Compounds that can be used as active compounds in organic electronic devices

Abstract

The present invention relates to compounds that can be used as active compounds in organic electronic devices, in particular compounds for use in electronic devices. The present invention further relates to a process for producing the compounds according to the invention, and to electronic devices comprising the compounds.

Description

[Technical field]

[0001] The present invention relates to compounds, especially for use in electronic devices. The present invention further relates to methods of making the compounds of the invention and to electronic devices containing these compounds.

[0002] The structure of organic electroluminescent devices (OLEDs) in which organic semiconductors are used as functional materials is described, for example, in US4539507, US5151629, EP0676461 and WO98 / 27136. The emitting materials used are often organometallic complexes that exhibit phosphorescence. For quantum mechanical reasons, the use of organometallic compounds allows up to four times the energy and power efficiency compared to phosphorescent emitters. In general terms, there is still a need for improvements in OLEDs, especially in OLEDs that exhibit phosphorescence, for example in terms of efficiency, operating voltage and lifetime. Organic electroluminescent devices that contain fluorescent emitters or emitters that exhibit TADF (thermally activated delayed fluorescence) are also known.

[0003] The properties of organic electroluminescent devices are not only determined by the emitter used. 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 importance here. Improvements in these materials can lead to obvious improvements in electroluminescent devices.

[0004] According to the prior art, compounds having bi- or tricyclic ring systems are used in particular for the preparation of metal complexes that exhibit phosphorescence. These compounds function in particular as ligands in the corresponding complexes. This prior art includes in particular documents WO2014 / 094960A1, WO2014 / 094961A1, WO2015 / 104045A1, WO2015 / 117718A1 and WO2016 / 124304. Matrix materials, electron transport materials, hole transport materials, fluorescent emitters or emitters exhibiting TADF (thermally activated delayed fluorescence) are not described in these documents.

[0005] Furthermore, document WO2015 / 036078 discloses heterocyclic compounds which can be used inter alia 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 further fused.

[0006] Generally speaking, for these materials used, for example, as matrix materials, hole-conducting materials or electron-transporting materials, there is still a need for improvement, especially with regard to lifetime, but also with regard to device efficiency and operating voltage. Furthermore, the compounds must have a high color purity.

[0007] It is a further object of the present invention to provide compounds which are suitable for use as fluorescent emitters or emitters exhibiting TADF (thermally activated delayed fluorescence) in organic electronic devices, in particular organic electroluminescent devices, which, when used in such devices, lead to good device properties, and to provide corresponding electronic devices.

[0008] It is therefore an object of the present invention to provide compounds which are suitable for use in organic electronic devices, in particular organic electroluminescent devices, and which, when used in such devices, lead to good device properties, and to provide corresponding electronic devices.

[0009] A particular object of the present invention is to provide a compound that provides long life, high efficiency and low operating voltage. In particular, the properties of the matrix material, hole conducting material or electron transporting material also essentially affect the life and efficiency of organic electroluminescent devices.

[0010] A further problem addressed by the present invention can be considered to be that of providing compounds suitable for use, inter alia, as matrix materials in phosphorescent or fluorescent OLEDs. More particularly, the problem addressed by the present invention is that of providing matrix materials suitable for red, yellow and green phosphorescent OLEDs.

[0011] In addition, the compounds, especially when used as matrix materials, hole conducting materials or electron transporting materials in organic electroluminescent devices, should result in devices with excellent color purity.

[0012] Furthermore, the compounds should be processable in a very simple manner and should exhibit, inter alia, good solubility and film-forming properties, for example, they should exhibit increased oxidative stability and improved glass transition temperatures.

[0013] A further objective can be considered to be to provide electronic devices with excellent performance at very low cost and with consistent quality.

[0014] Furthermore, the electronic devices must be capable of being used or adapted for many purposes, and more particularly, the performance of the electronic devices must be maintained over a wide temperature range.

[0015] Surprisingly, it has been found that certain compounds, which are described in detail below, solve these problems and eliminate the shortcomings of the prior art. The use of these compounds leads to very good properties of organic electronic devices, especially organic electroluminescent devices, especially in terms of lifetime, efficiency and operating voltage. The present invention therefore provides electronic devices, especially organic electroluminescent devices, comprising such compounds, and corresponding preferred embodiments.

[0016] The present invention therefore provides compounds which can be used as active compounds in organic electronic devices, characterized in that they have at least one aromatic or heteroaromatic ring system having 5 to 60 carbon atoms and fused to an aliphatic polycyclic ring system having at least three rings.

[0017] Preferably, the largest ring of an aliphatic polycyclic ring system having at least three rings may have no more than 14, preferably no more than 12, more preferably no more than 10, and especially preferably no more than 7 atoms in the corresponding ring.

[0018] Additionally, when an aliphatic polycyclic ring system having at least three rings is fused to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms, the intervening ring may contain six ring atoms and at least two non-adjacent nitrogen atoms.

[0019] Additionally, when an aliphatic polycyclic ring system having at least three rings is fused to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms, the intervening ring may contain six ring atoms and no nitrogen atoms.

[0020] Additionally, an aliphatic polycyclic ring system having at least three rings may be fused to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms, provided that the intervening ring contains six ring atoms and at least one nitrogen atom, and no further ring system is fused to that ring.

[0021] Active compounds are generally organic or inorganic materials, such as charge-injecting, charge-transporting or charge-blocking materials, but especially light-emitting materials and matrix materials, that are introduced between the anode and the cathode, for example in organic electronic devices, especially organic electroluminescent devices.

[0022] Compounds that can be used as active compounds in organic electronic devices may preferably be selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, exciton blocking materials, electron injection materials, hole conducting materials, hole injection materials, n-dopants, p-dopants, wide band gap materials, electron blocking materials and / or hole blocking materials. Here, fluorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, exciton blocking materials, electron injection materials, hole conducting materials, hole injection materials, n-dopants, p-dopants, wide band gap materials, electron blocking materials and / or hole blocking materials are preferred.

[0023] In a preferred embodiment, the compound of the present invention is represented by the formula (I) to (XVIII)

[0024] [ka]

[0025] [ka]

[0026] [ka]

[0027] [ka]

[0028] (wherein the symbols used are as follows: Y, in each occurrence, is the same or different and is O, S, C(R), CArR, C(Ar), Si(Ar), SiArR or Si(R), NR, or NAr, preferably O, S, NAr, more preferably NAr; X, in each occurrence, is the same or different and is N or CR, preferably CR; R is the same or different in each occurrence and is H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar)2, N(R 1 )2, C(=O)N(Ar)2, C(=O)N(R 1 )2, 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)2Ar, S(=O)2R 1 , OSO2Ar, OSO2R 1 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is in each case composed of one or more R 1 radicals), where one or more non-adjacent CH groups are 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, in each case one or more R 1 Aromatic or heteroaromatic ring systems, optionally substituted by radicals, or having 5 to 40 aromatic ring atoms and one or more R 1an aryloxy or heteroaryloxy group optionally substituted by a radical; at the same time, two R radicals may also together form a mono- or polycyclic aliphatic or aromatic or heteroaromatic ring system; Ar, in each occurrence, is the same or different, has 5 to 60 aromatic ring atoms, and is selected from one or more R 1 at the same time, two Ar radicals bonded to the same silicon, nitrogen, phosphorus or boron atom are also bonded to a single bond, or to a B(R 1 ), C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, O, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 and are capable of being linked together by a bridge selected from: R 1 are the same or different in each case and are H, D, OH, F, Cl, Br, I, CN, NO2, 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 straight chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms (each of which may be selected from the group consisting of one or more R 2 radicals), where one or more non-adjacent CH groups are optionally substituted by -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 SO2, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2), 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 one or more R 2 an aryloxy or heteroaryloxy group optionally substituted by a radical, or a aryloxy group having 5 to 40 aromatic ring atoms and one or more R 2 aralkyl or heteroaralkyl groups, optionally substituted by radicals, or combinations of these systems; at the same time, two or more, preferably adjacent R 1 the radicals may together form a mono- or polycyclic aliphatic or aromatic or heteroaromatic ring system; Ar 1 are the same or different in each occurrence and have 5 to 30 aromatic ring atoms and one or more preferably non-aromatic R 2 at the same time, two Ar are bonded to the same silicon, nitrogen, phosphorus or boron atom. 1 The radical can also be a single bond or B(R 2 ), C(R 2 )2, Si(R 2 )2, C=O, C=NR 2 , C=C(R 2 )2, O, S, S=O, SO2, N(R 2 ), P(R 2 ) and P(=O)R 2 and are capable of being linked together by a bridge selected from: R 2are the same or different in each case and are H, D, F, Cl, Br, I, CN, B(OR 3 )2, NO2, C(=O)R 3 , C.R. 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, NO2, P(=O)(R 3 )2, OSO2R 3 , OR 3 , S(=O)R 3 , S(=O)2R 3 , a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be represented by one or more R 3 radicals), where one or more non-adjacent CH groups are optionally substituted by -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 SO2, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2), or having 5 to 40 aromatic ring atoms, in each case having one or more R 3 Aromatic or heteroaromatic ring systems, optionally substituted by radicals, or having 5 to 40 aromatic ring atoms and one or more R 3 an aryloxy or heteroaryloxy group, optionally substituted by a radical, or a combination of these systems; at the same time, two or more, preferably adjacent, substituents R 2may also together form a mono- or polycyclic aliphatic or aromatic or heteroaromatic ring system; R 3 are in each case the same or different and are selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms; at the same time, two or more, preferably adjacent, substituents R 3 may also together form a mono- or polycyclic aliphatic or aromatic or heteroaromatic ring system; The subscript s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2; The subscript 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; The index 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. It may include at least one structure of:

[0029] Adjacent carbon atoms in the context of the present invention are carbon atoms that are directly bonded to each other. In addition, "adjacent radicals" in the definition of a radical means that these radicals are bonded to the same carbon atom or to adjacent carbon atoms. Correspondingly, these definitions also apply to the terms "adjacent groups" and "adjacent substituents", among others.

[0030] In the context of this specification, the expression that two or more radicals may join together to form a ring is understood to mean, inter alia, that the two radicals are linked to each other by a chemical bond involving the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0031] [ka]

[0032] However, in addition, the above expression should also be understood to mean that if one of the two radicals is hydrogen, the second radical is bonded to the position where the hydrogen atom was bonded to form a ring. This is illustrated by the following scheme:

[0033] [ka]

[0034] A fused aryl group, fused aromatic ring system, or fused heteroaromatic ring system in the context of the present invention is a group in which two or more aromatic groups are fused together along a common edge, i.e., fused rings, such as in naphthalene, for example, such that two carbon atoms belong to at least two aromatic or heteroaromatic rings.In contrast, for example, fluorene is not a fused aryl group in the context of the present invention, since the two aromatic groups in fluorene do not have a common edge.The corresponding definition also applies to heteroaryl groups and fused ring systems, which may contain, but do not necessarily contain, further heteroatoms.

[0035] Two or more preferably adjacent R, R 1 , R 2 and / or R 3 When the radicals taken together form a ring system, the result may be a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system.

[0036] An aryl group in the context of the present invention contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms; a heteroaryl group in the context of the present invention contains 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. An aryl or heteroaryl group here is understood to mean either a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

[0037] An aromatic ring system in the context 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 context 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 context of the present invention is of course understood to mean a system which does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of atoms other than H), such as carbon, nitrogen or oxygen atoms or carbonyl groups. Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, stilbenes, etc. are also considered aromatic ring systems in the context 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 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 also considered aromatic or heteroaromatic ring systems.

[0038] A cyclic alkyl, alkoxy or thioalkoxy group in the context of this invention is understood to mean a monocyclic, bicyclic or polycyclic group.

[0039] In the context of the present invention, C1-C2 are each independently selected from the group consisting of C1-C2, in which the individual hydrogen atoms or CH2 groups may be further replaced by the above-mentioned groups. 20Examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, and the like. 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-hex-1-yl, 1,1-dimethyl-n-hepta- 1-yl, 1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl, 1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-oct-1-yl, 1,1-diethyl-n-dec-1-yl, 1, It is understood to mean the radicals 1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl, 1,1-diethyl-n-hexadec-1-yl, 1,1-diethyl-n-octadec-1-yl, 1-(n-propyl)cyclohex-1-yl, 1-(n-butyl)cyclohex-1-yl, 1-(n-hexyl)cyclohex-1-yl, 1-(n-octyl)cyclohex-1-yl and 1-(n-decyl)cyclohex-1-yl. An alkenyl group is understood to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl.An alkynyl group is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. C1-C. 40 An alkoxy group is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy.

[0040] Aromatic or heteroaromatic ring systems having 5 to 60, preferably 5 to 40, more preferably 5 to 30, aromatic ring atoms, which in each case may be further substituted by the abovementioned radicals and which may be linked to the aromatic or heteroaromatic system via any desired position, are, for example, benzene, naphthalene, anthracene, benzoanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzofluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, ter ... fluorene, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, 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, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazo , isoxazole, 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-tetraazapyrylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,It is understood to mean the radicals derived from 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.

[0041] Also preferred are compounds having structures of Formulae (I)-(XVIII) wherein not 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, of the X groups per ring are selected from CH and CD.

[0042] In a further configuration, compounds having structures of Formulae (I)-(XVIII) in which two X groups per ring are N are preferred, where these X groups are not adjacent.

[0043] Further, preferred are compounds having structures of formulae (I)-(XVIII) in which not more than four, preferably not more than two, X groups are N, more preferably all X groups are CR, and in which preferably not more than four, more preferably not more than three, particularly preferably not more than two of the CR groups represented by X are not CH groups.

[0044] In a further configuration, compounds having structures of Formulae (I)-(XVIII) in which two X groups are N are preferred, where these X groups are not adjacent.

[0045] The compounds of the present invention are preferably represented by the formulae (Ia) to (XVIIIa)

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] in which the symbols Y, R, v, t and s have the definitions given above especially with respect to formulae (I) to (XVIII), 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, 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 in which Y is preferably O, S, NR or NAr, more preferably NAr. It may include at least one structure of:

[0050] Additionally, in the structures of formulae (Ia)-(XVIIIa), the sum of the subscripts v, t, s, o, n, m and l may be 6 or less, preferably 4 or less, and more preferably 2 or less.

[0051] When X is CR or when the aromatic and / or heteroaromatic groups are substituted by substituents R, these substituents R are preferably H, D, F, CN, N(Ar)2, C(=O)Ar, P(=O)(Ar)2, linear alkyl or alkoxy groups having 1 to 10 carbon atoms or branched or cyclic alkyl or alkoxy groups having 3 to 10 carbon atoms or alkenyl groups having 2 to 10 carbon atoms, each of which may be selected from the group consisting of one or more R 1 radicals) (wherein one or more non-adjacent CH groups may be replaced by O and one or more hydrogen atoms may be replaced by D or F), having 5 to 24 aromatic ring atoms, in each case one or more R 1An aromatic or heteroaromatic ring system, or a heteroaromatic ring system having 5 to 25 aromatic ring atoms, which may be substituted by a radical, but is preferably unsubstituted, and which is 1 at the same time, preferably two substituents R attached to adjacent carbon atoms are selected from the group consisting of aralkyl or heteroaralkyl groups, optionally substituted by radicals; 1 It is optionally possible to form mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems, which may be substituted by radicals; in which the Ar group has the definition given above, especially with respect to formulae (I) to (XVIII).

[0052] More preferably, these substituents R are H, D, F, CN, N(Ar), a linear alkyl group having from 1 to 8 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having from 3 to 8 carbon atoms, preferably having 3 or 4 carbon atoms, or an alkenyl group having from 2 to 8 carbon atoms, preferably having 2, 3 or 4 carbon atoms, each of which may be represented by one or more R 1 radicals, but preferably unsubstituted), or 5 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, in each case one or more non-aromatic R 1 at the same time, two substituents R 1 But there is one or more R 2 It is optionally possible for the radicals to form an optionally substituted, but preferably unsubstituted, monocyclic or polycyclic aliphatic ring system, where Ar may have the definition given above.

[0053] Most preferably, the substituent R is selected from the group consisting of H and an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably having 6 to 13 aromatic ring atoms, each of which may be joined by one or more non-aromatic R1 Examples of suitable substituents R are selected from the group consisting of phenyl, ortho, meta or para 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-dibenzothienyl, 1-, 2-, 3- or 4-carbazolyl and indenocarbazolyl, each of which may be substituted by one or more R 1 It may be substituted with a radical, but is preferably unsubstituted.

[0054] In addition, the substituent R of the heteroaromatic ring system of formulae (I) to (XVIII) and / or (Ia) to (XVIIIa) may not together with the ring atoms of the aromatic or heteroaromatic ring system form a fused aromatic or heteroaromatic ring system, and preferably may not form any fused ring system. This is because R 1 Possible substituents R that may be attached to the radical 1 , R 2 , R 3 together with to form a fused ring system.

[0055] In further preferred embodiments, compounds that can be used as active compounds in organic electronic devices can include at least two, preferably at least three, aliphatic polycyclic ring systems having at least three rings.

[0056] Furthermore, the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which the aliphatic polycyclic ring system having at least three rings is fused may be selected from phenyl, ortho-, meta- or para-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-dibenzothienyl, pyrenyl, triazinyl, imidazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1-, 2-, 3- or 4-carbazolyl, indenocarbazolyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl and / or triphenylenyl, each of which may be selected from one or more of R and / or R 1 These may be substituted by radicals, and phenyl, spirobifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene and triphenylene groups are particularly preferred.

[0057] In a further preferred embodiment, the aliphatic polycyclic ring system having at least three rings and fused to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms is represented by the formulas (N-1) to (N-6):

[0058] [ka]

[0059] (Wherein, the symbol R 1 , v, t and s have the definitions given above, especially with respect to formulae (I) to (XVIII), and the dotted line represents the linkage of an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which is fused an aliphatic polycyclic ring system having at least three rings. The double bond shown in the structures of formulae (N-1) to (N-6) may be considered herein as part of an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which one of the structures of formulae (N-1) to (N-6) is fused.

[0060] Furthermore, an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which an aliphatic polycyclic ring system having at least three rings is condensed is represented by the formulas (Ar-1) to (Ar-66):

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] (wherein X' is N or CR 1 , preferably CR 1 and Y' is O, S, C(R 1 )2, Si(R 1 )2, NR 1 and NAr 1 , preferably O, S, NAr 1 More preferably, NAr 1 and U is O, S, C(R 1 )2, N(R 1 ), B(R 1 ), Si(R 1 )2, C=O, S=O, SO2, P(R 1 ) and P(=O)R 1 where R 1 has the definition given above with respect to formulae (I) to (XVIII), in particular, where the aliphatic polycyclic ring system having at least three rings is linked to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms at each position specified by ○ to form a ring. Here, the structures of the formulae (Ar-2) to (Ar-66) are preferred, and the structures of the formulae (Ar-4) to (Ar-15) and (Ar-23) to (Ar-44) are particularly preferred.

[0070] No more than two X' groups per ring are N, and preferably all X' groups in the ring are CR 1 Also preferred are compounds having partial structures of formulae (Ar-1) to (Ar-66), preferably in which at least one, more preferably at least two, of the X' groups per ring are selected from CH and CD.

[0071] In a further configuration, compounds having structures of Formulae (I)-(XVIII) in which two X' groups per ring are N are preferred, where these X' groups are not adjacent.

[0072] Further, no more than four, preferably no more than two, X' groups are N, and more preferably all X' groups are CR 1In particular, compounds having a partial structure of the formulae (Ar-1) to (Ar-66) are preferred, in which X′ represents CR 1 Preferably no more than 4, more preferably no more than 3, especially preferably no more than 2 of the groups are not CH groups.

[0073] In a further configuration, compounds having a substructure of formula (Ar-1) to (Ar-66) in which two X′ groups are N are preferred, where these X groups are not adjacent.

[0074] In still further configurations, compounds having partial structures of formulae (Ar-55) to (Ar-66) in which preferably no more than two X' groups are N are preferred.

[0075] In a preferred embodiment, the combinations according to the following table are especially preferred:

[0076] [Table 1-1]

[0077] [Table 1-2]

[0078] [Table 1-3]

[0079] [Table 1-4]

[0080] [Table 1-5]

[0081] [Table 1-6]

[0082]

Table 1-7

[0083]

Table 1-8

[0084]

Table 1-9

[0085]

Table 1-10

[0086]

Table 1-11

[0087]

Table 1-12

[0088]

Table 1-13

[0089]

Table 1-14

[0090]

Table 1-15

[0091]

Table 1-16

[0092] [Table 1-17]

[0093] [Table 1-18]

[0094] [Table 1-19]

[0095] [Table 1-20]

[0096] [Table 1-21]

[0097] [Table 1-22]

[0098] [Table 1-23]

[0099] CR 1 A group X′ that is a group CR 1 The X' group, which is not a CH group, is preferably selected from hole-conducting groups and / or electron-conducting groups, where the electron-conducting group preferably comprises at least two nitrogen atoms in one six-membered ring or two condensed 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.

[0100] Among the compounds described above, compounds having fused, more preferably two-dimensionally fused, aromatic or heteroaromatic ring systems, such as compounds having partial structures of the formulae (Ar-2) to (Ar-12), (Ar-19) to (Ar-35) and (Ar-45) to (Ar-54), more preferably (Ar-4) to (Ar-9), (Ar-23) to (Ar-32) and (Ar-46) to (Ar-54), particularly preferably (Ar-4), (Ar-5), (Ar-23) to (Ar-25), (Ar-46) and (Ar-49), are particularly preferred.

[0101] In a further embodiment of the present invention, compounds containing fluorene, dibenzofuran, dibenzothiofuran, carbazole, spirobifluorene and similar structures are preferred, in particular compounds having partial structures of, for example, 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).

[0102] To clarify the above combinations, it should be emphasized that, for example, the combination of the moiety N-1 with the moiety Ar-1 results in a compound of formula (I). Similarly, for example, the combination of the moiety N-2 with the moiety Ar-45 results in a structure of formula (V). The same applies to further combinations.

[0103] Furthermore, an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which an aliphatic polycyclic ring system having at least three rings is condensed is represented by the formulas (Ar'-1) to (Ar'-65):

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] (In the formula, R 1 has the definition given above, especially with respect to formulae (I) to (XVIII), the symbols Y' and U have the definition given above, especially with respect to formulae (Ar-1) to (Ar-65), the subscript o is 0, 1 or 2, preferably 0 or 1, the subscript n is 0, 1, 2 or 3, preferably 0, 1 or 2, the subscript m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the subscript l is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1 or 2, and the aliphatic polycyclic ring system having at least three rings is bonded to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms at each position specified by ○ to form a ring). Here, structures of the formulae (Ar'-2) to (Ar'-53) are preferred, and structures of the formulae (Ar'-4) to (Ar'-15) and (Ar'-22) to (Ar'-43) are particularly preferred.

[0113] Additionally, in the partial structures of formulae (Ar'-1) to (Ar'-65), the sum of the subscripts o, n, m and l may be 6 or less, preferably 4 or less, and more preferably 2 or less.

[0114] The partial structures of the formulae (Ar'-54) to (Ar'-65) are more preferred.

[0115] In a preferred embodiment, the combinations according to the following table are especially preferred:

[0116] [Table 2-1]

[0117] [Table 2-2]

[0118] [Table 2-3]

[0119] [Table 2-4]

[0120] [Table 2-5]

[0121] [Table 2-6]

[0122] [Table 2-7]

[0123] [Table 2-8]

[0124]

Table 2-9

[0125]

Table 2-10

[0126]

Table 2-11

[0127]

Table 2-12

[0128]

Table 2-13

[0129]

Table 2-14

[0130]

Table 2-15

[0131]

Table 2-16

[0132]

Table 2-17

[0133]

Table 2-18

[0134]

Table 2-19

[0135]

Table 2-20

[0136]

Table 2-21

[0137]

Table 2-22

[0138]

Table 2-23

[0139]

Table 2-24

[0140]

Table 2-25

[0141]

Table 2-26

[0142]

Table 2-27

[0143]

Table 2-28

[0144] [Table 2-29]

[0145] [Table 2-30]

[0146] R 1 R in the above combinations where the group is not a H group 1 The group is preferably selected from hole-conducting groups and / or electron-conducting groups, where the electron-conducting group preferably comprises at least two nitrogen atoms in one six-membered ring or two condensed six-membered rings, and more preferably is selected from triazine and pyrimidine. Depending on the end use of the compound of the present invention, groups that promote TADF (thermally activated delayed fluorescence) are further preferred.

[0147] Among the compounds described above, compounds having fused, more preferably two-dimensionally fused, aromatic or heteroaromatic ring systems, such as compounds having partial structures of the formulae (Ar'-2) to (Ar'-12), (Ar'-18) to (Ar'-34) and (Ar'-44) to (Ar'-53), more preferably (Ar'-4) to (Ar'-9), (Ar'-22) to (Ar'-31) and (Ar'-45) to (Ar'-53), particularly preferably (Ar'-4), (Ar'-5), (Ar'-22) to (Ar'-24), (Ar'-45) and (Ar'-48), are particularly preferred.

[0148] In a further embodiment of the present invention, compounds containing fluorene, dibenzofuran, dibenzothiofuran, carbazole, spirobifluorene and similar structures are preferred, in particular compounds having partial structures of, for example, 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).

[0149] In a further configuration, the compound that can be used as an active compound in an organic electronic device can also include a fused aromatic or heteroaromatic ring system having at least two, preferably three, fused rings, which can be optionally substituted.

[0150] In a further embodiment, the compound usable as an active compound in an organic electronic device may comprise a hole transporting group, where preferably in the structures of formulae (I) to (XVIII) and / or (Ia) to (XVIIIa) an Ar group present in the Y group or in the R group comprises, preferably represents, a hole 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 comprises, and preferably represents, a hole transport group. Hole transport groups are known in the art and preferably comprise a triarylamine or carbazole group.

[0151] Preferably, the hole transport group is represented by the formula (H-1) to (H-3):

[0152] [ka]

[0153] (In the formula, the bond shown by the dotted line indicates the bond position, Ar 2 , Ar 3 , Ar 4 are each independently an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which is represented by one or more R 1 may be substituted with a radical; p is 0 or 1; Z is a bond or C(R 1 )2, Si(R 1 )2, C=O, NR 1 , N-Ar 1 , B.R. 1 , P.R. 1 , PO(R 1), SO, SO2, 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 definition given above especially with respect to formulae (I) to (XVIII) Here, the substituent R in the structures of the formulae (H-1) to (H-3) may include, and preferably may be, a group selected from the following: 1 is a substituent R in the structures of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53). 2 In addition, the presence of NN bonds is preferably excluded.

[0154] In addition, the hole transport group is represented by the formulas (H-4) to (H-26)

[0155] [ka]

[0156] [ka]

[0157] [ka]

[0158] (In the formula, Y 1 is O, S, C(R 1 )2, NR 1 or NAr 1 where the dotted bond indicates the position of attachment, e is 0, 1 or 2, j is 0, 1, 2 or 3, h is the same or different in each occurrence and is 0, 1, 2, 3 or 4, p is 0 or 1, and Ar 1 and R 1 has the definition given above, especially for formulae (I) to (XVIII), and Ar2 has the definition given above especially for formula (H-1) or (H-2) Here, the substituent R in the structures of the formulae (H-3) to (H-26) may include, and preferably may be, a group selected from the following: 1 is a substituent R in the structures of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53). 2 In addition, the presence of NN bonds is preferably excluded.

[0159] The hole transport groups of the formulae (H-1) to (H-26) detailed above can be selected from the group consisting of the preferred R 1 In this case, R 1 The group is R 2 It must be replaced by a radical.

[0160] From the above expression, when the subscript p=0, the corresponding Ar 2 It is clear that the group is not present and the bond is formed.

[0161] Preferably, Ar 2 The group is represented by the formula (H-1) to (H-26) 2 The group may form a through-conjugation with the aromatic or heteroaromatic radical or nitrogen atom to which it may be attached.

[0162] In a further 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, which may be joined by one or more R 1 may be substituted by a radical, but is preferably unsubstituted, where R 1 may have the definition given above, especially with respect to formulae (I) to (XVIII). More preferably, Ar2 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 is represented by one or more R 1 may be substituted by a radical, but is preferably unsubstituted, where R 1 may have the definition given above especially with respect to formulas (I)-(XVIII).

[0163] More preferably, the symbol Ar 2 is especially an aryl or heteroaryl radical having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, in which the aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is bonded directly, i.e. via an atom of the aromatic or heteroaromatic group, to the respective atom of the further group.

[0164] Furthermore, Ar 2 The group contains an aromatic ring system having up to two fused aromatic and / or heteroaromatic 6-membered rings; preferably, it may not contain any fused aromatic or heteroaromatic ring system having fused 6-membered rings. Thus, naphthyl structures are preferred over anthracene structures. In addition, fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structures are preferred over naphthyl structures. Structures without fusion, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures, are particularly preferred.

[0165] Furthermore, Ar 2 The radical may in particular have up to one nitrogen atom, preferably up to two heteroatoms, particularly preferably up to one heteroatom and especially preferably no heteroatoms.

[0166] In a further preferred embodiment of the present invention, Ar 3 and / or Ar 4are the same or different in each occurrence and are 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 represented by one or more R 1 may be substituted by a radical, but is preferably unsubstituted, where R 1 may have the definition given above especially in formulas (I) to (XVIII).

[0167] In a further preferred embodiment, the compound usable as an active compound in an organic electronic device may also comprise a radical comprising an electron transport group, where preferably in the structures of formulae (I) to (XVIII) and / or (Ia) to (XVIIIa) the Ar group present in the Y group or in the R group comprises a radical comprising an electron transport group, preferably represents a radical comprising an electron 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 includes, and preferably represents, a radical comprising an electron transport group. Electron transport groups are well known in the art and enhance the ability of a compound to transport and / or conduct electrons.

[0168] In addition, surprising advantages are shown by compounds that can be used as active compounds in organic electronic devices, comprising at least one structure selected from the group of pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and / or benzimidazole, with pyrimidine, triazine and quinazoline being particularly preferred. These structures generally promote the ability of the compound to transport and / or conduct electrons.

[0169] In a preferred embodiment of the invention, the radical comprising an electron transport group is of formula (QL)

[0170] [ka]

[0171] (In the formula, L 1 has a bond or 5 to 40, preferably 5 to 30, aromatic ring atoms and one or more R 1 represents an aromatic or heteroaromatic ring system optionally substituted by radicals, Q is an electron transport group, where R 1 has the definition given above, especially with respect to formulae (I) to (XVIII), and the bond indicates the position of attachment. Here, the substituent R in the structure of formula (QL) can be a group that can be represented by 1 is a substituent R in the structures of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53). 2 must be replaced by

[0172] Preferably, L 1 The group is a Q group and L of formula (QL). 1 The group may form a through conjugation together with the atom to which it is attached, preferably a carbon or nitrogen atom. The through conjugation of an aromatic or heteroaromatic system is formed as soon as a direct bond is formed between adjacent aromatic or heteroaromatic rings. Further bonds between the above-mentioned conjugated groups, for example via sulfur, nitrogen or oxygen atoms or carbonyl groups, do not adversely affect the conjugation. In the case of fluorene systems, two aromatic rings are directly bonded, where the 9-position sp 3 Although the hybridized carbon atom prevents fusion of these rings, conjugation is possible, which is due to the sp 9-position. 3 This is because there is not necessarily a hybridized carbon atom between the electron transporting Q group and the atom through which the group of formula (QL) is bonded to a further structural element of the compound of the invention. In contrast, in the case of the second spirobifluorene structure, the Q group and the L of formula (QL) 1Through conjugation can occur when the bond between the aromatic or heteroaromatic radical to which the Q group is attached is through the same phenyl group in the spirobifluorene structure or through phenyl groups in the spirobifluorene structure that are directly bonded to each other and in the same plane. 1 The bond between the aromatic or heteroaromatic radical to which the group is attached is sp 3 Conjugation is interrupted when it is via a different phenyl group in a second spirobifluorene structure that is bonded via a hybridized carbon atom.

[0173] In a further 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, which may be joined by one or more R 1 may be substituted by a radical, but is preferably unsubstituted, where R 1 may have the definition given above, especially with respect to 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 is represented by one or more R 2 may be substituted by a radical, but is preferably unsubstituted, where R 2 may have the definition given above especially with respect to formulas (I)-(XVIII).

[0174] More preferably, the symbol L shown in formula (QL) 1 are in each case the same or different and are aryl or heteroaryl radicals having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, in which a bond or an aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is linked directly, i.e. via an atom of the aromatic or heteroaromatic group, to the respective atom of the further group.

[0175] In addition, L shown in formula (QL) 1 The group may contain an aromatic ring system having up to two fused aromatic and / or heteroaromatic 6-membered rings, and preferably does not contain any fused aromatic or heteroaromatic ring system. Thus, naphthyl structures are preferred over anthracene structures. In addition, fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structures are preferred over naphthyl structures.

[0176] Structures that have no fusion, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures, are particularly preferred.

[0177] Suitable aromatic or heteroaromatic ring systems L 1 Examples of are selected from the group consisting of ortho-, meta- or para-phenylene, ortho-, meta- or para-biphenylene, terphenylene, especially branched terphenylene, quaterphenylene, especially branched quaterphenylene, fluorenylene, spirobifluorenylene, dibenzofuranylene, dibenzothienylene and carbazolylene, each of which may be selected from the group consisting of one or more R 1 It may be substituted with a radical, but is preferably unsubstituted.

[0178] Furthermore, in particular, L shown in formula (QL) 1 The group may have up to one nitrogen atom, preferably up to two heteroatoms, especially preferably up to one heteroatom, and more preferably no heteroatoms.

[0179] Preferably, the Q group, or electron transport group, as shown in formula (QL), in particular, is selected from the group represented by formula (Q-1), (Q-2), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9) and / or (Q-10):

[0180] [ka]

[0181] (In the formula, the bond shown by the dotted line indicates the bond position, Q' is the same or different in each case, and CR 1 or N, Q” is NR 1 , O or S; where at least one Q' is N; R 1 is as defined above, especially in formulae (I) to (XVIII). may be selected from the structures:

[0182] Substituent R in the structures of formulas (Q-1) to (Q-10) 1 is a substituent R in the structures of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53). 2 must be replaced by

[0183] In addition, the Q group, or electron transport group, as shown in formula (QL), in particular, is preferably represented by formula (Q-11), (Q-12), (Q-13), (Q-14) and / or (Q-15):

[0184] [ka]

[0185] (Wherein, the symbol R 1 has the definition given above, especially for formulae (I) to (XVIII), and X′ is N or CR 1 where the dotted bond indicates the point of attachment, and X' is preferably a nitrogen atom. The substituent R in the structures of the formulae (Q-11) to (Q-15) may be selected from the following structures: 1 is a substituent R in the structures of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53). 2 must be replaced by

[0186] In further embodiments, the Q group, or electron transport group, as shown in formula (QL), among others, is selected from the group represented by formula (Q-16), (Q-17), (Q-18), (Q-19), (Q-20), (Q-21) and / or (Q-22):

[0187] [ka]

[0188] (Wherein, the symbol R 1 has the definitions detailed above, especially with respect to formulae (I) to (XVIII), the bond shown with a dotted line indicates the position of attachment, 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. Here, the structures of the formulae (Q-16), (Q-17), (Q-18) and (Q-19) are preferred. Furthermore, the substituent R 1 is a substituent R in the structures of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53). 2 must be replaced by

[0189] In a further embodiment, the Q group, or electron transport group, as shown in formula (QL), among others, is represented by formula (Q-23), (Q-24) and / or (Q-25):

[0190] [ka]

[0191] (Wherein, the symbol R 1 has the definition given above, especially with respect to formulae (I) to (XVIII), and the dotted bond indicates the position of attachment. In addition, the substituent R in the structures of the formulae (Q-23) to (Q-25) may be selected from the following structures: 1is a substituent R in the structures of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53). 2 must be replaced by

[0192] In further embodiments, the Q group, or electron transport group, as shown in formula (QL), among others, is selected from the group represented by formula (Q-26), (Q-27), (Q-28), (Q-29) and / or (Q-30):

[0193] [ka]

[0194] (Wherein, the symbol Ar 1 and R 1 has the definition given above, especially for formulae (I) to (XVIII), and X′ is N or CR 1 (where the dotted bonds indicate the bond positions) Preferably, in the structures of formulae (Q-26), (Q-27) and (Q-28), exactly one X' is a nitrogen atom. Furthermore, the substituent R 1 is a substituent R in the structures of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53). 2 must be replaced by

[0195] Preferably, the Q group, or electron transport group, as shown in particular in formula (QL), is selected from the group represented by 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):

[0196] [ka]

[0197] [ka]

[0198] [ka]

[0199] (Wherein, the symbol Ar 1 and R 1 has the definition given above especially with respect to formulae (I) to (XVIII), the bond shown with a dotted line indicates the position of attachment, 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 the formulae (Q-31) to (Q-44) may be selected from the structures shown below. 1 is a substituent R in the structures of the formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53). 2 must be replaced by

[0200] In a further preferred embodiment of the present invention, Ar 1 are in each occurrence the same or different and are an aromatic or heteroaromatic ring system, preferably an aryl or heteroaryl radical having 5 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, more preferably an aromatic ring system, preferably an aryl radical 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 represented by one or more R 2 may be substituted, but is preferably unsubstituted, by a radical, where R 2 may have the definitions detailed above, especially in formulas (I) to (XVIII).

[0201] Preferably, the symbol Ar 1is an aryl or heteroaryl radical in which the aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is bonded directly, i.e. via an atom of the aromatic or heteroaromatic group, to the respective atom of a further group, for example a carbon or nitrogen atom of the groups (H-1) to (H-26) or (Q-26) to (Q-44) shown above.

[0202] Advantageously, Ar in formulae (H-1) to (H-26) or (Q-26) to (Q-44) 1 has 6 to 12 aromatic ring atoms and one or more R 2 is an aromatic ring system which may be substituted, but is preferably unsubstituted, by a radical, where R 2 may have the definitions detailed above, especially with respect to formulae (I)-(XVIII).

[0203] Preferably, R in formulas (H-1) to (H-26) or (Q-1) to (Q-44) 1 or R 2 The radical is R 1 or R 2 The aryl or heteroaryl group Ar to which the radical is attached 1 , Ar 2 , Ar 3 and / or Ar 4 does not form a fused ring system with the ring atoms of R 1 or R 2 R that may be attached to the radical 2 , R 3 This includes, together with the substituents, forming a fused ring system.

[0204] Also, Ar, Ar 1 , Ar 2 , Ar 3 and / or Ar 4The radicals may also be selected from the group consisting of phenyl, ortho-, meta- or para-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-dibenzothienyl, pyrenyl, triazinyl, imidazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1-, 2-, 3- or 4-carbazolyl, indenocarbazolyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl and / or triphenylenyl, each of which may be selected from the group consisting of one or more R 1 and / or R 2 They may be substituted with a radical, but are preferably unsubstituted, and phenyl, spirobifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene, and triphenylene groups are particularly preferred.

[0205] X or X 1 CR 1 or when the aromatic and / or heteroaromatic groups are R 1 When substituted by a substituent, these R 1 The substituents are preferably H, D, F, CN, N(Ar 1 )2, C(=O)Ar 1 , P(=O)(Ar 1 2. A straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, or 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 one or more of R 2 radicals) (wherein one or more non-adjacent CH groups may be replaced by O and one or more hydrogen atoms may be replaced by D or F), having 5 to 24 aromatic ring atoms, in each case one or more R 2An aromatic or heteroaromatic ring system, or a heteroaromatic ring system having 5 to 25 aromatic ring atoms, which may be substituted by a radical, but is preferably unsubstituted, and which is 2 aryl or heteroaryl groups optionally substituted by a radical; and at the same time, preferably two R 1 The substituents are one or more R 1 It is optionally possible to form monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring systems, which may be substituted by radicals, where Ar 1 The radicals have the definitions given above especially with regard to formulae (I) to (XVIII).

[0206] More preferably, these substituents R 1 are H, D, F, CN, and N(Ar 1 ) 2, a straight-chain alkyl group having 1 to 8 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably having 3 or 4 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably having 2, 3 or 4 carbon atoms (each of which may be represented by one or more R 2 radicals, but preferably unsubstituted), or 5 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, in each case one or more non-aromatic R 1 at the same time, two substituents R 1 But there is one or more R 2 Optionally, a monocyclic or polycyclic aliphatic ring system may be formed which may be substituted, but preferably is unsubstituted, by radicals, where Ar 1 may have the definition given above.

[0207] Most preferably, the substituent R 1H or has 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, and in each case one or more non-aromatic R 2 Suitable substituents R are selected from the group consisting of aromatic or heteroaromatic ring systems which may be substituted, but are preferably unsubstituted, by radicals. 1 are selected from the group consisting of phenyl, ortho-, meta- or para-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-dibenzothienyl, 1-, 2-, 3- or 4-carbazolyl and indenocarbazolyl, each of which may be selected from the group consisting of one or more R 2 It may be substituted with a radical, but is preferably unsubstituted.

[0208] In addition, the substituents R of the heteroaromatic ring systems 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) 1 may not, together with the ring atoms of the aromatic or heteroaromatic ring system, form a fused aromatic or heteroaromatic ring system, and preferably not form any fused ring system. This is because R 1 Possible substituents R that may be attached to the radical 2 , R 3 together with to form a fused ring system.

[0209] Furthermore, 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 radical is of the formula (R 1 -1)~(R 1 -92)

[0210] [ka]

[0211] [ka]

[0212] [ka]

[0213] [ka]

[0214] [ka]

[0215] [ka]

[0216] [ka]

[0217] (wherein the symbols used are as follows: Y 1 is O, S or NR 2 , preferably O or S; k in each occurrence is independently 0 or 1; i in each occurrence is independently 0, 1, or 2; j in each occurrence is independently 0, 1, 2, or 3; h in each occurrence is independently 0, 1, 2, 3, or 4; g in each occurrence is independently 0, 1, 2, 3, 4, or 5; R 2 may have the definition given above especially with respect to formulae (I) to (XVIII), The dotted bonds indicate the bond positions. or in the structures of formulae (H-1) to (H-26) and (Q-1) to (Q-44), at least one Ar 1 or R 1 The radical is of the formula (R 1 -1)~(R 1 -92).

[0218] Here, the formula R 1 -1~R 1 The group 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 The group -45 is particularly preferred.

[0219] Preferably, the formula (R 1 -1)~(R 1 -92) the sum of the indices k, i, j, h and g in the structure may in each case be 3 or less, preferably 2 or less, more preferably 1 or less.

[0220] Preferably, the formula (R 1 -1)~(R 1 -92) 2 The radical is R 2 The radical does not, together with the ring atoms of the aryl or heteroaryl group to which it is attached, form a fused aromatic or heteroaromatic ring system, and preferably does not form any fused ring system. 2R that may be attached to the radical 3 This includes, together with the substituents, forming a fused ring system.

[0221] The formula detailed above (R 1 -1)~(R 1 -92) is a preferred Ar radical of the formulae (I) to (XVIII) or an Ar radical of the formulae (H-1) to (H-3) or a preferred embodiment of these formulae 3 , Ar 4 is a radical, in this case of the formula (R 1 -1)~(R 1 -92) shown in R 2 The group is R 1 The formula (R 1 -1)~(R 1 -92) are correspondingly applicable.

[0222] Ar 2 The group has the formula (L 1 -1)~(L 1 -108)

[0223] [ka]

[0224] [ka]

[0225] [ka]

[0226] [ka]

[0227] [ka]

[0228] [ka]

[0229] [ka]

[0230] [ka]

[0231] (wherein the bond shown in each case as a dotted line indicates the position of the bond, the subscript k is 0 or 1, the subscript l is 0, 1 or 2, the subscript j in each case is independently 0, 1, 2 or 3, the subscript h in each case is independently 0, 1, 2, 3 or 4, the subscript g is 0, 1, 2, 3, 4 or 5; 1 is O, S or NR 1 , preferably O or S; 1 has the definition given above especially with respect to formulae (I) to (XVIII) A compound having at least one structure of formulas (H-1) to (H-26) and / or L 1 The group is a bond or has the formula (L 1 -1)~(L 1 -108) is preferably a compound having a structure of formula (QL).

[0232] Preferably, the formula (L 1 -1)~(L 1 -108) the sum of the indices k, l, g, h and j in the structure may in each case be 3 or less, preferably 2 or less, more preferably 1 or less.

[0233] Preferred compounds of the present invention having groups of the formulae (H-1) to (H-26) are those of the formula (L 1 -1)~(L 1 -78) and / or (L1 -92)~(L 1 -108), preferably of the formula (L 1 -1)~(L 1 -54) and / or (L 1 -92)~(L 1 -108), particularly preferably of the formula (L 1 -1)~(L 1 -29) and / or (L 1 -92)~(L 1 -103) selected from 2 Advantageously, the compound of formula (L 1 -1)~(L 1 -78) and / or (L 1 -92)~(L 1 -108), preferably of the formula (L 1 -1)~(L 1 -54) and / or (L 1 -92)~(L 1 -108), particularly preferably of the formula (L 1 -1)~(L 1 -29) and / or (L 1 -92)~(L 1 -103) the sum of the indices k, l, g, h and j in the structure may be 3 or less, preferably 2 or less, more preferably 1 or less in each occurrence.

[0234] Preferred compounds of the invention having a group of formula (QL) are those which represent a bond or have the formula (L 1 -1)~(L 1 -78) and / or (L 1 -92)~(L 1 -108), preferably of the formula (L 1 -1)~(L 1 -54) and / or (L 1 -92)~(L 1 -108), particularly preferably of the formula (L 1 -1)~(L 1 -29) and / or (L 1 -92)~(L 1 -103) 1 Advantageously, the compound of formula (L 1-1)~(L 1 -78) and / or (L 1 -92)~(L 1 -108), preferably of the formula (L 1 -1)~(L 1 -54) and / or (L 1 -92)~(L 1 -108), particularly preferably of the formula (L 1 -1)~(L 1 -29) and / or (L 1 -92)~(L 1 -103) the sum of the indices k, l, g, h and j in the structure may be 3 or less, preferably 2 or less, more preferably 1 or less in each occurrence.

[0235] Preferably, the formula (L 1 -1)~(L 1 -108) 2 The radical is R 2 The radical does not, together with the ring atoms of the aryl or heteroaryl group to which it is attached, form a fused aromatic or heteroaromatic ring system, and preferably does not form any fused ring system. 2 R that may be attached to the radical 3 This includes, together with the substituents, forming a fused ring system.

[0236] In a preferred configuration, the compounds of the invention that can be used as active compounds in organic electronic devices are selected from the group consisting of phenyl, fluorene, indenofluorene, spirobifluorene, carbazole, indenocarbazole, indolocarbazole, spirocarbazole, pyrimidine, triazine, lactam, triarylamine, dibenzofuran, dibenzothien, imidazole, benzimidazole, benzoxazole, benzothiazole, 5-arylphenanthridin-6-one, 9,10-dehydrophenanthrene, fluoranthene, anthracene, benzanthracene, fluoraden.

[0237] In a preferred configuration, the compounds of the invention can be represented by the structures of formulae (I) to (XVIII) and / or (Ia) to (XVIIIa) or by a combination of the partial structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53). Preferably, the compounds that can be used as active compounds in organic electronic devices, preferably the compounds comprising the structures of formulae (I) to (XVIII) and / or (Ia) to (XVIIIa) or the compounds obtainable by a combination of the partial structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), have a molecular weight of 5000 g / mol or less, preferably 4000 g / mol or less, particularly preferably 3000 g / mol or less, especially preferably 2000 g / mol or less, very particularly preferably 1200 g / mol or less.

[0238] In addition, preferred compounds of the present invention are characterized by being sublimable. These compounds generally have a molar mass of less than about 1200 g / mol.

[0239] The compounds of the invention are aromatic or heteroaromatic R 1 or R 2 When substituted by group, it is preferred that they do not have any aryl or heteroaryl groups with more than two aromatic 6-membered rings directly fused to each other.More preferably, the substituent does not have any aryl or heteroaryl groups with 6-membered rings directly fused to each other.The reason for this preference is the low triplet energy of such structures.The fused aryl groups that have more than two aromatic 6-membered rings directly fused to each other but are still preferred according to the present invention are phenanthrene and triphenylene, because they also have high triplet levels.

[0240] In the case of the composition 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 are 1 Or R 2or (R 1 -1)~(R 1 -95) group, preferably (R 1 -33)~(R 1 -57) and (R 1 -76)~(R 1 -86), or (L 1 -1)~(L 1 -109), preferably (L 1 -30)~(L 1 -60) and (L 1 -71)~(L 1 -91) Substituent R 2 may also contain corresponding groups formed by corresponding substitution with, for example fluorene, anthracene and / or pyrene groups.

[0241] In a further preferred embodiment of the present invention, R 2 is, for example in the structures of formulae (I) to (XVIII) and in preferred embodiments of these structures or in structures to which these formulae refer, in each case the same or different and is selected from the group consisting of H, D, an aliphatic hydrocarbyl 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 may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, but preferably is unsubstituted.

[0242] Preferably, R 2 The radical is R 2 The radical, together with the ring atoms of the aryl or heteroaryl group to which it is attached, does not form a fused aromatic or heteroaromatic ring system, and preferably does not form any fused ring system. 2 R that may be attached to the radical 3 This includes, together with the substituents, forming a fused ring system.

[0243] In a further preferred embodiment of the present invention, R3 is, for example in the structures of formulae (I) to (XVIII) and in preferred embodiments of these structures or in structures to which these formulae refer, in each case the same or different and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl 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 having 5 to 24 aromatic ring atoms, more preferably having 5 to 13 aromatic ring atoms, which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, but which are preferably unsubstituted.

[0244] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-1, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0245] [Table 3]

[0246] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-1′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v is particularly preferably 0, and which have the following characteristics:

[0247] [Table 4]

[0248] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-4, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0249] [Table 5]

[0250] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-4′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 2, and in which the indices v is particularly preferably 0, and which have the following characteristics:

[0251] [Table 6]

[0252] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-5, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0253] [Table 7]

[0254] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-5′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 2, and in which the indices v is particularly preferably 0, and which have the following characteristics:

[0255] [Table 8]

[0256] In a further aspect of the invention, there is provided a compound obtained by combining the partial structure N-1 with Ar-10, wherein the U radical is C(R 1)2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 The radical is preferably R 1 Preference is given to compounds which are derived from -2 and which together form a ring system to which further structural elements, preferably obtainable by combination of the partial structures N-1 and Ar-10, are attached, these compounds having the following characteristics:

[0257] [Table 9]

[0258] In a further aspect of the invention, there is provided a compound obtained by combining the moieties N-1 and Ar'-10, wherein the U radical is C(R 1 ) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1 The radical is preferably R 1 Preference is given to compounds which are derived from N-2 and which together form a ring system to which further structural elements, preferably obtainable by combination of the moieties N-1 and Ar'-10, are attached, and which have the following characteristics:

[0259] [Table 10]

[0260] In a further aspect of the invention, there is provided a compound obtained by combining the partial structure N-1 with Ar-10, wherein the U radical is Si(R 1 )2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 Preference is given to compounds in which the radical forms a structural element which can preferably be obtained by combination of the substructures N-1 and Ar-10, these compounds having the following characteristics:

[0261] [Table 11]

[0262] In a further aspect of the invention, there is provided a compound obtained by combining the partial structure N-1 with Ar'-10, wherein the U radical is Si(R 1 ) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1 Preference is given to compounds in which the radical forms a structural element which can preferably be obtained by combination of the substructures N-1 and Ar'-10, these compounds having the following characteristics:

[0263] [Table 12]

[0264] In a further aspect of the invention, there is provided a compound obtained by combining the partial structure N-1 with Ar-11, wherein the U radical is C(R 1 )2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 The radical is preferably R 1 Preference is given to compounds which are derived from N-2 and which together form a ring system to which further structural elements, preferably obtainable by combination of the partial structures N-1 and Ar-11, are attached, these compounds having the following characteristics:

[0265] [Table 13]

[0266] In a further aspect of the invention, there is provided a compound obtained by combining the moieties N-1 and Ar'-11, wherein the U radical is C(R 1) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1 The radical is preferably R 1 Preference is given to compounds which are derived from -2 and which together form a ring system to which further structural elements, preferably obtainable by combination of the partial structures N-1 and Ar'-11, are attached, and which have the following characteristics:

[0267] [Table 14]

[0268] In a further aspect of the invention, there is provided a compound obtained by combining the partial structure N-1 with Ar-11, wherein the U radical is Si(R 1 )2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 Preference is given to compounds in which the radical forms a structural element which can preferably be obtained by combination of the substructures N-1 and Ar-11, these compounds having the following characteristics:

[0269] [Table 15]

[0270] In a further aspect of the invention, there is provided a compound obtained by combining the partial structure N-1 with Ar'-11, wherein the U radical is Si(R 1 ) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1 Preference is given to compounds in which the radical forms a structural element which can preferably be obtained by combination of the substructures N-1 and Ar'-11, these compounds having the following characteristics:

[0271] [Table 16]

[0272] In a further aspect of the invention, there is provided a compound obtained by combining the moieties N-1 and Ar-12, wherein the U radical is C(R 1 )2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 The radical is preferably R 1 Preference is given to compounds which are derived from N-2 and which together form a ring system to which further structural elements, preferably obtainable by combination of the partial structures N-1 and Ar-12, are attached, and which have the following characteristics:

[0273] [Table 17]

[0274] In a further aspect of the invention, there is provided a compound obtained by combining the moieties N-1 and Ar'-12, wherein the U radical is C(R 1 ) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1 The radical is preferably R 1 Preference is given to compounds which are derived from N-2 and which together form a ring system to which further structural elements, preferably obtainable by combination of the moieties N-1 and Ar'-12, are attached, and which have the following characteristics:

[0275] [Table 18]

[0276] In a further aspect of the invention, there is provided a compound obtained by combining the partial structure N-1 with Ar-10, wherein the U radical is Si(R 1)2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 Preference is given to compounds in which the radical forms a structural element which can preferably be obtained by combination of the substructures N-1 and Ar-10, these compounds having the following characteristics:

[0277] [Table 19]

[0278] In a further aspect of the invention, there is provided a compound obtained by combining the partial structure N-1 with Ar'-12, in which the U radical is Si(R 1 ) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1 Preference is given to compounds in which the radical forms a structural element which can preferably be obtained by combination of the substructures N-1 and Ar'-12, these compounds having the following characteristics:

[0279] [Table 20]

[0280] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-13, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0281] [Table 21]

[0282] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-13′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v is particularly preferably 0, and which have the following characteristics:

[0283] [Table 22]

[0284] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-14, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0285] [Table 23]

[0286] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-14′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v is particularly preferably 0, and which have the following characteristics:

[0287] [Table 24]

[0288] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-15, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' which are not CH or CD, have the following characteristics:

[0289] [Table 25]

[0290] In a further configuration of the invention, preference is given to compounds obtained by combining the partial structures N-1 and Ar-15′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v is particularly preferably 0, and which have the following characteristics:

[0291] [Table 26]

[0292] In a further configuration of the invention, preference is given to compounds obtained by combining two partial structures N-1 with one partial structure Ar-23, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0293] [Table 27]

[0294] In a further configuration of the invention, preference is given to compounds obtained by combining two partial structures N-1 and one partial structure Ar-22′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 2, and in which the indices v is particularly preferably 0, and which have the following characteristics:

[0295] [Table 28]

[0296] In a further configuration of the invention, preference is given to compounds obtained by combining two partial structures N-1 with one partial structure Ar-24, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0297] [Table 29]

[0298] In a further aspect of the invention, compounds obtained by combining two partial structures N-1 and one partial structure Ar-23′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 2, and in which the indices v is particularly preferably 0, are preferred, which have the following characteristics:

[0299] [Table 30]

[0300] In a further configuration of the invention, preference is given to compounds obtained by combining two partial structures N-1 with one partial structure Ar-25, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0301] [Table 31]

[0302] In a further aspect of the invention, compounds obtained by combining two partial structures N-1 and one partial structure Ar-24′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 2, and in which the indices v is particularly preferably 0, are preferred, which have the following characteristics:

[0303] [Table 32]

[0304] In a further aspect of the invention, there is provided a compound obtained by combining two substructures N-1 and one substructure Ar-33, in which the U radical is C(R 1 )2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 The radical is preferably R 1 Preference is given to compounds which are derived from N-2 and which together form a ring system with further structural elements preferably obtainable by combination of two partial structures N-1 and one partial structure Ar-33, and which have the following properties:

[0305] [Table 33]

[0306] In a further aspect of the invention, there is provided a compound obtained by combining two substructures N-1 and one substructure Ar'-32, in which the U radical is C(R 1 ) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1 The radical is preferably R 1 Preference is given to compounds which are derived from N-2 and which together form a ring system to which further structural elements, preferably obtainable by combination of two partial structures N-1 and one partial structure Ar'-32, are attached, and which have the following characteristics:

[0307] [Table 34]

[0308] In a further aspect of the invention, a compound obtained by combining two substructures N-1 and one substructure Ar-33, in which the U radical is Si(R 1)2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 Preference is given to compounds in which the radical forms a structural element which can be obtained by the combination of preferably two substructures N-1 and one substructure Ar-33, these compounds having the following characteristics:

[0309] [Table 35]

[0310] In a further aspect of the invention, there is provided a compound obtained by combining two substructures N-1 and one substructure Ar'-32, in which the U radical is Si(R 1 ) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1 Preference is given to compounds in which the radical forms a structural element which can preferably be obtained by the combination of two substructures N-1 and one substructure Ar'-32, these compounds having the following characteristics:

[0311] [Table 36]

[0312] In a further aspect of the invention, there is provided a compound obtained by combining two substructures N-1 and one substructure Ar-34, in which the U radical is C(R 1 )2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 The radical is preferably R 1 Preference is given to compounds which are derived from N-2 and which together form a ring system with further structural elements preferably obtainable by combination of two partial structures N-1 and one partial structure Ar-34, and which have the following characteristics:

[0313] [Table 37]

[0314] In a further aspect of the invention, there is provided a compound obtained by combining two substructures N-1 and one substructure Ar'-33, in which the U radical is C(R 1 ) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1 The radical is preferably R 1 Preference is given to compounds which are derived from N-2 and which together form a ring system to which further structural elements, preferably obtainable by combination of two partial structures N-1 and one partial structure Ar'-33, are attached, and which have the following characteristics:

[0315] [Table 38]

[0316] In a further embodiment of the invention, a compound obtained by combining two substructures N-1 and one substructure Ar-34, in which the U radical is Si(R 1 )2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 Preference is given to compounds in which the radical forms a structural element which can preferably be obtained by combination of two substructures N-1 and one substructure Ar-34, these compounds having the following characteristics:

[0317] [Table 39]

[0318] In a further aspect of the invention, there is provided a compound obtained by combining two substructures N-1 and one substructure Ar'-33, in which the U radical is Si(R 1 ) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1 Preference is given to compounds in which the radical forms a structural element which can preferably be obtained by the combination of two substructures N-1 and one substructure Ar'-33, these compounds having the following characteristics:

[0319] [Table 40]

[0320] In a further aspect of the invention, there is provided a compound obtained by combining two substructures N-1 and one substructure Ar-35, in which the U radical is C(R 1 )2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 The radical is preferably R 1 Preference is given to compounds which are derived from N-2 and which together form a ring system with further structural elements preferably obtainable by combination of two partial structures N-1 and one partial structure Ar-35, and which have the following properties:

[0321] [Table 41]

[0322] In a further aspect of the invention, there is provided a compound obtained by combining two substructures N-1 and one substructure Ar'-34, in which the U radical is C(R 1 ) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1The radical is preferably R 1 Preference is given to compounds which are derived from -2 and which together preferably form a ring system with further structural elements which can be obtained by combining two partial structures N-1 and one partial structure N-1 and Ar'-34, and which have the following properties:

[0323] [Table 42]

[0324] In a further embodiment of the invention, a compound obtained by combining two substructures N-1 and one substructure Ar-35, wherein the U radical is Si(R 1 )2, in which not more than 6, preferably not more than 4, particularly preferably not more than 2 radicals of the formula X′ are CH or CD and two R 1 Preference is given to compounds in which the radical forms a structural element which can be obtained by the combination of preferably two substructures N-1 and one substructure Ar-35, these compounds having the following characteristics:

[0325] [Table 43]

[0326] In a further aspect of the invention, there is provided a compound obtained by combining two substructures N-1 and one substructure Ar'-34, in which the U radical is Si(R 1 ) 2, the sum of the indices v, o and m is not more than 5, preferably not more than 3, particularly preferably 2, the indices v are particularly preferably 0, and two R 1 Preference is given to compounds in which the radical forms a structural element which can be obtained by combining preferably two substructures N-1 and one substructure N-1 and Ar'-34, these compounds having the following characteristics:

[0327] [Table 44]

[0328] In a further configuration of the invention, preference is given to compounds obtained by combining two partial structures N-1 with one partial structure Ar-36, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0329] [Table 45]

[0330] In a further configuration of the invention, preference is given to compounds obtained by combining two partial structures N-1 and one partial structure Ar-35′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v is particularly preferably 0, and which have the following characteristics:

[0331] [Table 46]

[0332] In a further configuration of the invention, preference is given to compounds obtained by combining two partial structures N-1 with one partial structure Ar-37, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0333] [Table 47]

[0334] In a further aspect of the invention, compounds obtained by combining two partial structures N-1 and one partial structure Ar-36′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v are particularly preferably 0, are preferred, which have the following characteristics:

[0335] [Table 48]

[0336] In a further configuration of the invention, preference is given to compounds obtained by combining two partial structures N-1 with one partial structure Ar-38, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0337] [Table 49]

[0338] In a further aspect of the invention, compounds obtained by combining two partial structures N-1 and one partial structure Ar-37′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v is particularly preferably 0, are preferred, which have the following characteristics:

[0339] [Table 50]

[0340] In a further configuration of the invention, preference is given to compounds obtained by combining two partial structures N-1 with one partial structure Ar-39, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0341] [Table 51]

[0342] In a further aspect of the invention, compounds obtained by combining two partial structures N-1 and one partial structure Ar-38', in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v is particularly preferably 0, are preferred, which have the following characteristics:

[0343] [Table 52]

[0344] In a further configuration of the invention, preference is given to compounds obtained by combining two partial structures N-1 and one partial structure Ar-40, in which a total of not more than six, preferably not more than four and particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0345] [Table 53]

[0346] In a further aspect of the invention, compounds obtained by combining two partial structures N-1 and one partial structure Ar-39′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v is particularly preferably 0, are preferred, which have the following characteristics:

[0347] [Table 54]

[0348] In a further configuration of the invention, preference is given to compounds obtained by combining four substructures N-1 with one substructure Ar-41, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0349] [Table 55]

[0350] In a further configuration of the invention, compounds obtained by combining four substructures N-1 and one substructure Ar-40′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v is particularly preferably 0, are preferred, which have the following characteristics:

[0351] [Table 56]

[0352] In a further configuration of the invention, preference is given to compounds obtained by combining four partial structures N-1 with one partial structure Ar-42, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0353] [Table 57]

[0354] In a further aspect of the invention, compounds obtained by combining four substructures N-1 and one substructure Ar-41′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v is particularly preferably 0, are preferred, which have the following characteristics:

[0355] [Table 58]

[0356] In a further configuration of the invention, preference is given to compounds obtained by combining four partial structures N-1 with one partial structure Ar-43, in which a total of not more than six, preferably not more than four, particularly preferably not more than two radicals of the formula X' are not CH or CD, which have the following characteristics:

[0357] [Table 59]

[0358] In a further aspect of the invention, compounds obtained by combining four substructures N-1 and one substructure Ar-42′, in which the sum of the indices v, o and m is less than or equal to 5, preferably less than or equal to 3, particularly preferably 1, and in which the indices v is particularly preferably 0, are preferred, which have the following characteristics:

[0359] [Table 60]

[0360] Furthermore, compounds that can be used as active compounds in organic electronic devices may not be in direct contact with a metal atom and preferably are not ligands for metal complexes.

[0361] Examples of suitable compounds of the present invention are those of formulas 1-108 shown below:

[0362] [ka]

[0363] [ka]

[0364]

change

[0365]

change

[0366]

change

[0367]

change

[0368]

change

[0369]

change

[0370]

change

[0371]

change

[0372]

change

[0373] The structures of formulae 1-18 are particularly suitable as hole conducting materials (HTM) and possibly as electron blocking materials (EBM). The structures of formulae 1-33 are particularly suitable as triplet matrix materials (TMM) for phosphorescent emitters and as matrix materials for TADF compounds. The structures of formulae 34-45 are particularly suitable as wide band gap materials. The structures of formulae 46-60 are particularly suitable as electron transport materials (ETM) or as electron conducting triplet matrix materials (eTMM). The structures of formulae 61-67 are particularly suitable as matrix material fluorescent emitters (SMB). The structures of formulae 67-93 are particularly suitable as fluorescent emitters (SEB). The structures of formulae 94-105 are particularly suitable as emitters exhibiting TADF (thermally activated delayed fluorescence) and as TADF compounds in hyperfluorescence.

[0374] Preferred embodiments of the compounds of the invention are specifically described in the examples, but these compounds can be used for all purposes of the invention alone or in combination with further compounds.

[0375] The preferred embodiments described above can be combined with one another as appropriate, provided that the conditions specified in claim 1 are fulfilled. In a particularly preferred embodiment of the invention, the preferred embodiments described above are applied simultaneously.

[0376] The compounds of the invention can in principle be prepared by a variety of methods, however the methods described below have been found to be particularly suitable.

[0377] Thus, the present invention further provides a method for preparing the compounds of the present invention, preferably compounds comprising the structure of formulae (I)-(XVIII), by attaching a compound comprising at least one aliphatic polycyclic ring system having at least three rings to a compound comprising at least one aromatic or heteroaromatic group in a coupling reaction.

[0378] Suitable compounds containing at least one aliphatic polycyclic ring system having at least three rings are often commercially available, and the starting compounds detailed in the examples can be obtained by known methods, for which reason reference is made thereto.

[0379] These compounds can be reacted with further compounds containing at least one aromatic or heteroaromatic group by known coupling reactions, the conditions necessary for this purpose are known to those skilled in the art and the detailed specifications in the examples will assist the skilled artisan in carrying out these reactions.

[0380] Particularly suitable and preferred coupling reactions, both of which result in the formation of CC bonds and / or CN bonds, are those according to Buchwald, Suzuki, Yamamoto, Stille, Heck, Negishi, Sonogashira and Hiyama. These reactions are widely known and the examples provide further guidance to the skilled artisan.

[0381] The principles of the preparation methods detailed above are in principle known from the literature for similar compounds and can be easily adapted by those skilled in the art to the preparation of the compounds of the invention. Further information can be found in the examples.

[0382] By these methods, if necessary after purification, for example recrystallization or sublimation, the compounds of the present invention containing the structures of formulae (I) to (XVIII) can be obtained in high purity, preferably 99% ( 1 It is possible to obtain higher purity (as determined by 1 H NMR and / or HPLC).

[0383] The compounds of the present invention may also have suitable substitutions, for example with 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 provide a solubility in standard organic solvents such that the compounds are soluble at room temperature, for example in toluene or xylene, in sufficient concentrations to allow processing of the compounds from solution. These soluble compounds have a particularly good compatibility with processing from solution, for example by printing methods. In addition, it should be emphasized that the compounds of the present invention, which include at least one structure of formulae (I) to (XVIII), already have a high solubility in these solvents.

[0384] The compounds of the present invention may also be mixed with polymers. It is likewise possible to incorporate these compounds covalently into polymers. This is especially possible in the case of compounds substituted with reactive leaving groups, such as bromine, iodine, chlorine, boronic acid or boronic ester, or with reactive polymerizable groups, such as olefins or oxetanes. They can find use as monomers for producing corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably carried out via halogen or boronic acid functional groups, or via polymerizable groups. In addition, it is possible to crosslink the polymers via such groups. The compounds and polymers of the present invention may be used in the form of crosslinked or non-crosslinked layers.

[0385] Thus, the present invention further provides oligomers, polymers or dendrimers containing one or more of the structures of formulae (I) to (XVIII) or the compounds of the present invention as detailed above, where there is a bond of one or more of the compounds of the present invention or the structures of formulae (I) to (XVIII) to the polymer, oligomer or dendrimer. The bonds of the structures or compounds of formulae (I) to (XVIII) result in the formation of side chains of the oligomer or polymer or in the backbone being bonded thereto. The polymers, oligomers or dendrimers may be conjugated, partially conjugated or non-conjugated. The oligomers or polymers may be linear, branched or dendritic. The same preferences as above apply for the repeating units of the compounds of the present invention in the oligomers, dendrimers and polymers.

[0386] To prepare oligomers or polymers, the monomers of the invention are homopolymerised or copolymerised with further monomers. Preference is given to copolymers in which units of formulae (I) to (XVIII) or the preferred embodiments described above or below are present in the range of 0.01 to 99.9 mol %, preferably 5 to 90 mol %, more preferably 20 to 80 mol %. Suitable preferred comonomers forming the polymer backbone are fluorene (for example according to EP 842208 or WO 2000 / 022026), spirobifluorene (for example according to EP 707020, EP 894107 or WO 2006 / 061181), paraphenylene (for example according to WO 92 / 18552), carbazole (for example according to WO 2004 / 070772 or WO 2004 / 113468), thiophene (for example according to According to EP1028136), dihydrophenanthrenes (for example according to WO2005 / 014689), cis- and trans-indenofluorenes (for example according to WO2004 / 041901 or WO2004 / 113412), ketones (for example according to WO2005 / 040302), phenanthrenes (for example according to WO2005 / 104264 or WO2007 / 017066), or a plurality of these units. The polymers, oligomers and dendrimers may also contain further units, for example hole transporting units, especially those based on triarylamines, and / or electron transporting units.

[0387] In addition, the compounds of the present invention are particularly interesting because they are characterized by a high glass transition temperature.In this context, the compounds of the present invention that can be used as active compounds in organic electronic devices in particular are preferably those that comprise the structures of formulae (I) to (XVIII) and / or formulae (Ia) to (XVIIIa), or those that can be obtained by combining the partial structures of formulae (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), or the above or below preferred embodiments that have a glass transition temperature of at least 70°C, more preferably at least 110°C, even more preferably at least 125°C, and particularly preferably at least 150°C, as determined according to DIN 51005 (edition 2005-08).

[0388] To process the compounds of the invention from a liquid phase, for example by spin-coating or printing methods, formulations of the compounds of the invention are necessary. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone ... xylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 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, hexamethylindane, or a mixture of these solvents.

[0389] Thus, the present invention further provides a formulation comprising the compound of the present invention and at least one further compound.The further compound may be, for example, a solvent, in particular one of the above-mentioned solvents or a mixture of these solvents.Alternatively, the further compound may be at least one further organic or inorganic compound, such as a light-emitting compound, for example a fluorescent dopant, a phosphorescent dopant or a compound exhibiting TADF (thermally activated delayed fluorescence), in particular a phosphorescent dopant, and / or a further matrix material, also used in electronic devices.This further compound may also be a polymer.

[0390] Therefore, the present invention still further provides a composition comprising the compound of the present invention and at least one additional organic functional material.The functional material is generally an organic or inorganic material that is introduced between anode and cathode.Preferably, the organic functional material is selected from the group consisting of fluorescent emitter, phosphorescent emitter, emitter that exhibits TADF (thermally activated delayed fluorescence), host material, electron transport material, electron injection material, hole conduction material, hole injection material, electron blocking material, hole blocking material, wide band gap material, and n-dopant.

[0391] The present invention therefore also relates to a composition comprising at least one compound according to the invention, preferably a compound comprising the structure of formula (I) to (XVIII) or the above or below preferred embodiments, and at least one further matrix material, which according to a particular aspect of the invention has hole transport properties.

[0392] The present invention further provides compositions comprising at least one compound of the invention, preferably a compound comprising at least one of the structures of formulae (I) to (XVIII) or the preferred embodiments described above or below, and at least one wide band gap material, the wide band gap material being understood to mean a material within the meaning of the disclosure of US 7,294,849. These systems show exceptionally advantageous performance data in electroluminescent devices.

[0393] Preferably, the additional compound may have a band gap of 2.5 eV or more, preferably 3.0 eV or more, and most preferably 3.5 eV or more. One way to calculate the band gap is in terms of the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

[0394] Molecular orbitals, especially the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), their energy levels, as well as the energy of the lowest triplet state T1 and the lowest excited singlet state S1 of the material are also determined by quantum chemical calculations. For calculations of metal-free organic substances, first, the structure is optimized by the "ground state / semiempirical / default spin / AM1 / charge 0 / spin singlet" method. Then, energy calculations are performed based on the optimized structure. This is done using the "TD-SCF / DFT / default spin / B3PW91" method with the "6-31G(d)" basis set (charge 0, spin singlet). For metal-containing compounds, the structure is optimized by the "ground state / Hartree-Fock / default spin / LanL2MB / charge 0 / spin singlet" method. Energy calculations are performed similarly to the method described above for organic materials, with the difference that for metal atoms the "LanL2DZ" basis set is used, and for ligands the "6-31G(d)" basis set is used. From the energy calculations, the HOMO energy level HEh or the LUMO energy level LEh is obtained in Hartree units. This is used to determine the HOMO and LUMO energy levels in electron volts, calibrated by cyclic voltammetry measurements, as follows: HOMO(eV)=((HEh*27.212)-0.9899) / 1.1206LUMO(eV)=((LEh*27.212)-2.0041) / 1.385 In the context of this application, these values ​​will be considered to be the HOMO and LUMO energy levels of the material.

[0395] The lowest triplet state T1 is defined as the energy of the triplet state with the lowest energy, which is evident from the quantum chemical calculations given.

[0396] The lowest excited singlet state S1 is defined as the energy of the excited singlet state having the lowest energy, which is evident from the quantum chemical calculations given.

[0397] The method described here is independent of the software package used and always gives the same results. Examples of programs frequently used for this purpose are "Gaussian09W" (Gaussian Inc.) and Q-Chem4.1 (Q-Chem, Inc.).

[0398] The present invention also relates to a composition comprising at least one compound comprising a structure of formula (I)-(XVIII) or the above and below preferred embodiments, and at least one phosphorescent emitter, the term "phosphorescent emitter" also being understood to mean phosphorescent dopant.

[0399] In a system comprising a matrix material and a dopant, the dopant is understood to mean the component which is the minor component in the mixture, and correspondingly, in a system comprising a matrix material and a dopant, the matrix material is understood to mean the component which is the major component in the mixture.

[0400] Preferred phosphorescent dopants for use in the matrix system, preferably the mixed matrix system, are the preferred phosphorescent dopants defined below.

[0401] The term "phosphorescent dopant" typically encompasses compounds in which emission results from a spin-forbidden transition, such as an excited triplet state or a state having a higher spin quantum number, such as a quintet state.

[0402] Suitable phosphorescent compounds (= triplet emitters) are especially compounds that emit light, preferably in the visible range, when appropriately excited, and further contain at least one atom with 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. Preferred phosphorescent emitters used 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 context of the present invention, all luminescent compounds containing the above-mentioned metals are considered as phosphorescent compounds.

[0403] Examples of such luminophores are described in applications WO00 / 70655, WO2001 / 41512, WO2002 / 02714, WO2002 / 15645, EP1191613, EP1191612, EP1191614, WO05 / 033244, WO05 / 019373, US2005 / 0258742, WO2009 / 14 6770, WO2010 / 015307, WO2010 / 031485, WO2010 / 054731, WO2010 / 054728, WO2010 / 08 6089, WO2010 / 099852, WO2010 / 102709, WO2011 / 032626, WO2011 / 066898, WO2011 / 15 7339, WO2012 / 007086, WO2014 / 008982, WO2014 / 023377, WO2014 / 094961, WO2014 / 09 4960, WO2015 / 036074, WO2015 / 104045, WO2015 / 117718, WO2016 / 015815, WO2016 / 12 4304, WO2016 / 124304, WO2017 / 032439, WO2018 / 019687, WO2018 / 019688, WO2018 / 041769, WO2018 / 054798, WO2018 / 069196, WO2018 / 069197, WO2018 / 069273.

[0404] In general, all phosphorescent complexes used in phosphorescent OLEDs according to the prior art and known to a person skilled in the art in the field of organic electroluminescence are suitable, and a person skilled in the art can use further phosphorescent complexes without resorting to inventive techniques.

[0405] Specific examples of phosphorescent dopants are listed in the table below:

[0406] [ka]

[0407] [ka]

[0408] [ka]

[0409] [ka]

[0410] [ka]

[0411] [ka]

[0412] [ka]

[0413] [ka]

[0414] The above compounds comprising the structure of formula (I)-(XVIII) or the preferred embodiments detailed above can preferably be used as active components in electronic devices. Electronic devices are understood to mean any device comprising an anode, a cathode, and at least one layer between the anode and the cathode, said layer comprising at least one organic or organometallic compound. Thus, the electronic device of the present invention comprises an anode, a cathode, and at least one intervening layer containing at least one compound comprising the structure of formula (I). Preferred electronic devices here are selected from the group consisting of organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), organic electrosensors, light emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic plasmonic light emitting devices (DMKoller et al., Nature Photonics, 2008, 1-4), preferably organic electroluminescent devices (OLEDs, PLEDs), especially phosphorescent OLEDs containing at least one compound comprising the structure of formula (I) in at least one layer. Organic electroluminescent devices are particularly preferred. The active component is generally an organic or inorganic material introduced between the anode and the cathode, for example a charge injection, charge transport or charge blocking material, but especially a light emitting material and a matrix material.

[0415] A preferred embodiment of the present invention is an organic electroluminescent device. An organic electroluminescent device comprises a cathode, an anode and at least one light-emitting layer. In addition to these layers, it may comprise further separate 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, it is possible to p-dope one or more hole transport layers, for example with metal oxides, for example MoO3 or WO3, or with (per)fluorinated electron-deficient aromatic systems, and / or n-dope one or more electron transport layers. It is also possible to introduce intermediate layers between two light-emitting layers, for example with exciton blocking function and / or to control the charge balance in the electroluminescent device. However, it should be pointed out that each of these layers does not necessarily have to be present.

[0416] In this case, the organic electroluminescent device can contain an emitting layer or contain several emitting layers. If several emitting layers are present, they preferably have several emission maxima at 380 nm to 750 nm, and produce a white light emission as a whole; in other words, various emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. Particularly preferred are three-layer systems (for basic configurations, see, for example, WO2005 / 011013) in which three layers exhibit blue, green and orange or red emission, or systems with four or more emitting layers. Furthermore, tandem OLEDs are also preferred. The system can also be a hybrid system in which one or more layers fluoresce and one or more other layers phosphoresce.

[0417] In a preferred embodiment of the present invention, the organic electroluminescent device contains the compound of the present invention, preferably a compound comprising the structure of formula (I)-(XVIII) or the preferred embodiment detailed above, as a matrix material, preferably as an electron-conducting matrix material, in one or more light-emitting layers, preferably in combination with a further matrix material, preferably a hole-conducting matrix material. In a further preferred embodiment of the present invention, the further matrix material is an electron transport compound. In another further preferred embodiment, the further matrix material is a compound with a large band gap that is not involved to a significant extent, if at all, in hole and electron transport in the layer. The light-emitting layer comprises at least one light-emitting compound.

[0418] In a further particularly preferred embodiment of the present invention, the organic electroluminescent device of the present invention comprises a compound of the present invention, preferably a compound comprising the structure of formula (I)-(XVIII) or the preferred embodiments detailed above, in a hole-conducting layer or an electron-conducting layer.

[0419] Suitable matrix materials which can be used in combination with the compounds of the formulae (I) to (XVIII) or according to 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, especially monoamines, carbazole derivatives, such as CBP(N,N-biscarbazolylbiphenyl) or carbazole derivatives disclosed in WO2005 / 039246, US2005 / 0069729, JP2004 / 288381, EP1205527 or WO2008 / 086851, such as indolocarbazole derivatives according to WO2007 / 063754 or WO2008 / 056746, such as indenocarbazole derivatives according to WO2010 / 136109 and WO2011 / 000455, such as EP1617710 azacarbazole derivatives according to EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, for example, according to WO 2007 / 137725, silanes, for example, according to WO 005 / 111172, azaboroles or boronic 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, also for example EP 652273 or zinc complexes according to WO 2009 / 062578, diazasirol or tetraazasirol derivatives, for example, according to WO 2010 / 054729, diazaphosphole 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, triphenyl derivatives, for example, according to WO 2012 / 048781, Nylene derivatives, for example lactams according to WO2011 / 116865, WO2011 / 137951 or WO2013 / 064206, 4-spirocarbazole derivatives, for example according to WO2014 / 094963 or WO2015 / 192939, or dibenzofuran derivatives, for example according to WO2015 / 169412, WO2016 / 015810, WO2016 / 023608 or the unpublished applications EP16158460.2 and EP16159829.7. It is likewise possible for further phosphorescent emitters, which emit at shorter wavelengths than the actual emitter, to be present in the mixture as cohosts.

[0420] Preferred co-host materials are triarylamine derivatives, especially monoamines, indenocarbazole derivatives, 4-spirocarbazole derivatives, lactams, and carbazole derivatives.

[0421] A preferred triarylamine derivative for use as a co-host material with the compounds of the present invention has the following formula (TA-1):

[0422] [ka]

[0423] (In the formula, Ar 5 are the same or different in each occurrence, have 6 to 40 carbon atoms, and in each occurrence, one or more R 2 an aromatic or heteroaromatic ring system optionally substituted by a radical, where two or more adjacent R 2 The substituents are one or more R 3 Optionally, a monocyclic or polycyclic aliphatic ring system, optionally substituted by radicals, may be formed, where the symbol R 2 is as defined above, especially with respect to formulae (I) to (XVIII). Preferably, the compound is selected from the group consisting of Ar 5 are in each occurrence the same or different and have 5 to 24, preferably 5 to 12, aromatic ring atoms, and in each occurrence one or more R 2 The radical is an aryl or heteroaryl group which may be substituted, but is preferably unsubstituted.

[0424] Preferred Ar 5Exemplary groups are selected from the group consisting of phenyl, ortho, meta or para 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, indenocarbazolyl, 1-, 2-, 3- or 4-dibenzothienyl and 1-, 2-, 3- or 4-carbazolyl, each of which may be selected from the group consisting of one or more R 2 It may be substituted with a radical, but is preferably unsubstituted.

[0425] Preferably, Ar 5 The groups are in each case the same or different and are defined as R 1 -1~R 1 -92 group, more preferably R 1 -1~R 1 -54 are selected.

[0426] In a preferred embodiment of the compound of formula (TA-1), at least one Ar 5 The group is selected from a biphenyl group, which may be an ortho, meta or para biphenyl group. In a further preferred embodiment of the compound of formula (TA-1), at least one Ar 5 The group is selected from a fluorene group or a spirobifluorene group, where these groups may be attached to the nitrogen atom at the 1, 2, 3 or 4 position, respectively. In an even more preferred embodiment of the compound of formula (TA-1), at least one Ar 5 The radicals are selected from phenylene or biphenyl radicals, where the radicals are ortho-, meta- or para-linked radicals substituted with dibenzofuran, dibenzothiophene or carbazole radicals, especially dibenzofuran radicals, the dibenzofuran or dibenzothiophene radicals being linked to the phenylene or biphenyl radical via the 1-, 2-, 3- or 4-position, and the carbazole radicals being linked to the phenylene or biphenyl radical via the 1-, 2-, 3- or 4-position or a nitrogen atom.

[0427] In a particularly preferred embodiment of the compound of formula (TA-1), one Ar 5 The radicals are selected from fluorene or spirobifluorene radicals, in particular 4-fluorene or 4-spirobifluorene radicals, with one Ar 5 The group is selected from a biphenyl group, in particular a parabiphenyl group, or a fluorene group, in particular a 2-fluorene group, and the third Ar 5 The radicals are selected from dibenzofuran radicals, especially paraphenylene or parabiphenyl radicals substituted by 4-dibenzofuran radicals, or carbazole radicals, especially N-carbazole or 3-carbazole radicals.

[0428] A preferred indenocarbazole derivative for use as a cohost material with the compounds of the present invention is represented by the following formula (TA-2):

[0429] [ka]

[0430] (In the formula, Ar 5 and R 1 has the definition given above, especially with respect to formula (I) and / or (TA-1) The compound is selected from the group consisting of the compounds of Ar 5 Preferred embodiments of the group are those of the structure R 1 -1~R 1 -92, more preferably R 1 -1~R 1 It is -54.

[0431] A preferred embodiment of the compound of formula (TA-2) is the compound of formula (TA-2a):

[0432] [ka]

[0433] (In the formula, Ar 5 and R 1 has the definition given above, especially with respect to formula (I) and / or (TA-1) The compound is represented by the formula: 1 The groups are preferably the same or different and are alkyl groups having 1 to 4 carbon atoms, especially methyl groups, or aromatic ring systems having 6 to 12 carbon atoms, especially phenyl groups. More preferably, two R 1 More preferably, the R bonded to the indenocarbazole basic skeleton in formula (TA-2a) is a methyl group. 1 The substituents are H or a carbazole group which may be bonded to the indenocarbazole base skeleton via the 1, 2, 3 or 4 position or via a nitrogen atom, especially via the 3 position.

[0434] A preferred 4-spirocarbazole derivative for use as a co-host material with the compounds of the present invention has the following formula (TA-3):

[0435] [ka]

[0436] (In the formula, Ar 5 and R 1 has the definition given above, especially with respect to formula (I) and / or (TA-1) The compound is selected from the group consisting of the compounds of Ar 5 Preferred embodiments of the group are those of the structure R 1 -1~R 1 -92, more preferably R 1 -1~R 1 It is -54.

[0437] A preferred embodiment of the compound of formula (TA-3) is the compound of formula (TA-3a):

[0438] [ka]

[0439] (In the formula, Ar 5 and R 1has the definition given above, especially with respect to formula (I) and / or (TA-1) It is a compound of Ar 5 Preferred embodiments of the group are those of the structure R 1 -1~R 1 -92, more preferably R 1 -1~R 1 It is -54.

[0440] Preferred lactams for use as co-host materials with the compounds of the present invention have the formula (LAC-1):

[0441] [ka]

[0442] (In the formula, R 1 has the definition given above, especially with respect to formula (I). The compound is selected from the group consisting of

[0443] A preferred embodiment of the compound of formula (LAC-1) is the compound of formula (LAC-1a):

[0444] [ka]

[0445] (In the formula, R 1 has the definition given above especially with respect to formulae (I) to (XVIII) Here, R 1 are preferably the same or different in each occurrence and are H, or have 5 to 40 aromatic ring atoms and one or more R 2 an aromatic or heteroaromatic ring system optionally substituted by radicals, where R 2 may have the definition given above, especially with respect to formulae (I) to (XVIII). Most preferably, R 1 The substituents are H and 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, and in each case one or more non-aromatic R2 The preferred R is selected from the group consisting of aromatic or heteroaromatic ring systems which may be substituted, but are preferably unsubstituted, by the radical. 1 Examples of substituents are selected from the group consisting of phenyl, ortho-, meta- or para-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-dibenzothienyl and 1-, 2-, 3- or 4-carbazolyl, each of which may be selected from the group consisting of one or more R 2 The preferred R 1 The structure is preferably R-1 to R-79, more preferably R 1 -1~R 1 This is the same structure as illustrated above for -51.

[0446] It may be preferable to use a mixture of several different matrix materials, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material. It is also preferable to use a mixture of a charge-transporting matrix material and an electrically inactive matrix material which participates in the charge transport, if not to a significant extent at all, as described, for example, in WO 2010 / 108579.

[0447] It is further preferred to use a mixture of two or more triplet emitters with a matrix, in which case a triplet emitter with a short wavelength emission spectrum acts as a co-matrix for a triplet emitter with a longer wavelength emission spectrum.

[0448] More preferably, in a preferred embodiment, the compounds of the present invention comprising the structure of formulae (I)-(XVIII) can be used as a matrix material in the light-emitting layer of an organic electronic device, especially an organic electroluminescent device, such as an OLED or an OLEC, in which case the matrix material containing the compound comprising the structure of formulae (I)-(XVIII) or the preferred embodiments described above or below is present in the electronic device in combination with one or more dopants, preferably phosphorescent dopants.

[0449] In this case, the ratio of the matrix material in the light-emitting layer is 50.0% to 99.9% by volume in the case of a fluorescent light-emitting layer, preferably 80.0% to 99.5% by volume, more preferably 92.0% to 99.5% by volume, and is 85.0% to 97.0% by volume in the case of a phosphorescent light-emitting layer.

[0450] Correspondingly, the proportion of the dopant is 0.1% to 50.0% by volume for the fluorescent-emitting layer, preferably 0.5% to 20.0% by volume, and more preferably 0.5% to 8.0% by volume, and 3.0% to 15.0% by volume for the phosphorescent-emitting layer.

[0451] The light-emitting layer of an organic electroluminescent device may also comprise a system containing several matrix materials (mixed matrix system) and / or several dopants. In this case, too, the dopant is generally the material with the lower proportion in the system and the matrix material is the material with the higher proportion in the system. However, in individual cases, the proportion of a single matrix material in the system may be lower than the proportion of a single dopant.

[0452] In a further preferred embodiment of the present invention, the compounds comprising the formulae (I) to (XVIII) or the structures of the above or below preferred embodiments are used as components of a mixed matrix system. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. In this case, preferably 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 components may also be mainly or completely combined by a single mixed matrix component, in which case the further mixed matrix component(s) perform the other function. Here, the two different matrix materials may 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. It is preferred to use a mixed matrix system in a phosphorescent organic electroluminescent device. One source of further details on mixed matrix systems is application WO2010 / 108579.

[0453] The present 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.

[0454] Preferred cathodes are metals, metal alloys, multilayer structures made of various metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.) with low work functions. In addition, suitable are alloys made of alkali metals or alkaline earth metals and silver, such as alloys made of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, it is also possible to use further metals with relatively high work functions, such as Ag, in which case metal combinations such as Mg / Ag, Ca / Ag or Ba / Ag are commonly used. It may be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between the metallic cathode and the organic semiconductor. Examples of materials useful for this purpose are alkali metal or alkaline earth metal fluorides as well as the corresponding oxides or carbonates (e.g. LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Also useful for this purpose are organic alkali metal complexes, such as Liq (lithium quinolinate). The thickness of this layer is preferably 0.5 to 5 nm.

[0455] Preferred anodes are materials with a high work function. Preferably, the anode has a work function of more than 4.5 eV vs. vacuum. Firstly, metals with high redox potentials are suitable for this purpose, such as Ag, Pt or Au. Secondly, metal / metal oxide electrodes (e.g. Al / Ni / NiO x , Al / PtO x) may be preferred. Depending on the application, at least one of the electrodes must be transparent or partially transparent to allow either irradiation (O-SC) or light emission (OLED / PLED, O-laser) of the organic material. Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Furthermore, conductive doped organic materials are preferred, especially conductive doped polymers, such as PEDOT, PANI or derivatives of these polymers. It is further preferred to apply a p-doped hole transport material to the anode as a hole injection layer, in which case suitable p-dopants are metal oxides, such as MoO3 or WO3, or (per)fluorinated electron-deficient aromatic systems. Further suitable p-dopants are HAT-CN (hexacyanohexaazatriphenylene) or the compound NPD9 from Novaled. Such a layer simplifies hole injection into materials with a low HOMO, i.e. a high HOMO in terms of intensity.

[0456] In the further layers it is generally possible to use any material as is used according to the prior art for layers, and the skilled person can combine any of these materials with the materials of the invention in an electronic device without the use of inventive techniques.

[0457] Correspondingly, the devices are structured (depending on the application), the contacts are connected and finally sealed, since the lifetime of such devices is significantly shortened in the presence of water and / or air.

[0458] Additionally preferred are electronic devices, especially organic electroluminescent devices, characterized in that one or more layers are coated by a sublimation process. In this case, the material is deposited in a vacuum sublimation system, typically at 10 -5 Less than mbar, preferably less than 10 -6 The initial pressure may be lower or higher, for example 10 -7It is also possible to go below mbar.

[0459] Likewise preferred are electronic devices, especially organic electroluminescent devices, characterized in that one or more layers are coated by the OVPD (organic vapor phase deposition) method or with the aid of carrier gas sublimation. In this case, the materials are preferably -5 It is applied at pressures 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 by a nozzle and thus structured (eg, MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0460] In addition, electronic devices, especially organic electroluminescent devices, are preferred, 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 by LITI (Light Induced Thermal Imaging, Thermal Transfer Printing) or inkjet printing. For this purpose, soluble compounds are required, which can be obtained, for example, by suitable substitution.

[0461] Electronic devices, especially organic electroluminescent devices, can also be fabricated as hybrid systems by applying one or more layers from solution and one or more other layers by vapor deposition. For example, a light-emitting layer comprising a compound of the invention comprising the structure of formulae (I)-(XVIII) and a matrix material can be applied from solution, to which a hole-blocking layer and / or an electron-transporting layer can be applied by vapor deposition under reduced pressure.

[0462] These methods are generally known to those skilled in the art and can be applied without difficulty to electronic devices, particularly organic electroluminescent devices, that contain the compounds of the present invention comprising the structures of formulae (I)-(XVIII) or the preferred embodiments detailed above.

[0463] The electronic devices, and particularly the organic electroluminescent devices, of the present invention are notable for one or more of the following surprising advantages over the prior art: 1. Electronic devices, in particular organic electroluminescent devices, comprising the compounds, oligomers, polymers or dendrimers of the invention which can be used as active compounds in organic electronic devices, or the preferred embodiments described above or below, in particular as electron conducting material and / or hole conducting material or as matrix material, have a very good lifetime.

[0464] 2. Electronic devices, especially organic electroluminescent devices, comprising the compounds, oligomers, polymers or dendrimers of the invention, or the preferred embodiments described above or below, usable as active compounds in organic electronic devices, especially as electron transport materials, hole conducting materials and / or host materials, have excellent efficiency. More specifically, the efficiency is clearly higher compared to similar compounds that do not contain an aliphatic polycyclic ring system having at least three rings and fused to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms. An advantage of the compounds, oligomers, polymers or dendrimers of the invention, or the preferred embodiments described above or below, usable as active compounds in organic electronic devices, is a low operating voltage when used in electronic devices. In this context, these compounds especially result in a low roll-off, i.e. only a slight decrease in the power efficiency of the device at high luminance.

[0465] 3. An electronic device, particularly an organic electroluminescent device, comprising the compound, oligomer, polymer or dendrimer that can be used as an active compound in an organic electronic device, or the preferred embodiments described above or below, as an electron transport material, hole conduction material and / or host material, has excellent color purity.

[0466] 4. The compounds, oligomers, polymers or dendrimers of the invention, or preferred embodiments thereof described above or below, that can be used as active compounds in organic electronic devices, exhibit very high thermal and photochemical stability, resulting in compounds with very long lifetimes.

[0467] 5. By using the compounds, oligomers, polymers or dendrimers usable as active compounds in organic electronic devices or the preferred embodiments described above or below, it is possible to avoid the formation of optical loss paths in electronic devices, in particular in organic electroluminescent devices, as a result of which these devices are characterized by high PL efficiency and therefore high EL efficiency of the emitter and good energy transfer from the matrix to the dopant.

[0468] 6. The compounds, oligomers, polymers or dendrimers that can be used as active compounds in organic electronic devices, or preferred embodiments thereof described above or below, have excellent glass film forming properties.

[0469] 7. The compounds, oligomers, polymers or dendrimers that can be used as active compounds in organic electronic devices, or preferred embodiments thereof described above or below, form very good films from solution.

[0470] These above mentioned advantages are not accompanied by any further degradation of the electronic properties.

[0471] The compounds and mixtures of the present invention are suitable for use in electronic devices. Electronic devices here are understood to mean devices that contain at least one layer that contains at least one organic compound. However, the components may also contain inorganic materials or other layers that are entirely made of inorganic materials.

[0472] Thus, the present invention further provides the use of the compounds or mixtures of the present invention in electronic devices, especially organic electroluminescent devices.

[0473] The present invention still 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-conducting 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 conducting materials and / or electron transport materials.

[0474] The present invention further provides an electronic device comprising at least one of the compounds or mixtures of the present invention as detailed above.In this case, the preferences for the compounds as detailed above also apply to the electronic device.More preferably, the electronic device is selected from the group consisting of organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quenching devices (O-FQDs), organic electrical sensors, light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic plasmonic light-emitting devices (DMKoller et al., Nature Photonics, 2008, 1-4), preferably organic electroluminescent devices (OLEDs, PLEDs), especially phosphorescent OLEDs.

[0475] In a further embodiment of the present invention, the organic electroluminescent device of the present invention does not contain any separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, which means that the light-emitting layer is directly adjacent to the hole injection layer or anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode, as described, for example, in WO2005 / 053051.In addition, it is also possible to use the same or similar metal complex as the metal complex in the light-emitting layer as the hole transport or hole injection material directly adjacent to the light-emitting layer, as described, for example, in WO2009 / 030981.

[0476] In the further layer of the organic electroluminescent device of the present invention, it is possible to use any material as typically used according to the prior art.Therefore, those skilled in the art can use all materials known for organic electroluminescent devices without inventive techniques in combination with the compound of the present invention that can be used as active compound in organic electronic devices, preferably the compound that comprises the structure of formula (I) to (XVIII) and / or formula (Ia) to (XVIIIa), or the compound that can be obtained by combining the partial structures of formula (N-1) to (N-6), (Ar-1) to (Ar-54) and / or (Ar'-1) to (Ar'-53), or according to preferred embodiments.

[0477] The compounds of the present invention generally have very good properties when used in organic electroluminescent devices.In particular, when the compounds of the present invention are used in organic electroluminescent devices, their lifetime is significantly better than that of similar compounds according to the prior art.At the same time, the further properties of organic electroluminescent devices, especially efficiency and voltage, are also improved or at least equal.

[0478] It should be pointed out that variations of the embodiments described in the present invention are included within the scope of the present invention. Any feature disclosed in the present invention may be replaced by an alternative feature serving the same purpose or an equivalent or similar purpose, unless expressly excluded. Therefore, any feature disclosed in the present invention should be considered as an example of a generic series, or an equivalent or similar feature, unless otherwise specified.

[0479] All features of the present invention may be combined with one another in any manner, unless certain features and / or steps are mutually exclusive. This is particularly true for preferred features of the present invention. Similarly, features of non-essential combinations may be used individually (and not in combination).

[0480] It should further be pointed out that many features, particularly those of the preferred embodiments of the invention, are inventive in themselves and should not be considered as merely part of an embodiment of the invention, and that independent protection can be sought for these features in addition to, or as an alternative to, any invention claimed herein.

[0481] The technical teachings disclosed by the present invention may be extracted and combined with other examples.

[0482] The present invention will be illustrated in more detail in the examples that follow, without any intention of limiting the invention thereby.

[0483] Using the details given, a person skilled in the art can manufacture further electronic devices of the present invention without the use of inventive techniques, and thus can practice the present invention throughout the entire scope of the claims.

[0484] [example] The syntheses that follow are carried out in dry solvents under a protective gas atmosphere unless otherwise stated. In addition, metal complexes are handled under the exclusion of light or under yellow light. Solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective numbers in brackets or cited numbers for individual compounds refer to the CAS number of that compound known from the literature. In the case of compounds that can be displayed in multiple tautomeric forms, one tautomeric form is shown as a representative.

[0485] 1) Synthesis of Synthon S: Example S1:

[0486] [ka]

[0487] 27.2 g (100 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-97-4], 32.4 g (100 mmol) of 2-(6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononen-2-yl)-4,4,5,5-tetrahydro-4,4,5,5-tetramethyl-2,5-diphenyl-1,2-dioxane [1801624-97-4] A well-stirred mixture of methyl-1,3,2-dioxaborolane [1801624-63-4], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolyl-phosphine, 225 mg (1 mmol) of palladium(II) acetate, 350 ml of toluene, 80 ml of dioxane and 300 ml of water is heated under reflux for 16 hours. After cooling, the organic phase is separated from the aqueous phase, washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, then dried over magnesium sulfate. The absorbent is filtered off using a silica gel bed in the form of a toluene slurry and the filtrate is concentrated to dryness. The glassy residue is recrystallized from isopropanol. Yield: 30.8 g (78 mmol), 78%. 1 Approximately 97% purity by H NMR.

[0488] In a similar manner, the following compounds can be prepared:

[0489] [ka]

[0490] Example S2:

[0491] [ka]

[0492] To a well-stirred solution of 39.5 g (100 mmol) of S1 in 500 ml of dichloromethane, a mixture of 3.1 ml (120 mmol) of bromine and 100 ml of dichloromethane is added dropwise in the dark over a period of 3 h. After the end of the addition, the mixture is stirred under reflux for 4 h and at room temperature for 8 h. Excess bromine is neutralized by adding 200 ml of saturated sodium sulfite solution, 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 absorbent 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%. 1 Approximately 95% purity by H NMR.

[0493] The following compounds can be prepared similarly:

[0494] [ka]

[0495] Example S3:

[0496] [ka]

[0497] Prepared similarly to S2, except that 6.4 ml (240 mmol) of bromine was used. Also, 100 mg of iron powder was added to a solution of S1 in dichloromethane. Yield: 33.7 g (61 mmol), 61%. 1 Approximately 97% purity by H NMR.

[0498] The following compounds can be prepared similarly:

[0499] [ka]

[0500] Example S4:

[0501] [ka]

[0502] To a well-stirred solution of 27.6 g (50 mmol) of S3 in 500 ml of THF cooled to -78 °C, add dropwise 65.6 ml (105 mmol) of 1.6 M n-BuLi in hexane and stir the mixture for another 30 min. Add dropwise slowly a mixture of 5.1 ml (55 mmol) of dimethylcarbamoyl chloride [79-44-7] (WARNING: toxic, carcinogenic) and 50 ml of THF and stir the mixture for another 30 min, then allow it to warm up gradually to room temperature. After 2 h at room temperature, add 200 ml of saturated ammonium chloride solution, increase the mixture with 300 ml of ethyl acetate, separate the aqueous phase and concentrate the organic phase to dryness. Take up the residue in 250 ml of dichloromethane (DCM), wash 3 times with 300 ml of water, once with 300 ml of saturated sodium chloride solution and dry over magnesium sulfate. The absorbent is filtered off, the filtrate is concentrated to dryness under reduced pressure and the residue is recrystallized from acetonitrile. Yield: 18.1 g (43 mmol), 85%. 1 Approximately 97% purity by H NMR.

[0503] Example S5:

[0504] [ka]

[0505] To a well-stirred solution of 47.4 g (100 mmol) of S2 in 500 ml of THF cooled to -78°C, 65.6 ml (105 mmol) of n-BuLi 1.6 M in hexane is added dropwise, and the mixture is stirred for another 3 hours. Then, a solution of 27.2 g (105 mmol) of 2-bromo-9-fluorenone [3096-56-3] in 300 ml of THF is slowly added dropwise, the mixture is stirred for another 30 minutes, and then allowed to warm gradually to room temperature. After 2 hours at room temperature, the THF is removed under reduced pressure, the residue is taken up in 500 ml of glacial acetic acid, 30 ml of concentrated hydrochloric acid are added, and the mixture is heated under reflux for 3 hours. The mixture is allowed to cool to 80°C, 500 ml of water is slowly added dropwise, and while the mixture is warm, the precipitated product is suction filtered, washed three times with 100 ml of water and then with 100 ml of methanol each time, and dried under reduced pressure. Yield: 56.6 g (89 mmol), 89%. 1 Approximately 97% purity by H NMR.

[0506] In a similar manner, the following compounds can be prepared:

[0507] [ka]

[0508] Example S20:

[0509] [ka]

[0510] A well-stirred mixture of 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-dimethano-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-tolyl-phosphine, 225 mg (1 mmol) of palladium(II) acetate, 350 ml of toluene, 60 ml of dioxane and 300 ml of water is heated under reflux for 16 hours. After cooling, the organic phase is separated from the aqueous phase, washed once with 300 ml of water, once with 300 ml of saturated sodium chloride solution, then dried over magnesium sulfate. The absorbent is filtered off using a bed of silica gel in the form of a toluene slurry, and the filtrate is concentrated to dryness. The residue is recrystallized from acetonitrile with the addition of a small amount of ethyl acetate. The secondary amine so obtained is dissolved in 300 ml of DMF, 45.4 g (250 mmol) of copper(II) acetate and 2.24 g (10 mmol) of palladium(II) acetate are added, and the mixture is stirred at 140 ° C for 4 hours. Most of the DMF is removed under reduced pressure, the residue is taken up in 500 ml of DCM, 300 ml of concentrated ammonia solution is added, the mixture is stirred at room temperature for 1 hour, the organic phase is separated, washed 3 times with 100 ml of concentrated ammonia solution, once with saturated sodium chloride solution, and dried over magnesium sulfate. The magnesium sulfate is filtered off using a bed of silica gel in the form of a DCM slurry, the filtrate is concentrated to dryness and the residue is recrystallized from acetonitrile / ethyl acetate. Yield: 18.7 g (47 mmol), 47%, 1 Approximately 95% purity by H NMR.

[0511] Example S25:

[0512] [ka]

[0513] A well-stirred mixture of 27.2 g (100 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-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 (diameter 3 mm) and 300 ml of dimethylacetamide is heated under reflux for 30 h. While the mixture is still warm, the salts are filtered off under suction through a bed of Celite in the form of a dimethylacetamide slurry, the filtrate is concentrated to dryness, the residue is taken up in 300 ml of DCM and filtered through a silica gel column (10 x 30 cm) to extract the core fraction. The DCM is removed from the column under reduced pressure; the residue is recrystallized from acetonitrile. Yield: 33.4 g (88 mmol), 88%, 1 Approximately 99% pure by H NMR.

[0514] Example S26:

[0515] [ka]

[0516] To a well-stirred solution of 38.0 g (100 mmol) of S25 in 500 ml of DCM cooled to 0° C., a solution of 17.8 g (100 mmol) of N-bromosuccinimide in 300 ml of dichloromethane is added dropwise in the dark, and the mixture is then stirred for a further 12 h at room temperature. The reaction is washed once with 200 ml of saturated sodium bicarbonate solution, three times with 200 ml of water each time, once with 200 ml of saturated sodium chloride solution, and then dried over magnesium sulfate. The absorbent is filtered off, the filtrate is concentrated and the residue is chromatographed by flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 33.0 g (72 mmol), 72%. 1 Approximately 95% purity by HNMR.

[0517] Example S30:

[0518] [ka]

[0519] 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-dimethano-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-tolyl-phosphine, 225 mg (1 mmol) of palladium(II) acetate, 350 ml of toluene, 60 ml of ethanol and 300 ml of water is heated under reflux for 16 hours. After cooling, 60 ml of 10N aqueous HCl are added, the organic phase is separated from the aqueous phase, washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, then dried over magnesium sulfate. The absorbent is filtered off using a bed of silica gel in the form of a toluene slurry, and the filtrate is concentrated to dryness. The residue is recrystallized from isopropanol with the addition of a small amount of ethyl acetate. The phenol thus obtained is dissolved in 800 ml of mesitylene and the thoroughly stirred solution is mixed with 27.6 g (200 mmol) of potassium carbonate, 100 g of 3A molecular sieves, 9.3 g (50 mmol) of sodium 2,4,6-trimethylbenzoate [32642-28-7], 1.82 g (10 mmol) of 4,5-diazafluoren-9-one [50890-67-0], 4.26 g (10 mmol) of 1,3-bis[2,6-bis(1-methylethyl)phenyl]-1H-imidazolium chloride [250285-32-6] and 1.12 g (5 mmol) of palladium(II) acetate, and the mixture is then heated to 120° C. for 16 hours while introducing a gentle stream of air. While the mixture is still warm, it is suction filtered through a bed of silica gel in the form of a mesitylene slurry, the mesitylene is removed under reduced pressure and the residue is recrystallized from acetonitrile. Yield: 15.6 g (54 mmol), 54%. 1Approximately 95% purity by H NMR.

[0520] Example S31:

[0521] [ka]

[0522] To a well-stirred mixture of 33.2 g (100 mmol) of S30 and 500 ml of THF cooled to -78 ° C, 65.6 ml (105 mmol) of 1.6 M n-BuLi in hexane is added dropwise, and the mixture is stirred at -78 ° C for 60 min and then at -40 ° C for 30 min. After cooling again to -78 ° C, a mixture of 20.7 g (110 mmol) of triisopropyl borate [5419-55-6] and 50 ml of THF is added rapidly with good stirring, and the mixture is stirred for another 30 min. The reaction mixture is allowed to warm to room temperature, 100 ml of saturated ammonium chloride solution is added, the mixture is stirred for another 15 min, the organic phase is separated, made up to 500 ml of ethyl acetate, and washed three times with 300 ml of water each time and once with 200 ml of saturated sodium chloride solution. The organic phase is concentrated to dryness under reduced pressure and the residue is recrystallized from acetonitrile with the addition of a little water. Yield: 18.9 g (57 mmol), 57%. 1 Approximately 95% purity by H NMR.

[0523] Example S35:

[0524] [ka]

[0525] 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-dimethano-5H-benzocyclononene [1801624-66-7], 26.9 g (300 mmol) of copper(I) cyanide, 50 g of glass beads (diameter 3 mm) and 300 of NMP is heated to 170 ° C for 18 hours. While the mixture is warm, it is suction filtered through a bed of Celite in the form of an NMP slurry, 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%. 1 Approximately 95% purity by H NMR.

[0526] Example S36:

[0527] [ka]

[0528] 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-dimethano-5H-benzocyclononene [1801624-66-7] in 1000 ml of THF cooled to -100 ° C, 235 ml (400 mmol) of 1.7 M t-BuLi in pentane is added dropwise and the mixture is stirred for another 30 min. Then, a solution of 24.8 g (100 mmol) of S35 in 300 ml of THF is slowly added dropwise and the mixture is stirred for another 1 h, allowed to warm to room temperature and quenched by the addition of 50 ml of methanol. The THF is removed under reduced pressure, the residue is taken up in 300 ml of NMP, 30 ml of concentrated hydrochloric acid is added and the mixture is heated to about 150 ° C for 4 h. After cooling, the mixture is made up to 500 ml of ethyl acetate and the organic phase is 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 absorbent is filtered off, the filtrate is concentrated to dryness under reduced pressure and the yellow residue is recrystallized twice from acetonitrile. Yield: 19.4 g (43 mmol), 43%. 1Approximately 95% purity by H NMR.

[0529] In a similar manner, the following compounds can be prepared:

[0530] [ka]

[0531] Example S38:

[0532] [ka]

[0533] To a suspension of 44.9 g (100 mmol) of S36 in 500 ml of glacial acetic acid, 100 ml of aqueous hydroiodic acid (57% by weight) and 200 ml of aqueous hypophosphorous acid (50% by weight) are added and the mixture is heated under reflux for 18 h. The precipitated solid is filtered off with suction, washed five times with 300 ml of hot water each time, extracted by stirring with 300 ml of hot ethanol, washed with another 300 ml of hot ethanol and dried under reduced pressure. Yield: 38.6 g (92 mmol), 92%. 1 Approximately 95% purity by H NMR.

[0534] The following compounds can be prepared similarly:

[0535] [ka]

[0536] Example S40:

[0537] [ka]

[0538] To a solution of 41.9 g (100 mmol) of S38 in 500 ml of dichloromethane, 19.6 g (110 mmol) of N-bromosuccinimide are added in portions in the dark with good stirring and the mixture is stirred for 6 h at room temperature. The reaction mixture is washed once with 300 ml of saturated sodium bicarbonate solution, three times with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The absorbent 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 Approximately 98% purity by H NMR.

[0539] The following compounds can be prepared similarly:

[0540] [ka]

[0541] 2) Synthesis of amine A: Example A1

[0542] [ka]

[0543] To a solution of 63.6 g (100 mmol) of S5 and 38.6 g (120 mmol) of bis-p-biphenylamine [102113-98-4] in 500 ml of toluene, 4.0 ml (4.0 mmol) of a 1.0 M solution of tri-tert-butylphosphine in toluene, 449 mg (2 mmol) of palladium acetate and 16.0 g of sodium tert-butoxide (166 mmol) are added and the mixture is heated under reflux for 3 h. The reaction mixture is cooled to room temperature, weighed down with toluene and filtered through a bed of Celite. The filtrate is concentrated under reduced pressure and the residue is crystallized from ethyl acetate / n-heptane. The crude product is extracted three times with hot acetonitrile and purified by zone sublimation under reduced pressure (p ca. 10 -5Purify twice by HPLC (at 300 rpm, T approx. 310° C.). Yield: 63.1 g (72 mmol), 72%. Purity by HPLC >99.9%.

[0544] The following compounds can be prepared similarly:

[0545] [ka]

[0546] [ka]

[0547] [ka]

[0548] [ka]

[0549] [ka]

[0550] [ka]

[0551] [ka]

[0552] Example A22:

[0553] [ka]

[0554] A well-stirred mixture of 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, 100 ml of dioxane and 400 ml of water is heated under reflux for 16 hours. After cooling, the organic phase is separated from the aqueous phase, washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and then dried over magnesium sulfate. The absorbent is filtered off using a bed of silica gel in the form of a toluene slurry, and the filtrate is concentrated to dryness. The glassy residue is recrystallized from ethyl acetate / isopropanol. The crude product is extracted three times with hot toluene and purified by zone sublimation under reduced pressure (p ca. 10 -5 Purify twice by HPLC (at 300° C., mbar, T approx. 330° C.). Yield: 66.8 g (70 mmol), 70%. Purity by HPLC >99.9%.

[0555] The following compounds can be prepared similarly:

[0556] [ka]

[0557] [ka]

[0558] 3) Synthesis of carbazole C: Example C1:

[0559] [ka]

[0560] A well-stirred mixture of 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, 80 ml of dioxane and 300 ml of water is heated under reflux for 16 hours. After cooling, the aqueous phase is separated and the organic phase is concentrated to dryness. The residue is taken up in 500 ml of DCM and the organic phase is washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and then dried over magnesium sulfate. The absorbent is filtered off using a bed of silica gel in the form of a DCM slurry, and the filtrate is concentrated to dryness. The residue is extracted by stirring with hot butyl acetate / isopropanol, then extracted three times with hot toluene and purified by zone sublimation under reduced pressure (p ca. 10 -5 mbar, T about 320° C.). Yield: 40.0 g (66 mmol), 66%. Purity by HPLC >99.9%.

[0561] The following compounds can be prepared similarly:

[0562] [ka]

[0563] [ka]

[0564] [ka]

[0565] 4) Synthesis of Triazine T: Example T1:

[0566] [ka]

[0567] 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-dimethano-5H-benzocyclononen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1801624-63-4], 31.9 g (150 mmol) of potassium phosphate tripotassium, 821 mg (2 mmol) of S-Phos, 225 mg (1 mmol) of acetic acid A well-stirred mixture of palladium(II), 400 ml of toluene, 80 ml of dioxane and 300 ml of water is heated under reflux for 16 hours. After cooling, the organic phase is separated from the aqueous phase, washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, then dried over magnesium sulfate. The absorbent is filtered off using a bed of silica gel in the form of a toluene slurry, and the filtrate is concentrated to dryness. The residue is extracted by stirring with hot isopropanol, then five times with hot acetonitrile and purified by zone sublimation under reduced pressure (p ca. 10 -5 mbar, T ca. 310° C.). Yield: 37.8 g (65 mmol), 65%. Purity by HPLC >99.9%.

[0568] The following compounds can be prepared similarly:

[0569] [ka]

[0570] 5) Synthesis of host material for singlet emitter SH: Example SH1:

[0571] [ka]

[0572] A well-stirred mixture of 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 dioxane and 300 ml of water is heated under reflux for 16 hours. After cooling, the aqueous phase is separated and the organic phase is concentrated to dryness. The residue is taken up in 500 ml of DCM and the organic phase is washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and then dried over magnesium sulfate. The absorbent is filtered off using a bed of silica gel in the form of a DCM slurry and the filtrate is concentrated to dryness. The residue was extracted by stirring with hot butyl acetate / isopropanol, then extracted five times with hot toluene and purified by zone sublimation under reduced pressure (p ca. 10 -5 Purify by HPLC (at 375° C., mbar, T ca. 320° C.). Yield: 31.9 g (58 mmol), 58%, syn / anti isomer mixture. Purity by HPLC >99.9%.

[0573] 6) Synthesis of singlet emitter S Example SE1:

[0574] [ka]

[0575] The same procedure as for 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. Purification was performed five times by hot extraction with cyclohexane and zone sublimation under reduced pressure (p ca. 10 -5 mbar, T about 330° C.). Yield: 26.0 g (53 mmol), 53%. Purity by HPLC >99.9%.

[0576] The following compounds can be prepared similarly:

[0577] [ka]

[0578] 7) Synthesis of spiro material H: The following compounds can be prepared similarly to S5:

[0579] [ka]

[0580] OLED device manufacturing 1) Vacuum processed devices: The OLEDs of the invention and of the prior art are produced by the general methods according to WO2004 / 058911 adapted to the circumstances described therein (variations in layer thickness, materials used).

[0581] In the examples that follow, results are presented for various OLEDs. Glass plaques that have been cleaned (Miele laboratory glass washer cleaning, Merck Extran cleaning agent) and coated with a 50 nm thick structured ITO (indium tin oxide) are pretreated with UV ozone (PR-100 UV ozone generator from UVP) for 25 minutes and within 30 minutes are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate, purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from an aqueous solution) to improve processability, then baked at 180° C. for 10 minutes. These coated glass plaques form the substrates on which the OLEDs are applied.

[0582] The OLED basically has the following layer structure: substrate / Hole Injection Layer 1 (HIL1) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm / Hole Transport Layer 1 (HTL1) / Hole Transport Layer 2 (HTL2) / Emitting Layer (EML) / Hole Blocking Layer (HBL) / Electron Transport Layer (ETL) / Optional Electron Injection Layer (EIL) and finally the cathode. The cathode is formed by a 100 nm thick layer of aluminum.

[0583] First of all, the vacuum processed OLEDs are described. For this purpose, all materials are applied by thermal evaporation in a vacuum chamber. In this case, the emissive layer always consists of at least one matrix material (host material) and a light-emitting dopant (emitter) that is added to the matrix material(s) in a certain volumetric proportion by co-evaporation. Details given in the form TMM1:TMM2:Ir(L1) (55%:35%:10%) mean here that in the layer the material TMM1 is present in a proportion of 55% by volume, TMM2 in a proportion of 35% and Ir(L1) in a proportion of 10%. Similarly, the electron transport layer may also consist of a mixture of the two materials. The exact structure of the OLEDs can be found in Table 1. The materials used for the manufacture of the OLEDs are given in Table 4.

[0584] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W), and the external quantum efficiency (EQE, measured in percent) as a function of luminance calculated from the current-voltage-luminance characteristic (IUL characteristic) assuming Lambertian emission characteristics, and also the lifetime are determined. The electroluminescence spectrum is measured at 1000 cd / m 2 The luminance is then determined at 10000cd / m2 and the CIE1931x and y color coordinates are calculated. 2 It is defined as the time it takes for the brightness to decrease to 90% of the initial brightness when operating at the initial brightness of 100%.

[0585] The OLED can also be initially operated at different initial luminances, and the lifetime values ​​can then be converted to numbers at other initial luminances with the aid of conversion formulas known to those skilled in the art.

[0586] Use of the compounds of the present invention as materials in phosphorescent OLEDs The compounds of the present invention can be used in OLED as HTM (hole transport material), TMM (triplet matrix material), ETM (electron transport material) and emitter material in emitting layer.Compounds according to table 4 are used as prior art comparison.Results for OLED are shown in table 2.

[0587] [Table 61-1]

[0588] [Table 61-2]

[0589] [Table 61-3]

[0590] [Table 61-4]

[0591] [Table 61-5]

[0592] [Table 61-6]

[0593] [Table 62-1]

[0594] [Table 62-2]

[0595] [Table 62-3]

[0596] 2. Solution-processed devices: A: From low molecular weight soluble functional materials The materials of the invention can also be processed from solution, in which case the processing techniques are much simpler compared to vacuum-processed OLEDs, but still resulting in OLEDs with good properties. The production of such components is based on the production of polymer light-emitting diodes (PLEDs), which have already been described many times in the literature (e.g. WO2004 / 037887). The structure is composed of: substrate / ITO / hole injection layer (60 nm) / interlayer (20 nm) / emissive layer (60 nm) / hole blocking layer (10 nm) / electron transport layer (40 nm) / cathode. For this purpose, a Technoprint substrate (soda-lime glass) is used, to which an ITO structure (indium tin oxide, transparent conductive anode) is applied. In a clean room, the substrate is cleaned with DI water and a cleaning agent (Deconex 15PF) and then activated by UV / ozone plasma treatment. Then, also in a clean room, a 20 nm hole injection layer is applied by spin coating. The required spin speed depends on the degree of dilution and the specific spin coater configuration. To remove residual water from the layer, the substrate is baked on a hotplate at 200° C. for 30 min. The intermediate layer used serves for hole transport and in this case uses HL-X from Merck. Alternatively, the intermediate layer may also be replaced by one or more layers, which only have to fulfill the condition that they are not leached out again by the subsequent processing step of depositing the EML from solution. For the production of the emissive layer, the triplet emitter of the invention is dissolved in toluene or chlorobenzene together with a matrix material. The typical solid content of such a solution is 16-25 g / l, if, as in this case, a layer thickness of 60 nm typical of the device is to be achieved by spin coating. The solution-processed device contains an emissive layer of Matrix1:Matrix2:Ir-Ref.3 and optionally Ir-Ref.4. Optionally, Matrix3 is additionally used (see Table 3). The emissive layer is spun on in an inert gas atmosphere, in this case argon, and baked at 160° C. for 10 min. On top of that, a hole blocking layer (10 nm ETM1) and an electron transport layer (40 nm ETM1(50%) / ETM2(50%)) are deposited (e.g., in a Lesker deposition system, typical deposition pressure 5×10 -6mbar). Finally, an aluminium cathode (100 nm) (high purity metal from Aldrich) is applied by evaporation. To protect the device from air and atmospheric humidity, it is finally encapsulated and then characterized. The cited OLED example is not yet optimised. Table 3 summarises the data obtained. The lifetime LT50 is 1000 cd / m 2 This is defined as the time it takes for the luminance to drop to 50% of the initial luminance when activated with an initial brightness of 100%.

[0597] [Table 63-1]

[0598] [Table 63-2]

[0599] [Table 64-1]

[0600] [Table 64-2]

[0601] [Table 64-3]

Claims

1. A compound that can be used as an active compound in an organic electronic device, the compound having at least one aromatic or heteroaromatic ring system having 5 to 60 carbon atoms and fused to an aliphatic polycyclic ring system having at least three rings, The aliphatic polycyclic ring system having at least three rings and fused to an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms is represented by the formula (N-1): 【Chemistry 1】 (wherein the dotted line represents the bond of said aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which is fused an aliphatic polycyclic ring system having at least three rings; the symbol R １ and v has the definition given below, R １ are the same or different in each case, 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 straight chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be represented by one or more R ２ radicals) (wherein one or more non-adjacent CH ２ The group is -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 -, N.R. 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 one or more R ２ an aryloxy or heteroaryloxy group optionally substituted by a radical, or a aryloxy group having 5 to 40 aromatic ring atoms and one or more R ２ an aralkyl or heteroaralkyl group optionally substituted by a radical; R ２ are the same or different in each case and are H, D, F, Cl, Br, I, CN, B (OR ３ ) ２ , NO ２ , C(=O)R ３ , C.R. 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 straight chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be represented by one or more R ３ radicals) (wherein one or more non-adjacent CH ２ The group is -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 -, N.R. 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 5 to 40 aromatic ring atoms, in each case one or more R ３ an aromatic or heteroaromatic ring system, optionally substituted by a radical, or having 5 to 40 aromatic ring atoms and one or more R ３ an aryloxy or heteroaryloxy group optionally substituted by a radical; ２ may also together form a mono- or polycyclic aliphatic or aromatic or heteroaromatic ring system; R ３ are in each occurrence the same or different and are selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms; at the same time, two or more adjacent substituents R ３ may also together form a mono- or polycyclic aliphatic or aromatic or heteroaromatic ring system; Ar １ are the same or different in each occurrence and have 5 to 30 aromatic ring atoms and one or more preferably non-aromatic R ２ At the same time, two Ar are bonded to the same silicon, nitrogen, phosphorus or boron atom. １ The radical may also be a single bond or 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 and (b) a bridge selected from the group consisting of the subscript v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; and The aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which an aliphatic polycyclic ring system having at least three rings is condensed is represented by the formulae (Ar-4) to (Ar-11), (Ar-13) to (Ar-15), (Ar-23) to (Ar-25), and (Ar-34) to (Ar-44): 【Chemistry 2-1】 【Chemistry 2-2】 【Chemistry 2-3】 (Wherein, X′ is CR １ and U is 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 R １ has the definition as described above, and the aliphatic polycyclic ring system having at least three rings is bonded to the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms at each position specified by ○.

2. The compound according to claim 1, characterized in that the aromatic or heteroaromatic ring system having 5 to 60 carbon atoms to which the aliphatic polycyclic ring system having at least three rings is condensed forms a partial structure selected from the formulae (Ar-4) to (Ar-11), (Ar-13) to (Ar-15), (Ar-23) to (Ar-25), and (Ar-34) to (Ar-44).

3. The compound comprises a hole transport group selected from the group consisting of formulas (H-1) to (H-26), where formulas (H-1) to (H-3) are defined as follows: 【Chemistry 3】 (In the formula, the bond shown by the dotted line indicates the bond position, Ar ２ , Ar ３ , Ar ４ are each independently an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which is represented by one or more R １ may be substituted with a radical; p is 0 or 1; Z is a bond or C(R １ ) ２ , Si(R １ ) ２ , C=O, N-R １ , N-Ar １ , B.R. １ , P.R. １ , PO(R １ ), SO, SO ２ , Se, O or S) and Formulae (H-4) to (H-26) are defined as follows: 【Chemistry 4-1】 【Chemistry 4-2】 【Chemistry 4-3】 (In the formula, Y １ is O, S, C (R １ ) ２ , N.R. １ or NAr １ where the dotted bond indicates the attachment position, e is 0, 1 or 2, j is 0, 1, 2 or 3, h is the same or different in each occurrence and is 0, 1, 2, 3 or 4, p is 0 or 1, and Ar １ has the definition given in claim 1, and Ar ２ is as defined above, where R １ The group is R ２ must be replaced by a radical, R ２ has the definition given in claim 1) 3. A compound according to claim 1 or 2, characterized in that

4. The compound has the formula (QL) 【Chemistry 5】 (In the formula, L １ is a bond or has 5 to 40 aromatic ring atoms and is one or more R １ represents an aromatic or heteroaromatic ring system optionally substituted by radicals, Q is an electron transport group selected from the structures of formula (Q-1), (Q-2), (Q-3), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9) and / or (Q-10); 【Chemistry 6】 (In the formula, the bond shown by the dotted line indicates the bond position, Q′ is the same or different in each occurrence, CR １ or N, Q″ is NR １ , O or S; where at least one Q′ is N; R １ is as defined in claim 1, where the substituent R １ is a substituent R defined in claim 1 in the structures of formula (N-1), formula (Ar-4) to (Ar-11), formula (Ar-13) to (Ar-15), formula (Ar-23) to (Ar-25), and formula (Ar-34) to (Ar-44). ２ 4. The compound according to claim 1, further comprising an electron transport group which can be represented by the formula:

5. 5. An oligomer, polymer or dendrimer containing one or more compounds according to any one of claims 1 to 4, wherein there is one or more bonds of said compounds to said polymer, oligomer or dendrimer in place of a hydrogen atom or a substituent.

6. A composition comprising at least one compound according to any one of claims 1 to 4, or the oligomer, polymer or dendrimer according to claim 5, and at least one further compound selected from the group consisting of a fluorescent emitter, a phosphorescent 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 and a hole blocking material.

7. A formulation comprising at least one compound according to any one of claims 1 to 4, or an oligomer, polymer or dendrimer according to claim 5, or a composition according to claim 6, and at least one solvent.

8. Use of a compound according to any one of claims 1 to 4, an oligomer, polymer or dendrimer according to claim 5, or a composition according to claim 6 as a fluorescent emitter, an emitter exhibiting thermally activated delayed fluorescence (TADF), 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 band gap material in an electronic device.

9. A process for preparing a compound according to any one of claims 1 to 4 or an oligomer, polymer and / or dendrimer according to claim 5, characterized in that a compound comprising at least one aliphatic polycyclic ring system having at least three rings is attached to a compound comprising at least one aromatic or heteroaromatic group in a coupling reaction.

10. 10. An electronic device comprising at least one compound according to any one of claims 1 to 4, an oligomer, polymer or dendrimer according to claim 5, or a composition according to claim 6, the electronic device being selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells and organic laser diodes.

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