl group having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3 or 4 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms, each of which may be substituted by one or more R 2 substituted with, but preferably unsubstituted with, 5 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 replaced by one or more non-aromatic R 1 A substituted, but preferably unsubstituted aromatic or heteroaromatic ring system; at the same time, preferably two substituents R bonded to adjacent carbon atoms 1 Optionally, a monocyclic or polycyclic aliphatic ring system may be formed, which may be substituted by one or more R 2 substituted, but preferably unsubstituted, wherein Ar 1 May have the definitions given above.

[0229] Most preferably, the substituent R 1 is selected from H or an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, which may in each case be replaced by one or more non-aromatic R 2 Suitable substituents R are substituted with, but preferably are unsubstituted. 1 Examples of are selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophenyl, 1-, 2-, 3- or 4-carbazolyl and indenocarbazolyl, each of which may be substituted by one or more R 2 The group is substituted, but is preferably unsubstituted.

[0230] In addition, the following may be the case: the substituent R of the heteroaromatic ring system of formula (I) to (XVIII), (Ia) to (XVIIIa), (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53) 1 does not form a fused aromatic or heteroaromatic ring system with the ring atoms of the aromatic or heteroaromatic ring system, preferably does not form any fused ring system. This includes 1 Possible substituents R of the group 2 , R 3 A fused ring system is formed.

[0231] The following may also be the case: In the structures of formulae (I) to (XVIII), (Ia) to (XVIIIa), (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), at least one R 1 or Ar 1 The group is selected from the formula (R 1 -1) to (R 1 -92), or in the structures of formulae (H-1) to (H-26), (Q-1) to (Q-44), at least one Ar 1 or R 1 The group is selected from the formula (R 1 -1) to (R 1 -92) group:

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238] The symbols used are as follows:

[0239] Y 1 O, S or NR 2 , preferably O or S;

[0240] k is independently 0 or 1 at each occurrence;

[0241] i is independently 0, 1, or 2 at each occurrence;

[0242] j is independently 0, 1, 2, or 3 at each occurrence;

[0243] h is independently 0, 1, 2, 3, or 4 at each occurrence;

[0244] g is independently 0, 1, 2, 3, 4, or 5 at each occurrence;

[0245] R 2 may have the definitions given above, in particular for formulae (I) to (XVIII), and

[0246] Dashed keys mark the connection locations.

[0247] Here, the preferred formula R1 -1 to R 1 -54, particularly preferably R 1 -1. R 1 -3. R 1 -5. R 1 -6. R 1 -15, R 1 -29, R 1 -30, R 1 -31, R 1 -32, R 1 -33, R 1 -38, R 1 -39, R 1 -40, R 1 -41, R 1 -42, R 1 -43, R 1 -44 and / or R 1 -45 group.

[0248] The following situation is preferred: 1 -1) to (R 1 The sum of the indices k, i, j, h and g in the structure of -92) is in each case not greater than 3, preferably not greater than 2, more preferably not greater than 1.

[0249] Preferably, the formula (R 1 -1) to (R 1 -92) 2 The group does not correspond to the R 2 The ring atoms of the aryl or heteroaryl groups to which the group is bonded form a fused aromatic or heteroaromatic ring system, preferably without forming any fused ring system. This includes with groups that can be bonded to R 2 Possible substituents R of the group 3 A fused ring system is formed.

[0250] The formula (R 1 -1) to (R 1 -92) is a preferred Ar group of formula (I) to (XVIII) or an Ar group of formula (H-1) to (H-3) or a preferred embodiment of these formulas 3 ,Ar 4 A group, wherein, in this case, the formula (R 1 -1) to (R 1 -92) shown in R 2 The group will be R 1 The above formula (R 1 -1) to (R 1 -92) the preferences detailed are applicable accordingly.

[0251] Preferred are compounds comprising at least one structure of formula (H-1) to (H-26), wherein Ar 2 The group is selected from the formula (L 1 -1) to (L 1 -108), and / or a compound comprising a structure of formula (QL), wherein L 1 The group is a bond or is selected from the formula (L 1 -1) to (L 1 -108) group:

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259] wherein the dashed key marks the connection position in each case, the index k is 0 or 1, the index l is 0, 1 or 2, the index j is independently 0, 1, 2 or 3 at each occurrence, the index h is independently 0, 1, 2, 3 or 4 at each occurrence, the index g is 0, 1, 2, 3, 4 or 5; the symbol Y 1 O, S or NR 1 , preferably O or S; and the symbol R 1 has the definitions given above, in particular for formulae (I) to (XVIII).

[0260] The following situation is preferred: 1 -1) to (L 1 The sum of the indices k, l, g, h and j in the structure of -108) is in each case at most 3, preferably at most 2 and more preferably at most 1.

[0261] Preferred compounds of the invention having groups of formula (H-1) to (H-26) include a group selected from the group consisting of 1 -1) to (L 1 -78) and / or (L 1 -92) to (L 1 -108), preferably (L 1 -1) to (L 1 -54) and / or (L 1-92) to (L 1 -108), particularly preferably formula (L 1 -1) to (L 1 -29) and / or (L 1 -92) to (L 1 -103) 2 Advantageously, the formula (L 1 -1) to (L 1 -78) and / or (L 1 -92) to (L 1 -108), preferred formula (L 1 -1) to (L 1 -54) and / or (L 1 -92) to (L 1 -108), especially preferably (L 1 -1) to (L 1 -29) and / or (L 1 -92) to (L 1 -103) may in each case be not greater than 3, preferably not greater than 2, more preferably not greater than 1.

[0262] Preferred compounds of the invention having a group of formula (QL) comprise L 1 Group, the L 1 The group represents a bond or is selected from the formula (L 1 -1) to (L 1 -78) and / or (L 1 -92) to (L 1 -108), preferably formula (L 1 -1) to (L 1 -54) and / or (L 1 -92) to (L 1 -108), especially preferably formula (L 1 -1) to (L 1 -29) and / or (L 1 -92) to (L 1 -103). Advantageously, formula (L 1 -1) to (L 1 -78) and / or (L 1 -92) to (L 1 -108), preferred formula (L 1 -1) to (L 1 -54) and / or (L 1 -92) to (L 1 -108), especially preferably (L 1 -1) to (L 1-29) and / or (L 1 -92) to (L 1 -103) may in each case be not greater than 3, preferably not greater than 2, more preferably not greater than 1.

[0263] Preferably, the formula (L 1 -1) to (L 1 -108) 2 The group does not correspond to the R 2 The ring atoms of the aryl or heteroaryl groups to which the group is bonded form a fused aromatic or heteroaromatic ring system and preferably do not form any fused ring system. This includes ring atoms of aryl or heteroaryl groups that can be bonded to R 2 Possible substituents R of the group 3 A fused ring system is formed.

[0264] In a preferred configuration, the compounds of the invention which can be used as active compounds in organic electronic devices are selected from phenyl compounds, fluorenes, indenofluorenes, spirobifluorenes, carbazoles, indenocarbazoles, indolocarbazoles, spirocarbazoles, pyrimidines, triazines, lactams, triarylamines, dibenzofurans, dibenzothiophenes, imidazoles, benzimidazoles, ... oxazole, benzothiazole, 5-arylphenanthridin-6-one, 9,10-dihydrophenanthrene, fluoranthene, anthracene, benzanthracene, indeno[1,2,3-jk]fluorene.

[0265] In a preferred configuration, the compounds of the present invention can be represented by structures of formulae (I) to (XVIII) and / or formulae (Ia) to (XVIIIa), or by a combination of substructures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53). Preferably, the compounds useful as active compounds in organic electronic devices, preferably compounds comprising structures of formulae (I) to (XVIII) and / or formulae (Ia) to (XVIIIa), or compounds obtainable by a combination of substructures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), have a molecular weight of not more than 5000 g / mol, preferably not more than 4000 g / mol, particularly preferably not more than 3000 g / mol, particularly preferably not more than 2000 g / mol and very particularly preferably not more than 1200 g / mol.

[0266] In addition, preferred compounds of the invention are characterized in that they are sublimable. The molar mass of these compounds is generally less than about 1200 g / mol.

[0267] When the compounds of the present invention are 1 or R 2When groups are substituted, preferably they do not have any aryl or heteroaryl groups having more than two aromatic six-membered rings directly fused to each other. More preferably, the substituents do not have any aryl or heteroaryl groups having six-membered rings directly fused to each other at all. The reason for this preferred mode is that the triplet energy of such structures is low. Fused aryl groups having more than two aromatic six-membered rings directly fused to each other but still suitable according to the present invention are phenanthrene and terphenylenes, since they also have high triplet energy levels.

[0268] In the case of the structure of the compounds of the present invention which can be used as active compounds in organic electronic devices for use as fluorescent emitters or as blue OLED materials, preferred compounds may contain corresponding groups, such as fluorene, anthracene and / or pyrene groups, which groups may be substituted by R 1 or R 2 groups, or the groups are substituted by (R 1 -1) to (R 1 -95) groups, preferably (R 1 -33) to (R 1 -57) and (R 1 -76) to (R 1 -86), or (L 1 -1) to (L 1 -109), preferably (L 1 -30) to (L 1 -60) and (L 1 -71) to (L 1 -91) and are formed by being correspondingly substituted by the substituent R 2 .

[0269] In another preferred embodiment of the present invention, R 2 , for example in the structures of formulas (I) to (XVIII) and the preferred embodiments of this structure or the structures related to these formulas, is the same or different each time it appears and is selected from: H, D, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms, more preferably 5 to 13 aromatic ring atoms, which ring system may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0270] Preferably, the R 2 group does not form a fused aromatic or heteroaromatic ring system with the ring atoms of the aryl group or heteroaryl group to which the R 2 group is bonded, and preferably does not form any fused ring system. This includes forming a fused ring system with the possible substituent R 2 group that may be bonded to the R 3 group.

[0271] In another preferred embodiment of the present invention, R 3 , for example in the structures of formulae (I) to (XVIII) and preferred embodiments of such structures or structures relating to these formulae, is identical or different on each occurrence and is selected from: H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 10 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms, more preferably 5 to 13 aromatic ring atoms, which ring system may be substituted by one or more alkyl radicals each having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0272] In a further configuration of the invention, preference is given to compounds obtained by the combination of the substructures N-1 and Ar-1, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, said compounds having the following properties:

[0273]

[0274] In a further configuration of the invention, preference is given to compounds obtained by combining the substructures N-1 and Ar-1', wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0275]

[0276] In another configuration of the invention, preference is given to compounds obtained by combining the substructures N-1 and Ar-4, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, said compounds having the following properties:

[0277]

[0278] In a further configuration of the invention, preference is given to compounds obtained by combining the substructures N-1 and Ar-4', wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0279]

[0280] In another configuration of the invention, preference is given to compounds obtained by the combination of substructures N-1 and Ar-5, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, said compounds having the following properties:

[0281]

[0282] In a further configuration of the invention, preference is given to compounds obtained by combining the substructures N-1 and Ar-5', wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0283]

[0284] In another configuration of the invention, preferred are compounds obtained by combining substructures N-1 and Ar-10, wherein the U group is C(R 1 ) 2 and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R 1 The group is preferably derived from R 1 -2 and together form a ring system which is preferably in turn bonded to a structural unit obtainable by the combination of substructures N-1 and Ar-10, wherein these compounds have the following properties:

[0285]

[0286] In another configuration of the invention, preferred are compounds obtained by combining substructures N-1 and Ar'-10, wherein the U group is C(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The group is preferably derived from R 1 -2 and together form a ring system which is preferably in turn bonded to a structural unit obtainable by the combination of the substructures N-1 and Ar'-10, wherein these compounds have the following properties:

[0287]

[0288] In another configuration of the invention, preference is given to compounds obtained by combining substructures N-1 and Ar-10, wherein the U group is Si(R 1 ) 2 and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R 1 The groups preferably form structural units which can be obtained by combining the substructures N-1 and Ar-10, wherein these compounds have the following properties:

[0289]

[0290] In another configuration of the invention, preference is given to compounds obtained by the combination of substructures N-1 and Ar'-10, wherein the U group is Si(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The groups preferably form structural units which can be obtained by combining the substructures N-1 and Ar'-10, wherein these compounds have the following properties:

[0291]

[0292] In another configuration of the invention, preferred are compounds obtained by combining substructures N-1 and Ar-11, wherein the U group is C(R 1 ) 2 and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R 1 The group is preferably derived from R 1 -2 and together form a ring system which is preferably in turn bonded to a structural unit obtainable by the combination of substructures N-1 and Ar-11, wherein these compounds have the following properties:

[0293]

[0294] In another configuration of the invention, preference is given to compounds obtained by combining substructures N-1 and Ar'-11, wherein the U group is C(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The group is preferably derived from R 1 -2 and together form a ring system which is preferably in turn bonded to a structural unit obtainable by the combination of substructures N-1 and Ar'-11, wherein these compounds have the following properties:

[0295]

[0296] In another configuration of the invention, preference is given to compounds obtained by combining substructures N-1 and Ar-11, wherein the U group is Si(R 1 ) 2and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R 1 The groups preferably form structural units which can be obtained by combining the substructures N-1 and Ar-11, wherein these compounds have the following properties:

[0297]

[0298] In another configuration of the invention, preference is given to compounds obtained by the combination of substructures N-1 and Ar'-11, wherein the U group is Si(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The groups preferably form structural units which can be obtained by combining the substructures N-1 and Ar'-11, wherein these compounds have the following properties:

[0299]

[0300] In another configuration of the invention, preferred are compounds obtained by combining substructures N-1 and Ar-12, wherein the U group is C(R 1 ) 2 and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R 1 The group is preferably derived from R 1 -2 and together form a ring system which is preferably in turn bonded to a structural unit obtainable by the combination of the substructures N-1 and Ar-12, wherein these compounds have the following properties:

[0301]

[0302] In another configuration of the invention, preference is given to compounds obtained by the combination of substructures N-1 and Ar'-12, wherein the U group is C(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The group is preferably derived from R 1 -2 and together form a ring system, which is preferably in turn bonded to a structural unit obtainable by the combination of the substructures N-1 and Ar'-12, wherein these compounds have the following properties:

[0303]

[0304] In another configuration of the invention, preference is given to compounds obtained by combining substructures N-1 and Ar-10, wherein the U group is Si(R 1 ) 2 and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R 1 The groups preferably form structural units which can be obtained by combining the substructures N-1 and Ar-10, wherein these compounds have the following properties:

[0305]

[0306] In another configuration of the invention, preference is given to compounds obtained by the combination of substructures N-1 and Ar'-12, wherein the U group is Si(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The groups preferably form structural units which can be obtained by combining the substructures N-1 and Ar'-12, wherein these compounds have the following properties:

[0307]

[0308] In another configuration of the invention, preference is given to compounds obtained by combining the substructures N-1 and Ar-13, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0309]

[0310] In another configuration of the invention, preference is given to compounds obtained by combining the substructures N-1 and Ar'-13, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0311]

[0312] In another configuration of the invention, preference is given to compounds obtained by combining substructures N-1 and Ar-14, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, said compounds having the following properties:

[0313]

[0314] In another configuration of the invention, preference is given to compounds obtained by combining the substructures N-1 and Ar'-14, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0315]

[0316] In another configuration of the invention, preference is given to compounds obtained by combining substructures N-1 and Ar-15, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, said compounds having the following properties:

[0317]

[0318] In another configuration of the invention, preference is given to compounds obtained by combining the substructures N-1 and Ar'-15, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0319]

[0320] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar-23, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0321]

[0322] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar'-22, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0323]

[0324] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar-24, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0325]

[0326] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar'-23, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0327]

[0328] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar-25, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0329]

[0330] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar'-24, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0331]

[0332] In another configuration of the invention, preferred are compounds obtained by combining two substructures N-1 and one substructure Ar-33, wherein the U group is C(R 1 ) 2 and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R 1 The group is preferably derived from R 1 -2 and together form a ring system which is preferably in turn bonded to a structural unit obtainable by the combination of two substructures N-1 and one substructure Ar-33, wherein these compounds have the following properties:

[0333]

[0334] In another configuration of the invention, preferred are compounds obtained by combining two substructures N-1 and one substructure Ar'-32, wherein the U group is C(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The group is preferably derived from R 1-2 and together form a ring system, which is preferably in turn bonded to a structural unit obtainable by combining two substructures N-1 and one substructure Ar'-32, wherein these compounds have the following properties:

[0335]

[0336] In another configuration of the invention, preferred are compounds obtained by combining two substructures N-1 and one substructure Ar-33, wherein the U group is Si(R 1 ) 2 and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R 1 The radical preferably forms a structural unit which can be obtained by combining two substructures N-1 and one substructure Ar-33, wherein these compounds have the following properties:

[0337]

[0338] In another configuration of the invention, preference is given to compounds obtained by the combination of two substructures N-1 and one substructure Ar'-32, wherein the U group is Si(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The groups preferably form structural units which can be obtained by combining two substructures N-1 and one substructure Ar'-32, wherein these compounds have the following properties:

[0339]

[0340] In another configuration of the invention, preferred are compounds obtained by combining two substructures N-1 and one substructure Ar-34, wherein the U group is C(R 1 ) 2 and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R 1 The group is preferably derived from R 1 -2 and together form a ring system which is preferably in turn bonded to a structural unit obtainable by combining two substructures N-1 and one substructure Ar-34, wherein these compounds have the following properties:

[0341]

[0342] In another configuration of the invention, preferred are compounds obtained by combining two substructures N-1 and one substructure Ar'-33, wherein the U group is C(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The group is preferably derived from R 1 -2 and together form a ring system, which is preferably in turn bonded to a structural unit obtainable by combining two substructures N-1 and one substructure Ar'-33, wherein these compounds have the following properties:

[0343]

[0344] In another configuration of the invention, preference is given to compounds obtained by the combination of two substructures N-1 and one substructure Ar-34, wherein the U group is Si(R 1 ) 2 and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R 1 The radical preferably forms a structural unit which can be obtained by combining two substructures N-1 and one substructure Ar-34, wherein these compounds have the following properties:

[0345]

[0346] In another configuration of the invention, preference is given to compounds obtained by the combination of two substructures N-1 and one substructure Ar'-33, wherein the U group is Si(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The groups preferably form structural units which can be obtained by combining two substructures N-1 and one substructure Ar'-33, wherein these compounds have the following properties:

[0347]

[0348] In another configuration of the invention, preferred are compounds obtained by combining two substructures N-1 and one substructure Ar-35, wherein the U group is C(R 1 ) 2 and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R1 The group is preferably derived from R 1 -2 and together form a ring system, which is preferably in turn bonded to a structural unit obtainable by combining two substructures N-1 and one substructure Ar-35, wherein these compounds have the following properties:

[0349]

[0350] In another configuration of the invention, preferred are compounds obtained by combining two substructures N-1 and one substructure Ar'-34, wherein the U group is C(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The group is preferably derived from R 1 -2 and together form a ring system, which is preferably in turn bonded to a structural unit obtainable by a combination of two substructures N-1 and one substructure N-1 and Ar'-34, wherein these compounds have the following properties:

[0351]

[0352] In another configuration of the invention, preference is given to compounds obtained by the combination of two substructures N-1 and one substructure Ar-35, wherein the U group is Si(R 1 ) 2 and a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 radicals of the formula X' are not CH or CD, wherein two R 1 The radical preferably forms a structural unit which can be obtained by combining two substructures N-1 and one substructure Ar-35, wherein these compounds have the following properties:

[0353]

[0354] In another configuration of the invention, preference is given to compounds obtained by the combination of two substructures N-1 and one substructure Ar'-34, wherein the U group is Si(R 1 ) 2 and the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 2, wherein the indices v are particularly preferably 0, wherein the two R 1 The group preferably forms a structural unit which can be obtained by combining two substructures N-1 and one substructure N-1 and Ar'-34, wherein these compounds have the following properties:

[0355]

[0356] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar-36, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0357]

[0358] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar'-35, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0359]

[0360] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar-37, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0361]

[0362] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar'-36, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0363]

[0364] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar-38, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0365]

[0366] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar'-37, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0367]

[0368] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar-39, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0369]

[0370] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar'-38, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0371]

[0372] In another configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar-40, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0373]

[0374] In a further configuration of the invention, preference is given to compounds obtained by combining two substructures N-1 and one substructure Ar'-39, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0375]

[0376] In another configuration of the invention, preference is given to compounds obtained by combining four substructures N-1 and one substructure Ar-41, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0377]

[0378] In another configuration of the invention, preference is given to compounds obtained by combining four substructures N-1 and one substructure Ar'-40, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0379]

[0380] In another configuration of the invention, preference is given to compounds obtained by combining four substructures N-1 and one substructure Ar-42, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0381]

[0382] In another configuration of the invention, preference is given to compounds obtained by combining four substructures N-1 and one substructure Ar'-41, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0383]

[0384] In another configuration of the invention, preference is given to compounds obtained by combining four substructures N-1 and one substructure Ar-43, wherein a total of not more than 6, preferably not more than 4 and particularly preferably not more than 2 groups of the formula X' are not CH or CD, said compounds having the following properties:

[0385]

[0386] In another configuration of the invention, preference is given to compounds obtained by combining four substructures N-1 and one substructure Ar'-42, wherein the sum of the indices v, o and m is not greater than 5, preferably not greater than 3 and particularly preferably 1, wherein the indices v is particularly preferably 0, said compounds having the following properties:

[0387]

[0388] It may also be the case that the compounds which can be used as active compounds in organic electronic devices are not in direct contact with the metal atom and are preferably not ligands for metal complexes.

[0389] Examples of suitable compounds of the invention are the structures of Formulae 1 to 108 shown below:

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396]

[0397]

[0398]

[0399]

[0400] The structures of formulas 1 to 18 are particularly suitable as hole conductor materials (HTM) and may be suitable as electron blocking materials (EBM). The structures of formulas 1 to 33 are particularly suitable as triplet host materials (TMM), particularly suitable for phosphorescent emitters, and suitable as host materials for TADF compounds. The structures of formulas 34 to 45 are particularly suitable as wide bandgap materials. The structures of formulas 46 to 60 are particularly suitable as electron transport materials (ETM) or as electron conduction triplet host materials (eTMM). The structures of formulas 61 to 67 are particularly suitable as fluorescent emitter host materials (SMB). The structures of formulas 67 to 93 are particularly suitable as fluorescent emitters (SEB). The structures of formulas 94 to 105 are particularly suitable as emitters exhibiting TADF (thermally activated delayed fluorescence) and as highly fluorescent TADF compounds.

[0401] Preferred embodiments of the present invention are specifically exemplified in the examples, and these compounds can be used alone or in combination with other compounds for all purposes of the present invention.

[0402] The above-mentioned preferred embodiments can be combined with each other as needed as long as the conditions specified in claim 1 are met. In a particularly preferred embodiment of the present invention, the above-mentioned preferred embodiments are applicable simultaneously.

[0403] The compounds according to the invention can in principle be prepared by various methods. However, the methods described below have been found to be particularly suitable.

[0404] Therefore, the present invention further provides a process for preparing the compounds according to the invention, preferably compounds comprising structures of formula (I) to (XVIII), wherein, in a coupling reaction, a compound comprising at least one aliphatic polycyclic ring system having at least 3 rings is linked to a compound comprising at least one aromatic or heteroaromatic group.

[0405] Suitable compounds containing at least one aliphatic polycyclic ring system having at least 3 rings are commercially available in many cases, and the starting compounds detailed in the examples can be obtained by known methods, so reference can be made to known methods.

[0406] These compounds can be reacted with other compounds containing at least one aromatic or heteroaromatic group by known coupling reactions, the necessary conditions for this purpose being known to the person skilled in the art and the detailed description in the examples assisting the person skilled in the art in carrying out these reactions.

[0407] Particularly suitable and preferred coupling reactions, all leading to CC bond formation and / or CN bond formation, are those according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONGASHIRA and HIYAMA. These reactions are well known and these examples will provide further indications to those skilled in the art.

[0408] The principles of the preparation methods detailed above are known in principle from the literature for similar compounds and can be easily adapted by a person skilled in the art to prepare the compounds of the invention. Further information can be found in the examples.

[0409] By these methods, followed if necessary by purification, such as recrystallization or sublimation, a high purity, preferably greater than 99% (by 1 H NMR and / or HPLC) of the compounds of the present invention comprising the structures of Formula (I) to (XVIII).

[0410] The compounds of the invention may also have suitable substituents, for example by relatively long alkyl groups (about 4 to 20 carbon atoms), especially branched alkyl groups, or optionally substituted aryl groups such as xylyl, mesityl or branched terphenyl or quaterphenyl groups, which produce solubility in standard organic solvents, such that the compounds are soluble in toluene or xylene at room temperature, for example in sufficient concentration to enable the compounds to be processed from solution. These soluble compounds have particularly good suitability for processing from solution, for example by printing methods. In addition, it should be emphasized that the solubility of the compounds of the invention comprising at least one structure of formula (I) to (XVIII) in these solvents is already increased.

[0411] The compounds of the present invention can also be mixed with polymers. These compounds can also be covalently bound to polymers. Compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boric acid or boric esters or reactive polymerizable groups such as olefins or oxetanes are particularly suitable. These can be used as monomers for making corresponding oligomers, dendritic macromolecules or polymers. The oligomerization or polymerization is preferably achieved via halogen functionality or boric acid functionality or via polymerizable groups. It is also feasible to crosslink the polymers by this group. The compounds of the present invention and polymers can be used in the form of crosslinked or uncrosslinked layers.

[0412] The present invention therefore further provides oligomers, polymers or dendrimers containing one or more of the structures of formulae (I) to (XVIII) or compounds of the invention as described in detail above, wherein there are one or more bonds of the compounds of the invention or structures of formulae (I) to (XVIII) to said polymers, oligomers or dendrimers. According to said bonds of the structures of formulae (I) to (XVIII) or said compounds, they thus form side chains of the oligomers or polymers or are bonded within the main chain. The polymers, oligomers or dendrimers may be conjugated, partially conjugated or non-conjugated. The oligomers or polymers may be linear, branched or dendritic. For the repeating units of the compounds of the invention in the oligomers, dendrimers and polymers, the same preferences as above apply.

[0413] To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Preference is given to copolymers in which the units of the formulae (I) to (XVIII) or the preferred embodiments listed above and below are present in a range of 0.01 to 99.9 mol %, preferably 5 to 90 mol %, more preferably 20 to 80 mol %. Suitable and preferred comonomers forming the basic backbone of the polymer are selected from fluorene (for example according to EP 842208 or WO 2000 / 022026), spirobifluorene (for example according to EP 707020, EP 894107 or WO 2006 / 061181), p-phenylene (for example according to WO 92 / 18552), carbazole (for example according to WO 2004 / 070772 or WO 2004 / 113468), thiophene (for example according to EP 1028136), dihydrophenanthrene (for example according to WO 2005 / 014689), cis- and trans-indenofluorene (for example according to WO 2004 / 041901 or WO 2004 / 113412), ketone (for example according to WO 2005 / 040302), phenanthrene (for example according to WO 2004 / 070772 or WO 2004 / 113468), 2005 / 104264 or WO 2007 / 017066) or a combination of these units. The polymers, oligomers and dendrimers may also contain other units, such as hole transport units, especially those based on triarylamines, and / or electron transport units.

[0414] Of particular interest are also compounds according to the invention which are characterized by a high glass transition temperature. In particular in this regard, compounds according to the invention which can be used as active compounds in organic electronic devices are preferably compounds comprising structures of the formulae (I) to (XVIII) and / or (Ia) to (XVIIIa), or compounds obtainable by a combination of substructures of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), or the preferred embodiments listed above and below, whose glass transition temperature determined according to DIN 51005 (2005-08 edition) is at least 70° C., more preferably at least 110° C., even more preferably at least 125° C. and particularly preferably at least 150° C.

[0415] For processing the compounds of the invention from the liquid phase, for example by spin coating or by printing methods, formulations of the compounds of the invention are required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents may 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, dimethoxybenzene, alkanes, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenchone, 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, methyl benzoate, NMP, p-cymene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindan, or a mixture of these solvents.

[0416] Therefore, the present invention further provides a preparation comprising a compound of the present invention and at least one other compound. The other compound may be, for example, a solvent, in particular one of the above-mentioned solvents or a mixture of these solvents. Alternatively, the other compound may be at least one organic or inorganic compound also used in electronic devices, such as a luminescent compound, such as a fluorescent dopant, a phosphorescent dopant or a compound exhibiting TADF (thermally activated delayed fluorescence), in particular a phosphorescent dopant, and / or other matrix materials. The other compound may also be polymeric.

[0417] Therefore, the present invention further provides a composition comprising a compound of the present invention and at least one other organic functional material. The functional material is generally an organic or inorganic material introduced between the anode and the cathode. Preferably, the organic functional material is selected from: a fluorescent luminescent body, a phosphorescent luminescent body, a luminescent body exhibiting TADF (thermally activated delayed fluorescence), a host material, an electron transport material, an electron injection material, a hole conductor material, a hole injection material, an electron blocking material, a hole blocking material, a wide bandgap material and an n-type dopant.

[0418] Therefore, the present invention also relates to a composition comprising at least one compound of the present invention, preferably a compound comprising the structure of formula (I) to (XVIII) or the preferred embodiments listed above and below, and at least one other matrix material. According to a particular aspect of the present invention, the other matrix material has hole transport properties.

[0419] The present invention further provides a composition comprising at least one compound according to the invention, preferably a compound comprising at least one structure of the formula (I) to (XVIII) or the preferred embodiments listed above and below, and at least one wide bandgap material. Wide bandgap materials are understood to mean materials within the meaning of the disclosure of US 7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices.

[0420] Preferably, the further compound may have a band gap of 2.5 eV or more, preferably 3.0 eV or more, very preferably 3.5 eV or more.One way to calculate the band gap is via the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

[0421] The molecular orbitals of the material, in particular the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), their energy levels and the lowest triplet state T 1 The energy and lowest excited singlet state S 1The energy is determined by quantum chemical calculations. In order to calculate organic substances without metals, the geometry is first optimized by the "ground state / semi-empirical / default spin / AM1 / charge 0 / spin singlet" method. Subsequently, energy calculations are performed on the basis of the optimized geometry. This is performed using the "TD-SFC / DFT / default spin / B3PW91" method and the "6-31G (d)" basis set (charge 0, spin singlet). For metal-containing compounds, geometry optimization is performed by the "ground state / Hartree-Fock / default spin / LanL2MB / charge 0 / spin singlet" method. The energy calculation is performed similarly to the above-mentioned method for organic substances, except that the "LanL2DZ" basis set is used for metal atoms and the "6-31G (d)" basis set is used for ligands. From the energy calculation, the HOMO energy level HEh or the LUMO energy level LEh is obtained in units of Hartree. This was used to determine the HOMO and LUMO energy levels in electron volts, calibrated by cyclic voltammetry measurements as follows:

[0422] HOMO(eV)=((HEh*27.212)-0.9899) / 1.1206,

[0423] LUMO(eV)=((LEh*27.212)-2.0041) / 1.385.

[0424] In the sense of this application, these values ​​are to be regarded as the HOMO and LUMO energy levels of the material.

[0425] The lowest triplet state T 1 is defined as the energy of the triplet state with the lowest energy, which is evident from the described quantum chemical calculations.

[0426] The lowest excited singlet state S 1 is defined as the energy of the excited singlet state with the lowest energy, which is apparent from the described quantum chemical calculations.

[0427] The method described herein is independent of the software package used and always gives the same results. Examples of programs frequently used for this purpose are "Gaussian09W" (Gaussian Corporation) and Q-Chem 4.1 (Q-Chem Corporation).

[0428] The invention furthermore relates to a composition comprising at least one compound comprising the structure of the formulae (I) to (XVIII) or of the preferred embodiments listed above and below and at least one phosphorescent emitter. The term "phosphorescent emitter" is also understood to mean a phosphorescent dopant.

[0429] The term "doping agent" in a system comprising a matrix material and a doping agent is understood to mean the component with the smaller proportion in the mixture. Correspondingly, the term "matrix material" in a system comprising a matrix material and a doping agent is understood to mean the component with the larger proportion in the mixture.

[0430] Preferred phosphorescent dopants for use in matrix systems, preferably mixed-matrix systems, are the preferred phosphorescent dopants specified below.

[0431] The term "phosphorescent dopant" generally includes compounds in which light emission occurs via a spin-forbidden transition, for example from an excited triplet state or a state with a higher spin quantum number, such as a quintet state.

[0432] Suitable phosphorescent compounds (=triplet emitters) are especially compounds which, when suitably excited, emit light preferably in the visible region and which also 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, especially a metal with this atomic number. Preferably used 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. In the sense of the present invention, all emitting compounds containing the abovementioned metals are regarded as phosphorescent compounds.

[0433] Examples of the above-mentioned 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 2016124304, WO 2017032439, WO2018019687, WO 2018019688,WO 2018041769,WO 2018054798, WO 2018069196, WO2018069197, WO 2018069273.

[0434] In general, all phosphorescent complexes which are used according to the prior art for phosphorescent OLEDs and which are known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art will be able to use other phosphorescent complexes without inventive step.

[0435] Specific examples of phosphorescent dopants are listed in the following table:

[0436]

[0437]

[0438]

[0439]

[0440]

[0441]

[0442]

[0443] The above-mentioned compounds comprising the structures of the preferred embodiments of formula (I) to (XVIII) or as described above can preferably be used as active components in electronic devices. An electronic device is understood to mean any device comprising an anode, a cathode and at least one layer between the anode and the cathode, the layer comprising at least one organic compound or organometallic compound. The electronic device of the present invention therefore comprises an anode, a cathode and at least one intermediate layer containing at least one compound comprising the structure of formula (I). Preferred electronic devices are selected from the group consisting of organic electroluminescent devices (OLED, PLED), organic integrated circuits (O-IC), organic field effect transistors (O-FET), organic thin film transistors (O-TFT), organic light emitting transistors (O-LET), organic solar cells (O-SC), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQD), organic electrosensors, light emitting electrochemical cells (LEC), organic laser diodes (O-lasers) and organic plasma light emitting devices (DM Koller et al., Nature Photonics 2008, 1-4), preferably organic electroluminescent devices (OLED, PLED), especially phosphorescent OLEDs, which contain at least one compound comprising a structure of formula (I) in at least one layer. Particularly preferred are organic electroluminescent devices. The active components are usually organic or inorganic materials introduced between the anode and the cathode, such as charge injection, charge transport or charge blocking materials, but in particular luminescent materials and matrix materials.

[0444] A preferred embodiment of the present invention is an organic electroluminescent device. The organic electroluminescent device comprises a cathode, an anode and at least one emitting layer. In addition to these layers, it 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. At the same time, one or more hole transport layers may be p-doped, for example with metal oxides such as MoO 3 or WO 3 Or doped with (per)fluorinated electron-poor aromatic systems, and / or one or more electron transport layers may be n-doped. Interlayers may also be introduced between two emitting layers, which have, for example, exciton blocking functions and / or control the charge balance in the electroluminescent device. However, it should be noted that not every one of these layers necessarily needs to be present.

[0445] In this case, the organic electroluminescent device may contain one emitting layer, or it may contain a plurality of emitting layers. If a plurality of emitting layers are present, these emitting layers preferably have several emitting peaks generally between 380 nm and 750 nm, so that the overall result is white luminescence; in other words, a plurality of emitting compounds that can fluoresce or phosphoresce are used in the emitting layer. Particularly preferred are three-layer systems, in which the three layers exhibit blue, green and orange or red luminescence (for the basic structure, see, for example, WO 2005 / 011013); or systems with more than three emitting layers. In addition, tandem OLEDs are also preferred. The system may also be a mixed system in which one or more layers fluoresce and one or more other layers phosphoresce.

[0446] In a preferred embodiment of the invention, the organic electroluminescent device contains a compound of the invention, preferably a compound comprising the structure of the preferred embodiment described in detail above, as a matrix material in one or more luminescent layers, preferably as an electron-conducting matrix material, preferably in combination with other matrix materials, preferably hole-conducting matrix materials. In another preferred embodiment of the invention, the other matrix material is an electron-transporting compound. In yet another preferred embodiment, the other matrix material is a compound with a large band gap, which does not participate to a significant extent even if it participates in the hole and electron transport in the layer. The luminescent layer comprises at least one luminescent compound.

[0447] In a further particularly preferred embodiment of the invention, the organic electroluminescent device of the invention comprises a compound according to the invention, preferably a compound comprising the structures of the formulae (I) to (XVIII) or of the preferred embodiments detailed above, in a hole conductor layer or electron conductor layer.

[0448] Suitable matrix materials which can be used in combination with the compounds of the formula (I) to (XVIII) or according to the preferred embodiments are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, in particular monoamines, for example according to WO 2014 / 015935, carbazole derivatives, for example CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851, indolocarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 064376. 2008 / 056746, indenocarbazole derivatives, for example according to WO 2010 / 136109 and WO 2011 / 000455, azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP2005 / 347160, bipolar matrix materials, for example according to WO 2007 / 137725, silanes, for example according to WO 005 / 111172, borazolidines or boric acid esters, for example according to WO 2006 / 117052, triazine derivatives, for example according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes, for example according to EP 652273 or WO 2009 / 062578, siladiazolidine or siladiazolidine derivatives, for example according to WO 2010 / 054729, phosphodiazolidine derivatives, for example according to WO 2010 / 054730, bridged carbazole derivatives, for example according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107, WO 2011 / 088877 or WO 2012 / 143080, terphenylidene derivatives, for example according to WO 2012 / 048781, lactams, for example according to WO 2011 / 116865, WO 2011 / 137951 or WO 2013 / 064206, 4-spirocarbazole derivatives, for example according to WO 2014 / 094963 or WO 2015 / 192939, or dibenzofuran derivatives, for example according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608 or the as yet unpublished applications EP 16158460.2 and EP 16159829.7. Other phosphorescent emitters emitting at a shorter wavelength than the actual emitter may also be present as co-hosts in the mixture.

[0449] Preferred co-host materials are triarylamine derivatives, especially monoamines, indenocarbazole derivatives, 4-spirocarbazole derivatives, lactams, and carbazole derivatives.

[0450] Preferred triarylamine derivatives used as co-host materials with the compounds of the present invention are selected from the compounds of the following formula (TA-1):

[0451]

[0452] Among them, Ar 5 are identical or different at each occurrence and have 6 to 40 carbon atoms and may be replaced in each case by one or more R 2 Aromatic or heteroaromatic ring system substituted with a radical, wherein two or more adjacent R 2 The substituents may optionally form a monocyclic or polycyclic aliphatic ring system which may be substituted by one or more R 3 The symbol R 2 As defined above, in particular for formulae (I) to (XVIII). Preferably, Ar 5 is identical or different on each occurrence and is a radical having 5 to 24 and preferably 5 to 12 aromatic ring atoms and can be replaced in each case by one or more R 2 The aryl or heteroaryl groups are substituted but preferably unsubstituted.

[0453] Suitable Ar 5 Examples of radicals are selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, in particular branched terphenyl, quaterphenyl, in particular branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, indenocarbazolyl, 1-, 2-, 3- or 4-dibenzothiophenyl, and 1-, 2-, 3- or 4-carbazolyl, each of which may be substituted by one or more R 2 The group is substituted, but is preferably unsubstituted.

[0454] Preferably, Ar 5 The group is the same or different at each occurrence and is selected from the above R 1 -1 to R 1 -92 group, more preferably R 1 -1 to R 1 -54.

[0455] In a preferred embodiment of the compound of formula (TA-1), at least one Ar 5 The group is selected from biphenyl groups, which may be o-, m- or p-biphenyl groups. In another preferred embodiment of the compound of formula (TA-1), at least one Ar5 The group is selected from a fluorene group or a spirobifluorene group, wherein these groups can each be bonded to the nitrogen atom at the 1, 2, 3 or 4 position. In another preferred embodiment of the compound of formula (TA-1), at least one Ar 5 The group is selected from a benzylidene or biphenyl group, wherein the group is an ortho-, meta- or para-bonded group which is substituted by a dibenzofuran group, a dibenzothiophene group or a carbazole group, in particular a dibenzofuran group, wherein the dibenzofuran or dibenzothiophene group is bonded to the benzylidene or biphenyl group via the 1, 2, 3 or 4 position and wherein the carbazole group is bonded to the benzylidene or biphenyl group via the 1, 2, 3 or 4 position or via a nitrogen atom.

[0456] In a particularly preferred embodiment of the compound of formula (TA-1), one Ar 5 The group is selected from fluorene or spirobifluorene groups, especially 4-fluorene or 4-spirobifluorene groups, and one Ar 5 The group is selected from a biphenyl group, especially a p-biphenyl group, or a fluorene group, especially a 2-fluorene group, and the third Ar 5 The radical is selected from a p-phenylene radical or a p-biphenylene radical, which is substituted by a dibenzofuran radical, especially a 4-dibenzofuran radical, or a carbazole radical, especially an N-carbazole radical or a 3-carbazole radical.

[0457] Preferred indenocarbazole derivatives used as co-host materials together with the compounds of the present invention are selected from the compounds of the following formula (TA-2):

[0458]

[0459] Among them, Ar 5 and R 1 has the meanings given above, in particular for formula (I) and / or (TA-1). 5 A preferred embodiment of the group is the above structure R 1 -1 to R 1 -92, more preferably R 1 -1 to R 1 -54.

[0460] A preferred embodiment of the compound of formula (TA-2) is a compound of the following formula (TA-2a):

[0461]

[0462] Among them, Ar 5 and R 1 has the meanings given above, in particular for formula (I) and / or (TA-1). The two R bonded to the indene carbon atom 1The radicals here are preferably identical or different and are alkyl radicals having 1 to 4 carbon atoms, in particular methyl radicals, or aromatic ring systems having 6 to 12 carbon atoms, in particular phenyl radicals. More preferably, the two R 1 The group is a methyl group. It is also preferred that R bonded to the indenocarbazole basic skeleton in formula (TA-2a) 1 The substituent is H or a carbazole group which can be bonded to the indenocarbazole basic skeleton via the 1, 2, 3 or 4 position or via the nitrogen atom, in particular via the 3 position.

[0463] Preferred 4-spirocarbazole derivatives used as co-host materials together with the compounds of the present invention are selected from the compounds of the following formula (TA-3):

[0464]

[0465] Among them, Ar 5 and R 1 has the meanings given above, in particular for formula (I) and / or (TA-1). 5 A preferred embodiment of the group is the above structure R 1 -1 to R 1 -92, more preferably R 1 -1 to R 1 -54.

[0466] A preferred embodiment of the compound of formula (TA-3) is a compound of the following formula (TA-3a):

[0467]

[0468] Among them, Ar 5 and R 1 has the meanings given above, in particular for formula (I) and / or (TA-1). 5 A preferred embodiment of the group is the above structure R 1 -1 to R 1 -92, more preferably R 1 -1 to R 1 -54.

[0469] Preferred lactams used as co-host materials with the compounds of the present invention are selected from compounds of the following formula (LAC-1):

[0470]

[0471] Where R 1 has the definitions listed above, especially for formula (I).

[0472] A preferred embodiment of the compound of formula (LAC-1) is the compound of the following formula (LAC-1a):

[0473]

[0474] Where R 1 has the meanings given above, in particular for formula (I) or (XVIII). 1 It is preferred here that is identical or different on each occurrence and is H or has 5 to 40 aromatic ring atoms and may be replaced by one or more R 2 Aromatic or heteroaromatic ring system substituted with a radical, wherein R 2 may have the definitions given above, in particular for formulae (I) to (XVIII). Most preferably, the substituent R 1 selected from H and having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms and in each case substituted by one or more non-aromatic R 2 Suitable substituents R are substituted, but preferably unsubstituted, aromatic or heteroaromatic ring systems. 1 Examples of are selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophenyl, and 1-, 2-, 3- or 4-carbazolyl, each of which may be replaced by one or more R 2 The group is substituted, but preferably is unsubstituted. Suitable R 1 The structure is the same as above for R-1 to R-79, more preferably R 1 -1 to R 1 -The same structure as described in 51.

[0475] It is also preferred to use a plurality of different matrix materials as a mixture, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material. It is also preferred to use a mixture of a charge-transporting matrix material and an electrically inert matrix material which, even if it participates in charge transport, does not participate to a significant level, as described, for example, in WO 2010 / 108579.

[0476] Preference is also given to using a mixture of two or more triplet emitters together with a matrix. In this case, the triplet emitter with a shorter-wave emission spectrum serves as a co-matrix for the triplet emitter with a longer-wave emission spectrum.

[0477] More preferably, in a preferred embodiment, the compounds of the present invention comprising the structures of formula (I) to (XVIII) can be used as a matrix material in the light-emitting layer of an organic electronic device, in particular an organic electroluminescent device, such as an OLED or OLEC. In this case, the matrix material containing the compound comprising the structure of formula (I) to (XVIII) or the preferred embodiments listed above and below is present in the electronic device in combination with one or more dopants, preferably phosphorescent dopants.

[0478] 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.

[0479] Accordingly, the proportion of the dopant 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 emitting layer, and between 3.0% and 15.0% by volume for the phosphorescent emitting layer.

[0480] The light-emitting layer of the organic electroluminescent device may also comprise a system containing a plurality of matrix materials (mixed matrix system) and / or a plurality of dopants. Also in this case, the dopants are usually those materials with a smaller proportion in the system, and the matrix materials are those materials with a larger proportion in the system. However, in individual cases, the proportion of a single matrix material in the system may be less than the proportion of a single dopant.

[0481] In another preferred embodiment of the present invention, the compound comprising the structure of the preferred embodiment of formula (I) to (XVIII) or the context is used as a component of a mixed matrix system. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material with hole transport properties, and the other material is a material with electron transport properties. However, the desired 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 other one or more mixed matrix components perform other functions. The 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. A source of more detailed information about mixed matrix systems is application WO 2010 / 108579.

[0482] The invention further provides an electronic device, preferably an organic electroluminescent device, comprising one or more compounds according to the invention and / or at least one oligomer, polymer or dendrimer according to the invention as electron-conducting compound in one or more electron-conducting layers.

[0483] The preferred cathode is a metal, metal alloy or multilayer structure with a low work function, the metal alloy or multilayer structure being composed of a variety of metals such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). In addition, an alloy consisting of an alkali metal or alkaline earth metal and silver, such as an alloy consisting of magnesium and silver, is suitable. In the case of a multilayer structure, in addition to the metals mentioned, other metals with a relatively high work function, such as Ag, can also be used, in which case a combination of the metals such as Mg / Ag, Ca / Ag or Ba / Ag is usually used. A thin intermediate layer of a material with a high dielectric constant can also be preferably introduced between the metal cathode and the organic semiconductor. Examples of useful materials for this purpose are fluorides of alkali metals or alkaline earth metals, and corresponding oxides or carbonates (e.g. LiF, Li 2 O, BaF 2 、MgO、NaF、CsF、Cs 2 CO 3 etc.). Also useful for this purpose are organic alkali metal complexes such as Liq (lithium quinolate). The layer thickness of the layer is preferably between 0.5 nm and 5 nm.

[0484] Preferred anodes are materials with a high work function. Preferably, the anode has a work function of greater than 4.5 eV relative to vacuum. Firstly, metals with a high redox potential, such as Ag, Pt or Au, are suitable for this purpose. 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 enable the illumination of organic materials (O-SC) or the emission of light (OLED / PLED, O-laser). Preferred anode materials are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Furthermore preferred are conductive doped organic materials, in particular conductive doped polymers, such as PEDOT, PANI or derivatives of these polymers. It is also preferred that a p-doped hole transport material is applied to the anode as a hole injection layer, in which case suitable p-dopants are metal oxides, such as MoO 3 or WO 3, or (per)fluorinated electron-poor aromatic systems. Other suitable p-type dopants are HAT-CN (hexacyanohexaazaterphenylidene) or the compound NPD9 from Novaled. Such a layer simplifies hole injection in materials with a low HOMO, ie with a HOMO that is large in magnitude.

[0485] In the other layers, generally any materials as used in the prior art for said layers can be used and a person skilled in the art will be able to combine any of these materials with the materials of the invention in an electronic device without inventive step.

[0486] Since the lifetime of such components is severely shortened in the presence of water and / or air, the components are structured accordingly (depending on the application), provided with contact connections and finally hermetically sealed.

[0487] Also preferred is an electronic device, in particular an organic electroluminescent device, characterized in that one or more layers are applied by a sublimation process. In this case, the sublimation reaction is carried out in a vacuum sublimation system at a temperature of typically less than 10 -5 mbar, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of 10 mbar. The initial pressure can also be even lower or even higher, for example less than 10 -7 millibar.

[0488] Likewise preferred is an electronic device, in particular an organic electroluminescent device, characterized in that one or more layers are applied by the OVPD (organic vapor phase deposition) method or by sublimation with the aid of a carrier gas. -5 The material is applied at a pressure between mbar 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 (eg MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0489] Also preferred are electronic devices, especially organic electroluminescent devices, as described below, 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, offset printing or nozzle printing, but more preferably LITI (light-induced thermal imaging, thermal transfer) or inkjet printing. For this purpose, soluble compounds are required, which are obtained, for example, by appropriate substitution.

[0490] Electronic devices, in particular organic electroluminescent devices, can also be manufactured as hybrid systems by applying one or more layers from a solution and applying one or more other layers by vapor deposition. For example, a light-emitting layer comprising a compound of the invention having a structure of formula (I) to (XVIII) and a matrix material can be applied from a solution, and a hole blocking layer and / or an electron transport layer can be applied thereto by vapor deposition under reduced pressure.

[0491] These methods are generally known to those skilled in the art and can be applied without difficulty to electronic devices, especially organic electroluminescent devices, comprising compounds of the invention having structures comprising formulae (I) to (XVIII) or the preferred embodiments detailed above.

[0492] It is noteworthy that the electronic device of the present invention, especially the organic electroluminescent device, is superior to the prior art in one or more of the following surprising advantages:

[0493] 1. Electronic devices, in particular organic electroluminescent devices, which contain the compounds according to the invention, oligomers, polymers or dendrimers or the preferred embodiments listed above and below as active compounds in organic electronic devices, especially as electron-conducting materials and / or hole-conducting materials or as matrix materials, have very good lifetimes.

[0494] 2. Electronic devices, in particular organic electroluminescent devices, comprising the compounds, oligomers, polymers or dendrimers according to the invention or the preferred embodiments listed above and below, which can be used as active compounds in organic electronic devices, especially as electron transport materials, hole conductor materials and / or as host materials, have excellent efficiency. More particularly, the efficiency is significantly higher than similar compounds that do not contain an aliphatic polycyclic ring system having at least 3 rings and fused to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms. The effect of the compounds, oligomers, polymers or dendrimers according to the invention or the preferred embodiments listed above and below, which can be used as active compounds in organic electronic devices, is that the operating voltage is low when used in electronic devices. In this case, these compounds in particular produce a low roll-off, i.e. the power efficiency of the device decreases less at high brightness.

[0495] 3. An electronic device, in particular an organic electroluminescent device, comprising a compound, oligomer, polymer or dendrimer useful as an active compound in an organic electronic device or the preferred embodiments listed above and below as an electron transport material, hole conductor material and / or as a host material, having excellent color purity.

[0496] 4. The compounds, oligomers, polymers or dendrimers according to the invention or the preferred embodiments listed above and below, which can be used as active compounds in organic electronic devices, exhibit very high thermal and photochemical stability, resulting in compounds having very long lifetimes.

[0497] 5. By using the compounds, oligomers, polymers or dendrimers that can be used as active compounds in organic electronic devices or the preferred embodiments listed above and below, the formation of light loss channels in electronic devices, especially organic electroluminescent devices, can be avoided. As a result, these devices are characterized by high PL efficiency of the emitter and the resulting high EL efficiency, as well as excellent energy transfer from the host to the dopant.

[0498] 6. A compound, oligomer, polymer or dendrimer useful as an active compound in an organic electronic device or the preferred embodiments listed above and below, having excellent glass film forming properties.

[0499] 7. Compounds, oligomers, polymers or dendrimers useful as active compounds in organic electronic devices or the preferred embodiments listed above and below, forming good films from solution.

[0500] These aforementioned advantages are not accompanied by degradation of other electronic properties.

[0501] The compounds and mixtures according to the invention are suitable for use in electronic devices. An electronic device is understood here to mean a device which comprises at least one layer which contains at least one organic compound. However, the component may also comprise inorganic materials or layers which are formed completely from inorganic materials.

[0502] The present invention therefore further provides for the use of the compounds or mixtures according to the invention in electronic devices, especially in organic electroluminescent devices.

[0503] The present invention further provides the use of the compounds of the present invention and / or the oligomers, polymers or dendrimers of the present invention as fluorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole conduction materials, hole injection materials, electron blocking materials, hole blocking materials and / or wide band gap materials in electronic devices, preferably as fluorescent emitters (singlet emitters), host materials, hole conduction materials and / or electron transport materials.

[0504] The present invention further provides an electronic device comprising at least one of the compounds or mixtures of the present invention described in detail above. In this case, the preferred embodiments described above for the compounds also apply to the electronic device. More preferably, the electronic device is selected from: organic electroluminescent devices (OLED, PLED), organic integrated circuits (O-IC), organic field effect transistors (O-FET), organic thin film transistors (O-TFT), organic light emitting transistors (O-LET), organic solar cells (O-SC), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQD), organic electrical sensors, light emitting electrochemical cells (LEC), organic laser diodes (O-lasers) and organic plasma light emitting devices (DM Koller et al., Nature Photonics (Nature Photonics) 2008, 1-4), preferably organic electroluminescent devices (OLED, PLED), especially phosphorescent OLED.

[0505] In another embodiment of the invention, the organic electroluminescent device of the invention does not contain any separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, which means that the light-emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. In addition, metal complexes identical or similar to the metal complexes in the light-emitting layer can be used as hole transport or hole injection materials directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0506] 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 use all materials known for organic electroluminescent devices with compounds of the present invention that can be used as active compounds in organic electronic devices, preferably compounds containing structures of formula (I) to (XVIII) and / or formula (Ia) to (XVIIIa), or compounds obtainable by combining substructures of formula (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), or compounds according to preferred embodiments without inventive effort.

[0507] The compounds of the invention generally have very good properties when used in organic electroluminescent devices. In particular, when the compounds of the invention are used in organic electroluminescent devices, the lifetime is significantly better than similar compounds of the prior art. At the same time, other properties of the organic electroluminescent device, in particular efficiency and voltage, are also better or at least comparable.

[0508] It should be noted that variations of the embodiments described in the present invention are covered by the scope of the present invention. Unless explicitly excluded, any feature disclosed in the present invention can be replaced with an alternative feature serving the same purpose or an equivalent or similar purpose. Therefore, unless otherwise specified, any feature disclosed in the present invention should be considered as an example of a generic series or as an equivalent or similar feature.

[0509] All features of the present invention can be combined with each other in any way, unless specific features and / or steps are mutually exclusive. This is especially true for the preferred features of the present invention. Similarly, features of non-essential combinations can be used separately (without combination).

[0510] It should also be noted that many features, especially those of the preferred embodiments of the invention, should be considered creative in themselves, rather than just as some embodiments of the invention. For these features, independent protection may be sought to supplement or replace any currently claimed invention.

[0511] The technical teachings disclosed in the present invention may be extracted and combined with other examples. DETAILED DESCRIPTION

[0512] The following examples illustrate the present invention in more detail without any intention to limit the present invention thereto.

[0513] A person skilled in the art will be able, using the detailed information given, to produce other electronic devices of the invention without inventive step and thus to implement the invention within the entire scope of the claims.

[0514] Example

[0515] Unless otherwise stated, the following syntheses were carried out in dry solvents under a protective gas atmosphere. The metal complexes were additionally handled in dark or under yellow light. Solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. For individual compounds, the corresponding numbers or reference numbers in square brackets are related to the CAS number of the compound known from the literature. In the case of compounds that can show multiple tautomeric forms, one tautomeric form is representatively shown.

[0516] 1) Synthesis of synthon S:

[0517] Embodiment S1:

[0518]

[0519] 27.2 g (100 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethyl-5H-benzocyclononene [1801624-97-4], 32.4 g (100 mmol) of 2-(6,7,8,9,10,11-hexahydro-5,9:7,11-dimethyl-5H-benzocyclononene-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1801624-63-4], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium (II) acetate, 350 ml of toluene, 80 ml of dioxaborolane were added. A well-stirred mixture of oxane and 300 ml of water was heated under reflux for 16 hours. After cooling, the organic phase was separated from the aqueous phase and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and then dried over magnesium sulfate. The desiccant was filtered off using a silica gel bed in the form of a toluene slurry and the filtrate was concentrated to dryness. The glassy residue was recrystallized from isopropanol. Yield: 30.8 g (78 mmol) 78%. By 1 The purity was about 97% as determined by H NMR.

[0520] In a similar manner, the following compounds can be prepared:

[0521]

[0522] Example S2:

[0523]

[0524] To a well-stirred solution of 39.5 g (100 mmol) of S1 in 500 ml of dichloromethane is added dropwise a mixture of 3.1 ml (120 mmol) of bromine and 100 ml of dichloromethane over the course of 3 h in the dark. After the addition is complete, the mixture is stirred under reflux for 4 h and at room temperature for 8 h. 200 ml of saturated sodium sulfite solution are added to destroy the excess bromine, the organic phase is separated, washed with 500 ml of water and 300 ml of saturated sodium bicarbonate solution and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness and the red viscous residue is recrystallized from about 500 ml of isopropanol. Yield: 32.7 g (69 mmol) 69%. By 1 The purity determined by H NMR was about 95%.

[0525] The following compounds can be prepared similarly:

[0526]

[0527] Example S3:

[0528]

[0529] Preparation was similar to S2, except that 6.4 ml (240 mmol) bromine was used. 100 mg iron powder was also added to the dichloromethane solution of S1. Yield: 33.7 g (61 mmol) 61%. 1 The purity determined by H NMR was about 97%.

[0530] The following compounds can be prepared similarly:

[0531]

[0532]

[0533] Example S4:

[0534]

[0535] To a well-stirred solution of 27.6 g (50 mmol) S3 in 500 ml THF cooled to -78 ° C was added 65.6 ml (105 mmol) of 1.6 M n-BuLi in hexane, and the mixture was stirred for another 30 minutes. A mixture of 5.1 ml (55 mmol) dimethylaminoformyl chloride [79-44-7] (Caution: toxic, carcinogenic) and 50 ml THF was slowly added, and the mixture was stirred for another 30 minutes, and then gradually warmed to room temperature. After 2 hours at room temperature, 200 ml of saturated ammonium chloride solution was added, the mixture was expanded with 300 ml of ethyl acetate, the aqueous phase was separated, and the organic phase was concentrated to dryness. The residue was dissolved in 250 ml of dichloromethane (DCM), washed three times with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant was filtered out, the filtrate was concentrated to dryness under reduced pressure, and the residue was recrystallized from acetonitrile. Yield: 18.1 g (43 mmol) 85%. 1 The purity determined by H NMR was about 97%.

[0536] Embodiment S5:

[0537]

[0538] To a well-stirred solution of 47.4 g (100 mmol) of S2 in 500 ml of THF cooled to -78°C was added 65.6 ml (105 mmol) of a 1.6 M solution of n-BuLi in hexane, and the mixture was stirred for a further 3 hours. Then a solution of 27.2 g (105 mmol) of 2-bromo-9-fluorenone [3096-56-3] in 300 ml of THF was slowly added dropwise, and the mixture was stirred for a further 30 minutes and then allowed to gradually warm to room temperature. After 2 hours at room temperature, THF was removed under reduced pressure, the residue was dissolved in 500 ml of glacial acetic acid, 30 ml of concentrated hydrochloric acid was added, and the mixture was heated at reflux for 3 hours. The mixture was cooled to 80°C, 500 ml of water was slowly added dropwise, and the precipitated product was filtered off with suction while the mixture was still warm, washed with 100 ml of water, then three times with 100 ml of methanol each time, and dried under reduced pressure. Yield: 56.6 g (89 mmol) 89%. By 1 The purity determined by H NMR was about 97%.

[0539] In a similar manner, the following compounds can be prepared.

[0540]

[0541]

[0542] Embodiment S20:

[0543]

[0544] 28.3 g (100 mmol) of (2-bromo-4-chlorophenyl)phenylamine [2149611-39-0], 32.4 g (100 mmol) of 2-(6,7,8,9,10,11-hexahydro-5,9:7,11-dimethylbridge-5H-benzocyclononen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1801624-63-4], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium (II) acetate, 350 ml of toluene, and 60 ml of distilled water were added. The fully stirred mixture of alkane and 300ml of water was refluxed for 16 hours. After cooling, the organic phase was separated from the aqueous phase and washed once with 300ml of water and once with 300ml of saturated sodium chloride solution, then dried over magnesium sulfate. The desiccant was filtered out using a silica gel bed in the form of toluene slurry, and the filtrate was concentrated to dryness. The residue was recrystallized from acetonitrile to which a small amount of ethyl acetate was added. The secondary amine thus obtained was dissolved in 300ml of DMF, 45.4g (250mmol) of copper acetate (II) and 2.24g (10mmol) of palladium acetate (II) were added, and the mixture was stirred at 140°C for 4 hours. Most of the DMF was removed under reduced pressure, the residue was dissolved in 500ml of DCM, 300ml of concentrated ammonia solution was added, the mixture was stirred at room temperature for 1 hour, the organic phase was separated, washed three times with 100ml of concentrated ammonia solution and once with a saturated sodium chloride solution, and dried over magnesium sulfate. The magnesium sulfate was filtered off as a DCM slurry using a silica gel bed, the filtrate was concentrated to dryness and the residue was recrystallized from acetonitrile / ethyl acetate. Yield: 18.7 g (47 mmol) 47%. 1 The purity determined by H NMR was about 95%.

[0545] Embodiment S25:

[0546]

[0547] A well-stirred mixture of 27.2 g (100 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethyl-5H-benzocyclononene [1801624-97-4], 18.4 g (110 mmol) of carbazole [86-74-8], 41.5 g (300 mmol) of potassium carbonate, 1.9 g (10 mmol) of copper (I) iodide [7681-65-4], 100 g of glass beads (3 mm in diameter) and 300 ml of dimethylacetamide was heated under reflux for 30 hours. While the mixture was still warm, the salts were filtered off by suction as a dimethylacetamide slurry over a diatomaceous earth bed, the filtrate was concentrated to dryness, the residue was dissolved in 300 ml of DCM and filtered through a silica gel column (10×30 cm) to extract the core fraction. DCM was removed under reduced pressure; the residue was recrystallized from acetonitrile. Yield: 33.4 g (88 mmol) 88%. 1 The purity was determined to be about 99% by H NMR.

[0548] Embodiment S26:

[0549]

[0550] To a well-stirred solution of 38.0 g (100 mmol) S25 in 500 ml DCM cooled to 0° C., 17.8 g (100 mmol) of a solution of N-bromosuccinimide in 300 ml of dichloromethane were added dropwise in the dark, and the mixture was then stirred for a further 12 hours at room temperature. Wash once with 200 ml of saturated sodium bicarbonate solution, three times with 200 ml of water each time and once with 200 ml of saturated sodium chloride solution, and then dry over magnesium sulfate. The desiccant was filtered off, the filtrate was concentrated and the residue was chromatographed by flash chromatography (Combi-Flash Torrent, A. Semrau). Yield: 33.0 g (72 mmol) 72%. By 1 The purity determined by H NMR was about 95%.

[0551] Embodiment S30:

[0552]

[0553] A well-stirred mixture of 17.3 g (100 mmol) of 2-bromophenol [95-96-7], 32.4 g (100 mmol) of 2-(6,7,8,9,10,11-hexahydro-5,9:7,11-dimethyl-5H-benzocyclononen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1801624-63-4], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium (II) acetate, 350 ml of toluene, 60 ml of ethanol and 300 ml of water was heated under reflux for 16 hours. After cooling, add 60ml of 10N HCl aqueous solution, separate the organic phase from the aqueous phase and wash once with 300ml water and once with 300ml saturated sodium chloride solution, then dry over magnesium sulfate. Use silica gel bed to filter out the desiccant in the form of toluene slurry, and concentrate the filtrate to dryness. Residue is recrystallized from isopropanol adding a small amount of ethyl acetate. The phenol thus obtained is dissolved in 800ml of mesitylene, and the well-stirred solution is mixed with 27.6g (200mmol) of potassium carbonate, 100g of 3A molecular sieves, 9.3g (50mmol) of 2,4,6-trimethylbenzoic acid sodium [32642-28-7], 1.82g (10mmol) of 4,5-diazafluorene-9-one [50890-67-0], 4.26g (10mmol) of 1,3-bis [2,6-bis (1-methylethyl) phenyl] -1H-imidazole chloride [250285-32-6] and 1.12 g (5 mmol) of palladium (II) acetate were mixed and the mixture was then heated to 120° C. for 16 hours while introducing a gentle air stream. While the mixture was still warm, it was filtered through a silica gel bed as a mesitylene slurry with suction, the mesitylene was removed under reduced pressure, and the residue was recrystallized from acetonitrile. Yield: 15.6 g (54 mmol) 54%. By 1 The purity determined by H NMR was about 95%.

[0554] Embodiment S31:

[0555]

[0556] To a well-stirred mixture of 33.2 g (100 mmol) S30 and 500 ml THF cooled to -78°C was added dropwise 65.6 ml (105 mmol) of a 1.6 M solution of n-BuLi in hexane, and the mixture was stirred at -78°C for 60 minutes and then at -40°C for 30 minutes. After cooling to -78°C again, a mixture of 20.7 g (110 mmol) triisopropyl borate [5419-55-6] and 50 ml THF was added rapidly with well-stirred addition, and the mixture was stirred for a further 30 minutes. The reaction mixture was warmed to room temperature, 100 ml saturated ammonium chloride solution was added, the mixture was stirred for a further 15 minutes, the organic phase was separated, it was expanded with 500 ml ethyl acetate, washed three times with 300 ml water each time and once with 200 ml saturated sodium chloride solution. The organic phase was concentrated to dryness under reduced pressure, and the residue was recrystallized from acetonitrile to which a small amount of water was added. Yield: 18.9 g (57 mmol), 57%. 1 The purity determined by H NMR was about 95%.

[0557] Embodiment S35:

[0558]

[0559] A well-stirred mixture of 35.6 g (100 mmol) of 2,3-dibromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethyl-5H-benzocyclononene [1801624-66-7], 26.9 g (300 mmol) of copper (I) cyanide, 50 g of glass beads (3 mm in diameter) and 300 NMP is heated to 170° C. for 18 hours. While the mixture is still warm, it is filtered through a diatomaceous earth bed in the form of an NMP slurry with suction, the filtrate is concentrated to dryness under reduced pressure, and the residue is extracted by stirring in 300 ml of boiling MeOH. The crude product is extracted twice with hot acetonitrile. Yield: 15.0 g (60 mmol) 60%. By 1The purity determined by H NMR was about 95%.

[0560] Embodiment S36:

[0561]

[0562] To a well-stirred solution of 35.6 g (100 mmol) of 2,3-dibromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethylbridge-5H-benzocyclononene [1801624-66-7] in 1000 ml of THF cooled to -100°C was added 235 ml (400 mmol) of a 1.7 M t-BuLi solution in pentane, and the mixture was stirred for a further 30 minutes. A solution of 24.8 g (100 mmol) of S35 in 300 ml of THF was then slowly added dropwise, and the mixture was stirred for a further hour, allowed to warm to room temperature and quenched by adding 50 ml of methanol. THF was removed under reduced pressure, the residue was dissolved in 300 ml of NMP, 30 ml of concentrated hydrochloric acid was added, and the mixture was heated to about 150°C for 4 hours. After cooling, the mixture was expanded with 500 ml of ethyl acetate, the organic phase was washed three times with 500 ml of water each time and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The desiccant was filtered off, the filtrate was concentrated to dryness under reduced pressure, and the yellow residue was recrystallized twice from acetonitrile. Yield: 19.4 g (43 mmol) 43%. 1 The purity determined by H NMR was about 95%.

[0563] In a similar manner, the following compounds can be prepared.

[0564]

[0565] Embodiment S38:

[0566]

[0567] To a suspension of 44.9 g (100 mmol) of S36 in 500 ml of glacial acetic acid were added 100 ml of aqueous hydroiodic acid (57% by weight) and 200 ml of aqueous hypophosphorous acid (50% by weight), and the mixture was heated under reflux for 18 hours. The precipitated solid was filtered off by suction, washed 5 times with 300 ml of hot water each time, extracted by stirring with 300 ml of hot ethanol, washed with 300 ml of hot ethanol and dried under reduced pressure. Yield: 38.6 g (92 mmol) 92%. 1 The purity determined by H NMR was about 95%.

[0568] The following compounds can be prepared similarly:

[0569]

[0570] Embodiment S40:

[0571]

[0572] To a solution of 41.9 g (100 mmol) of S38 in 500 ml of dichloromethane are added 19.6 g (110 mmol) of N-bromosuccinimide in portions with sufficient stirring and in the dark, and the mixture is stirred at room temperature for 6 hours. The reaction mixture is washed once with 300 ml of saturated sodium bicarbonate solution, three times with 300 ml of water each time, and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness, and the solid is crystallized from acetonitrile / ethyl acetate. Yield: 50.2 g (87 mmol) 87%. 1 The purity determined by H NMR was about 98%.

[0573] The following compounds can be prepared similarly:

[0574]

[0575] 2) Synthesis of amine A:

[0576] Example A1

[0577]

[0578] To a solution of 63.6 g (100 mmol) of S5 and 38.6 g (120 mmol) of di-p-benzidine [102113-98-4] in 500 ml of toluene was added 4.0 ml (4.0 mmol) of a 1.0 M toluene solution of tri-tert-butylphosphine, 449 mg (2 mmol) of palladium acetate and 16.0 g of sodium tert-butoxide (166 mmol), and the mixture was heated at reflux for 3 hours. The reaction mixture was cooled to room temperature, increased with toluene and filtered through a diatomaceous earth bed. The filtrate was concentrated under reduced pressure and the residue was crystallized from ethyl acetate / n-heptane. The crude product was extracted three times with hot acetonitrile and purified by vacuum zone sublimation (p ~ 10 -5 mbar, T-310°C) were purified twice. Yield: 63.1 g (72 mmol), 72%. Purity determined by HPLC>99.9%.

[0579] The following compounds can be prepared similarly:

[0580]

[0581]

[0582]

[0583]

[0584]

[0585]

[0586] Embodiment A22:

[0587]

[0588] 63.6 g (100 mmol) of S5, 57.6 g (110 mmol) of N-[1,1'-biphenyl]-2-yl-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-[1,1'-biphenyl]-4-amine [1608462-54-9], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium (II) acetate, 500 ml of toluene, and 100 ml of distilled water were added. A well-stirred mixture of 1,2-dioxane and 400 ml of water was heated under reflux for 16 hours. After cooling, the organic phase was separated from the aqueous phase and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, then dried over magnesium sulfate. The desiccant was filtered out using a silica gel bed in the form of a toluene slurry, and the filtrate was concentrated to dryness. The glassy residue was recrystallized from ethyl acetate / isopropanol. The crude product was extracted three times with hot toluene and sublimed by reduced pressure zonal sublimation (p ~ 10 -5 mbar, T-330°C) were purified twice. Yield: 66.8 g (70 mmol), 70%. Purity determined by HPLC>99.9%.

[0589] The following compounds can be prepared similarly:

[0590]

[0591]

[0592] 3) Synthesis of carbazole C:

[0593] Example C1:

[0594]

[0595] 44.2 g (100 mmol) of S26, 36.9 g (100 mmol) of 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole [1126522-69-7], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium (II) acetate, 350 ml of toluene, and 80 ml of distilled water were added. A well-stirred mixture of 1,2-dioxane and 300 ml of water was heated under reflux for 16 hours. After cooling, the aqueous phase was separated and the organic phase was concentrated to dryness. The residue was dissolved in 500 ml of DCM and the organic phase was washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and then dried over magnesium sulfate. The desiccant was filtered out using a silica gel bed in the form of a DCM slurry and the filtrate was concentrated to dryness. The residue was extracted with hot butyl acetate / isopropanol by stirring, then extracted three times with hot toluene and sublimed by reduced pressure zoning (p~10 -5 mbar, T~320°C). Yield: 40.0 g (66 mmol), 66%. Purity determined by HPLC>99.9%.

[0596] The following compounds can be prepared similarly:

[0597]

[0598]

[0599]

[0600] 4) Synthesis of Triazine T: Example T1:

[0601]

[0602] 42.0 g (100 mmol) of (2,4-bis([1,1'-biphenyl]-3-yl)-6-chloro-1,3,5-triazine [1205748-61-3], 32.4 g (100 mmol) of 2-(6,7,8,9,10,11-hexahydro-5,9:7,11-dimethyl-5H-benzocyclononen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1801624-63-4], 31.9 g (150 mmol) of tripotassium phosphate, 821 mg (2 mmol) of S-Phos, 225 mg (1 mmol) of palladium (II) acetate), 400 ml of toluene, 80 ml of distilled water were added. A well-stirred mixture of 1,2-dioxane and 300 ml of water was heated under reflux for 16 hours. After cooling, the organic phase was separated from the aqueous phase and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, then dried over magnesium sulfate. The desiccant was filtered out using a silica gel bed in the form of a toluene slurry, and the filtrate was concentrated to dryness. The residue was extracted with hot isopropanol by stirring, then extracted five times with hot acetonitrile and sublimed by reduced pressure zonal sublimation (p ~ 10 -5 mbar, T~310°C). Yield: 37.8 g (65 mmol), 65%. Purity determined by HPLC>99.9%.

[0603] The following compounds can be prepared similarly:

[0604]

[0605]

[0606] 5) Synthesis of host materials for singlet luminophore SH:

[0607] Example SH1:

[0608]

[0609] 45.6 g (100 mmol) of S41, 37.8 g (220 mmol) of 1-naphthylboronic acid [13922-41-3], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium (II) acetate, 400 ml of toluene, 80 ml of distilled water, and 100 ml of ethanol were added. A well-stirred mixture of 1,2-dioxane and 300 ml of water was heated under reflux for 16 hours. After cooling, the aqueous phase was separated and the organic phase was concentrated to dryness. The residue was dissolved in 500 ml of DCM and the organic phase was washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and then dried over magnesium sulfate. The desiccant was filtered out using a silica gel bed in the form of a DCM slurry and the filtrate was concentrated to dryness. The residue was extracted with hot butyl acetate / isopropanol by stirring, then extracted five times with hot toluene and sublimed by reduced pressure zoning (p~10 -5 mbar, T~320°C). Yield: 31.9 g (58 mmol), 58%, mixture of cis / trans isomers. Purity determined by HPLC>99.9%.

[0610] 6) Synthesis of singlet luminophore S:

[0611] Example SE1:

[0612]

[0613] The procedure was similar to A1, except that 28.8 g (50 mmol) of S40 and 31.0 g (110 mmol) of 4-(1,1-dimethylethyl)-N-[4-(1,1-dimethylethyl)phenyl]phenylamine [4627-22-9] were used instead of S5. The product was prepared by five thermal extractions with cyclohexane and zoned sublimation under reduced pressure (p ~ 10 -5 mbar, T~330°C). Yield: 26.0 g (53 mmol) 53%. Purity determined by HPLC>99.9%.

[0614] The following compounds can be prepared similarly:

[0615]

[0616]

[0617] 7) Synthesis of spirocyclic material H:

[0618] The following compounds can be prepared similarly to S5:

[0619]

[0620] Fabrication of OLED devices

[0621] 1) Vacuum processed devices:

[0622] The OLEDs according to the invention and the OLEDs of the prior art are produced by the general method according to WO 2004 / 058911, which is adjusted to the circumstances described there (variation of layer thicknesses, materials used).

[0623] In the following examples, the results for various OLEDs are presented. Clean glass plates (cleaned in a Miele laboratory glass washer, Merck Extran cleaner) coated with structured ITO (indium tin oxide) with a thickness of 50 nm were pretreated with UV ozone for 25 min (PR-100 UV ozone generator from UVP) and, to improve processing, coated within 30 min with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) as CLEVIOS TM P VP AI4083 was purchased from Heraeus Precious Metals GmbH, Germany, and was spin-coated from aqueous solution) and then baked for 10 minutes at 180° C. These coated glass plates formed the substrate to which the OLEDs were applied.

[0624] The OLED essentially has the following layer structure: substrate / hole injection layer 1 (HIL1) consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm / hole transport layer 1 (HTL1) / hole transport layer 2 (HTL2) / luminescent layer (EML) / hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm.

[0625] First, a vacuum-processed OLED is described. For this purpose, all materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the light-emitting layer always consists of at least one matrix material (host material) and a luminescent dopant (luminophore) added to one or more matrix materials by co-evaporation in a specific volume ratio. Detailed information given in the form of TMM1:TMM2:Ir(L1) (55%:35%:10%) means here that the material TMM1 is present in the layer in a volume ratio of 55%, TMM2 in a ratio of 35% and Ir(L1) in a ratio of 10%. Similarly, the electron transport layer can also consist of a mixture of two materials. The exact structure of the OLED can be found in Table 1. The materials used to manufacture the OLED are shown in Table 4.

[0626] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in %) were determined, which were calculated as a function of the brightness from the current-voltage-brightness characteristics showing Lambertian emission behavior, and the lifetime was also determined. The electroluminescence spectrum was measured at 1000 cd / m 2 The luminance of the light is determined at 10 000 cd / m and the CIE 1931 x and y color coordinates are calculated from them. The lifespan LD90 is defined as the brightness of the light at 10 000 cd / m 2 At the initial brightness, the time it takes for the brightness during operation to drop to 90% of the initial brightness.

[0627] The OLED can also be initially operated at different initial brightnesses. The lifetime value can then be converted to values ​​at other initial brightnesses using conversion formulas known to those skilled in the art.

[0628] Use of the compounds of the invention as materials in phosphorescent OLEDs

[0629] The compounds of the invention can be used, inter alia, as HTM (hole transport material), TMM (triplet matrix material), ETM (electron transport material) and emitter material in the light-emitting layer in OLEDs. The compounds of Table 4 serve as a comparison of the prior art. The results of the OLEDs are summarized in Table 2.

[0630] Table 1: Structure of OLED

[0631]

[0632]

[0633]

[0634]

[0635]

[0636]

[0637] Table 2: Results for vacuum processed OLEDs

[0638]

[0639]

[0640]

[0641] 2. Solution processed devices:

[0642] A: Low molecular weight soluble functional materials

[0643] The material of the present invention can also be processed from solution, in which case the OLED is much simpler in processing technology than the OLED processed in vacuum, but still has good properties. The manufacture of such components is based on the manufacture of polymer light-emitting diodes (PLEDs), which has been described many times in the literature (for example in WO 2004 / 037887). The structure consists of substrate / ITO / hole injection layer (60nm) / intermediate layer (20nm) / luminescent layer (60nm) / hole blocking layer (10nm) / electron transport layer (40nm) / cathode. For this purpose, a substrate (soda-lime glass) from Technoprint was used, and an ITO structure (indium tin oxide, transparent conductive anode) was applied thereto. The substrate was cleaned with deionized water and detergent (Deconex 15PF) in a clean room and then activated by UV / ozone plasma treatment. Afterwards, a 20nm hole injection layer was applied by spin coating, also in a clean room. The required rotation rate depends on the dilution degree and the specific spin coater geometry. To remove residual water in the layer, the substrate was baked on a hotplate at 200° C. for 30 minutes. The intermediate layer used serves the purpose of hole transport; in this case, HL-X from Merck was used. Alternatively, the intermediate layer can also be replaced by one or more layers, which only have to meet the condition that they will not be leached out again due to the subsequent processing steps of depositing the EML from solution. To produce the emitting layer, the triplet emitter of the invention is dissolved in toluene or chlorobenzene together with the matrix material. The typical solids content of such a solution is between 16 and 25 g / l, and at such a concentration, a typical layer thickness of 60 nm for the device is obtained by spin coating. The solution-processed device contains an emitting layer of matrix 1: matrix 2: Ir-reference 3 and optionally Ir-reference 4. Optionally, matrix 3 is also used (see Table 3). The emitting layer is spin-coated in an inert gas atmosphere, in this case argon, and baked at 160° C. for 10 minutes. On top of the latter are vapor deposited a hole blocking layer (10 nm ETM1) and an electron transport layer (40 nm ETM1 (50%) / ETM2 (50%)) (from a vapor deposition system by Lesker et al., with a typical vapor deposition pressure of 5 × 10 -6 mbar). Finally, an aluminum (100 nm) (high purity metal from Aldrich) cathode was applied by vapor deposition. To protect the device against air and air humidity, the device was finally encapsulated and then characterized. The cited OLED example is yet to be optimized; Table 3 summarizes the data obtained. The lifetime LD50 is defined as the lifetime at 1000 cd / m 2 At the initial brightness, the time it takes for the running brightness to drop to 50% of the initial brightness.

[0644] Table 3: Results obtained with materials processed from solution

[0645]

[0646]

[0647] Table 4: Structural formula of materials used

[0648]

[0649]

[0650]

[0651]

Claims

1. A compound which can be used as an active compound in an organic electronic device, which has at least one aromatic or heteroaromatic ring system having 5 to 60 carbon atoms and is fused to an aliphatic polycyclic ring system having at least 3 rings, Features The aliphatic polycyclic ring system having at least 3 rings and fused to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms forms substructures of formulae (N-1) to (N-6): wherein the dotted line represents the bond of the aliphatic polycyclic ring system having at least 3 rings fused to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms, and wherein the symbol R 1 , v, t and s have the following definitions: R 1 be the same or different in each occurrence and be: H, D, OH, F, Cl, Br, I, CN, NO 2 ,N(Ar 1 ) 2 ,N(R 2 ) 2 , C(=O)Ar 1 , C(=O)R 2 , P(=O)(Ar 1 ) 2 , P(Ar 1 ) 2 , B(Ar 1 ) 2 , B(OR 2 ) 2 , Si(Ar 1 ) 3 ,Si(R 2 ) 3 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 group substitution, where one or more non-adjacent CH 2 The group can be -R 2 C=CR 2 -、-C≡C-、Si(R 2 ) 2 , Ge(R 2 ) 2 Sn(R 2 ) 2 , C=O, C=S, C=Se, C=NR 2 、-C(=O)O-、-C(=O)NR 2 -、NR 2 ,P(=O)(R 2 ), -O-, -S-, SO or SO 2 and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be replaced by one or more R 2 or having 5 to 40 aromatic ring atoms and may be substituted with one or more R 2 an aryloxy or heteroaryloxy group substituted with a group, or having 5 to 40 aromatic ring atoms and which may be replaced by one or more R 2 a substituted aralkyl or heteroaralkyl group; Ar 1 is the same or different at each occurrence and is a ring having 5 to 30 aromatic ring atoms and may be replaced by one or more non-aromatic R 2 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two Ar 1 The group may also be connected by a single bond or selected from B(R 2 )、C(R 2 ) 2 、Si(R 2 ) 2 、C=O、C=NR 2 , C=C(R 2 ) 2 ,O,S,S=O,SO 2 、N(R 2 )、P(R 2 ) and P(=O)R 2 The bridging groups are connected to each other; R 2 is the same or different in each occurrence and is: H, D, F, Cl, Br, I, CN, B (OR 3 ) 2 , NO 2 , C(=O)R 3 , CR 3 =C(R 3 ) 2 , C(=O)OR 3 ,C(=O)N(R 3 ) 2 ,Si(R 3 ) 3 , P(R 3 ) 2 , B(R 3 ) 2 ,N(R 3 ) 2 , NO 2 , P(=O)(R 3 ) 2 , OSO 2 R 3 , OR 3 , S(=O)R 3 ,S(=O) 2 R 3 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be replaced by one or more R 3 group substitution, where one or more non-adjacent CH 2 The group can be -R 3 C=CR 3 -、-C≡C-、Si(R 3 ) 2 , Ge(R 3 ) 2 Sn(R 3 ) 2 、C=O、C=S、C=NR 3 、-C(=O)O-、-C(=O)NR 3 -、NR 3 ,P(=O)(R 3 ), -O-, -S-, SO or SO 2 and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 or having 5 to 40 aromatic ring atoms and in each case being replaced by one or more R 3 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 40 aromatic ring atoms and substituted by one or more R 3 substituted aryloxy or heteroaryloxy groups, or combinations of these systems; at the same time, two or more adjacent R 2 The substituents together may also form a monocyclic or polycyclic aliphatic or aromatic or heteroaromatic ring system; R 3 are identical or different at each occurrence and are selected from: H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and in which the aromatic or heteroaromatic ring system may be substituted by one or more alkyl radicals each having 1 to 4 carbon atoms; at the same time, two or more adjacent R 3 The substituents together may also form a monocyclic or polycyclic aliphatic or aromatic or heteroaromatic ring system; The tag s is 0, 1, 2, 3, 4, 5, or 6; tag t is 0, 1, 2, 3, 4, 5, 6, 7, or 8; The tag v is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; and characterized in that an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms fused to an aliphatic polycyclic ring system having at least 3 rings forms a substructure of formula (Ar-1) or (Ar-12): Where X' is CR 1 or N, U is selected from O, S, C(R 1 ) 2 、N(R 1 )、B(R 1 )、Si(R 1 ) 2 、C=O、S=O、SO 2 , P(R 1 ) and P(=O)R 1 , and the aliphatic polycyclic ring system having at least 3 rings is combined with the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms at the corresponding positions identified by o to form a ring.

2. The compound according to claim 1, Features An aliphatic polycyclic ring system having at least 3 rings and fused to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms forms a substructure of formula (N-1):

3. The compound according to claim 1 or 2, Features An aromatic or heteroaromatic ring system having 5 to 60 carbon atoms fused to an aliphatic polycyclic ring system having at least 3 rings forms a substructure of formula (Ar-1):

4. The compound according to claim 1 or 2, Features The compound comprises a hole transport group, wherein R 1 The group includes a hole transporting group.

5. The compound according to claim 4, Features The hole transport group is a group selected from formula (H-1) to (H-26): The dotted bonds indicate the connection positions, and Ar 2 ,Ar 3 ,Ar 4 Each is independently an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which may be replaced by one or more R 1 group substitution; Y 1 O, S, C (R 1 ) 2 NR 1 or NAr 1 ; Z is a bond or C(R 1 ) 2 、Si(R 1 ) 2 、C=O、NR 1 、N-Ar 1 , BR 1 , PR 1 , PO(R 1 ), SO, SO 2 , Se, O or S; e is 0, 1, or 2; h is the same or different in each occurrence and is 0, 1, 2, 3, or 4; j is 0, 1, 2, or 3; p is 0 or 1; The symbol Ar 1 has the meaning given in claim 1, and wherein the substituent R in the structures of formula (H-1) to (H-26) is 1 In the structures of formulae (N-1) to (N-6), (Ar-1) and (Ar-12), the substituted group R 2 replace.

6. The compound according to claim 1 or 2, Features The compound comprises an electron transport group, wherein R 1 The group comprises an electron transporting group, wherein the electron conductor group comprises at least 2 nitrogen atoms in one six-membered ring or in two fused six-membered rings.

7. The compound according to claim 6, Features The electron transport group is selected from pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole or benzimidazole.

8. The compound according to claim 1 or 2, Features The compound is selected from:

9. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 8, wherein one or more bonds of said compounds to said polymer, oligomer or dendrimer are present in place of a hydrogen atom or a substituent.

10. A composition comprising at least one compound according to any one of claims 1 to 8 or an oligomer, polymer or dendrimer according to claim 9 and at least one other compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocking materials, and hole blocking materials.

11. A preparation comprising at least one compound according to any one of claims 1 to 8 or an oligomer, polymer or dendrimer according to claim 9 or a composition according to claim 9 and at least one solvent.

12. Use of a compound according to any one of claims 1 to 8 or an oligomer, polymer or dendrimer according to claim 9 or a composition according to claim 10 as a fluorescent emitter, an emitter exhibiting TADF (thermally activated delayed fluorescence), a host material, an electron transport material, an electron injection material, a hole conducting material, a hole injection material, an electron blocking material, a hole blocking material and / or a wide bandgap material in an electronic device.

13. A process for preparing a compound according to any one of claims 1 to 8 or an oligomer, polymer and / or dendrimer according to claim 9, It is characterized in that In the coupling reaction, a compound comprising at least one aliphatic polycyclic ring system having at least 3 rings is linked to a compound comprising at least one aromatic or heteroaromatic group.

14. An electronic device comprising at least one compound according to any one of claims 1 to 8, an oligomer, a polymer or a dendrimer according to claim 9 or a composition according to claim 10, wherein the electronic device is selected from an organic electroluminescent device, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light emitting electrochemical cell and an organic laser diode.

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