Aromatic heterocycles for organic electroluminescent devices.

Abstract

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

Description

[Technical field]

[0001] The present invention relates to aromatic heterocycles for use in electronic devices, particularly organic electroluminescent devices, and to electronic devices, particularly organic electroluminescent devices, comprising these heterocyclic compounds. [Background technology]

[0002] The light-emitting materials used in organic electroluminescent devices are often phosphorescent organometallic complexes or fluorescent compounds.In general, there is still a need for improvement in electroluminescent devices.

[0003] US Patent Publication No. 2010 / 0051928, WO 2010 / 104047, WO 2017 / 175690, WO 2019 / 132506, WO 2019 / 111971 and WO 2020 / 064666 disclose polycyclic compounds that can be used in organic electroluminescent devices.The compound according to the present invention is not disclosed.

[0004] The compounds described as preferred in WO 2019 / 111971 are in particular those represented by the formula (3-11) R 5 and R 14 and having no further substituents on the particular aromatic group to which the diarylamino group is attached (see WO 2019 / 111971, formula (3-13)).

[0005] In addition, Chinese Patent No. 109761981 discloses a compound with anthracene group that can be used as a matrix material. The use of this compound as a light emitter is not described or suitable. Similar compounds are also described in John B. Henry et al., J. Phys.Chem. A 2011, 115,5435-5442. Summary of the Invention

[0006] In general, there is still a need for improvements of these heterocyclic compounds, for example for use as emitters, especially fluorescent emitters, in particular with regard to lifetime and color purity, but also with regard to device efficiency and operating voltage.

[0007] 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 result in good device properties when used in such devices, and to provide corresponding electronic devices.

[0008] More specifically, the objective addressed by the present invention is to provide compounds that provide long life, good efficiency, and low operating voltage.

[0009] Furthermore, the compounds should have good processability and in particular should exhibit good solubility.

[0010] A further object of the present invention may be seen as providing compounds which are suitable for use, in particular as emitters, in phosphorescent or fluorescent electroluminescent devices. A particular problem addressed by the present invention is to provide emitters which are suitable for red, green or blue electroluminescent devices, preferably blue electroluminescent devices.

[0011] Furthermore, the compounds, especially when used as emitters in organic electroluminescent devices, should result in devices with excellent color purity.

[0012] A further objective may be seen as providing electronic components with excellent performance at very low cost and with consistent quality.

[0013] Additionally, the electronic devices need to be able to be used or adapted for many purposes. More specifically, the performance of the electronic devices needs to be maintained over a wide temperature range.

[0014] Surprisingly, it has been found that this object is achieved by the specific compounds described in detail below, which are preferably very suitable for use in electroluminescent devices, and lead to organic electroluminescent devices that exhibit very good properties, especially in terms of lifetime, color purity, efficiency and operating voltage.The present invention therefore provides these compounds and electronic devices, especially organic electroluminescent devices that comprise such compounds.

[0015] The present invention provides a compound comprising at least one structure of formula (I), preferably a compound of formula (I): [ka] in which A is in each case the same or different and is a substructure of the formula (A1) or (A2), preferably a substructure of the formula (A1), [ka] The substructure has two substructures B fused thereto, and is represented by the symbols o and * represents two condensation sites for each substructure B, one substructure B is condensed to A via the position labeled o, and one substructure B is * and at least one of the moieties B is selected from the moieties of formula (B1), [ka] The further substructure B is selected from the substructure of formula (B1) or the substructure of formula (B2) shown below: [ka] The dotted bond represents the site of condensation of substructures B and A; Ring C care the same or different in each occurrence and are a fused aliphatic or heteroaliphatic ring having 5 to 60 ring atoms and optionally substituted by one or more R groups, preferably an aliphatic or heteroaliphatic ring having 5 to 20, more preferably 5 to 18, and most preferably 5 to 12 ring atoms and optionally substituted by one or more R groups; Ring C b are the same or different in each occurrence and are a fused aliphatic or heteroaliphatic ring having 5 to 60 ring atoms and optionally substituted by one or more R groups, preferably an aliphatic or heteroaliphatic ring having 5 to 20, more preferably 5 to 18, and most preferably 5 to 12 ring atoms and optionally substituted by one or more R groups; Further symbols are as follows: Z is the same or different in each occurrence and is N, C-CN, or CR c is preferably N or C-CN, more preferably C-CN; Y is the same or different in each occurrence, O, P(=O)R c , SO, SO2, C(O)O, C(S)O, C(O)S, C(=O)NR c , C(═O)NAr′, preferably CO, P(═O)R c , SO, SO2, more preferably CO; W 1 , W 2 is in each occurrence the same or different and is C(R), O, S, Si(R), preferably C(R), X is the same or different in each occurrence and is N or CR, preferably CR, provided that X, X b Not more than two of the groups are N; X a is the same or different in each case, N or CR a and preferably CR a and X b is the same or different in each case, N or CR b and preferably CR bwhere X, X in one ring b Not more than two of the groups are N; X c is the same or different in each case, N or CR c and preferably CR c and R is the same or different in each case and is H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar)2, N(R d )2, C(=O)N(Ar)2, C(=O)N(R d )2, C(Ar)3, C(R d )3, Si(Ar)3, Si(R d )3, B(Ar)2, B(R d )2, C(=O)Ar, C(=O)R d , P(=O)(Ar)2, P(=O)(R d )2, P(Ar)2, P(R d )2, S(=O)Ar, S(=O)R d , S(=O)2Ar, S(=O)2R d , OSO2Ar, OSO2R d , a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is in each case independently selected from one or more R d groups, and one or more non-adjacent CH groups may be substituted by R d C=CR d , C≡C, Si(R d )2, C=O, C=S, C=Se, C=NR d , -C(=O)O-, -C(=O)NR d -, NR d , P(=O)(R d ), -O-, -S-, SO, or SO2), or having 5 to 60 aromatic ring atoms, in each case one or more R dan aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R d an aryloxy group or a heteroaryloxy group optionally substituted by a group, or a aryloxy group having 5 to 60 aromatic ring atoms and one or more R d an arylthio group or a heteroarylthio group optionally substituted by a group, or a arylthio group having 5 to 60 aromatic ring atoms and one or more R d A diarylamino group, an arylheteroarylamino group, a diheteroarylamino group, or a aryl group having 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl group, which may be substituted by a group, and one or more R d an aralkyl or heteroarylalkyl group, optionally substituted by a group, and at the same time one R group can be replaced by a further group, preferably R or R b may form a ring system together with Ar is the same or different in each occurrence, has 5 to 60 aromatic ring atoms, and is selected from one or more R d At the same time, two Ar groups bonded to the same carbon, silicon, nitrogen, phosphorus or boron atom are bridged by a single bond or separated by a B(R d ), C(R d )2, Si(R d )2, C=O, C=NR d , C=C(R d )2, O, S, S=O, SO2, N(R d ), P(R d ), and P(=O)R d and the linker may be linked via a bridge selected from R a , R b , R c , R d is the same or different in each case 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, C(Ar')3, C(R 1)3, Si(Ar')3, Si(R 1 )3, B(Ar')2, B(R 1 )2, C(=O)Ar', C(=O)R 1 , P(=O)(Ar')2, P(=O)(R 1 )2, P(Ar')2, P(R 1 )2, S(=O)Ar', S(=O)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is in each case independently selected from one or more R 1 groups, and one or more non-adjacent CH groups may be substituted by R 1 C=CR 1 , C≡C, Si(R 1 )2, C=O, C=S, C=Se, C=NR 1 , -C(=O)O-, -C(=O)NR 1 -, NR 1 , P(=O)(R 1 ), -O-, -S-, SO, or SO2), or having 5 to 60 aromatic ring atoms, in each case one or more R 1 an aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R 1 an aryloxy group or a heteroaryloxy group optionally substituted by a group, a , R b , R c , R d The radicals may form a ring system together with further radicals, preferably R, wherein Ar' is the same or different in each case and has 5 to 60 aromatic ring atoms and one or more R 1At the same time, two Ar′ groups bonded to the same carbon, silicon, nitrogen, phosphorus or boron atom are bridged by a single bond or separated by 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 the linker may be linked via a bridge selected from R 1 are the same or different in each case and are H, D, F, Cl, Br, I, CN, NO2, N(Ar'')2, N(R 2 )2, C(=O)Ar'', C(=O)R 2 , P(=O)(Ar'')2, P(Ar'')2, B(Ar'')2, B(R 2 )2, C(Ar'')3, C(R 2 )3, Si(Ar'')3, Si(R 2 ) 3, a linear alkyl group, an alkoxy group, or a thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl group, an alkoxy group, or a thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be selected from the group consisting of one or more R 2 groups, and one or more non-adjacent CH groups may be replaced by -R 2 C=CR 2 -, -C≡C-, Si(R 2 )2, C=O, C=S, C=Se, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 2 ), -O-, -S-, SO, or SO2, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN, or NO2), or having 5 to 60 aromatic ring atoms, in each case one or more R 2an aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R 2 an aryloxy group or a heteroaryloxy group optionally substituted by a group, or a aryloxy group having 5 to 60 aromatic ring atoms and one or more R 2 aryl or heteroaryl groups, or combinations of these systems, and at the same time, two or more, preferably adjacent, R 1 The groups may together form a ring system, and at the same time, one or more R 1 The group may form a ring system together with further moieties of the compound, Ar″, in each occurrence, is the same or different, has 5 to 30 aromatic ring atoms, and is selected from one or more R 2 Ar" groups bonded to the same carbon, silicon, nitrogen, phosphorus or boron atom are bridged by a single bond or separated by a 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 the linker may be linked via a bridge selected from R 2 are in each case the same or different and are selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon group 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, which may in turn be replaced by one or more alkyl groups each having 1 to 4 carbon atoms, and at the same time two or more, preferably adjacent, substituents R 2 may be joined together to form a ring system.

[0016] Preference is given here to structures / compounds of formula (I) in which the two substructures B are selected from the substructures of formula (B1).

[0017] In a preferred configuration, the compound of the present invention may comprise a structure of formula (I-1) to (I-4), and more preferably, the compound of the present invention may be selected from the compounds of formula (I-1) to (I-4): [ka] JPEG2025507608000006.jpg81170 where C b , C c , Y, W 1 , W 2 , Z, X, X a , X b , and X c has the definition given above in particular for formula (I).

[0018] Here, structures of formula (I-1) and / or (I-3) are preferred, and structures of formula (I-1) are particularly preferred.

[0019] Preferably, R, R a , R b , R c , R d At least one, preferably at least two of the groups are not H, preferably not H, D, OH, NO2, F, Cl, Br, I. Thus, preferably X b or R b The R group adjacent to the group is preferably CN, N(Ar), N(R d )2, C(=O)N(Ar)2, C(=O)N(R d )2, C(Ar)3, C(R d )3, Si(Ar)3, Si(R d )3, B(Ar)2, B(R d )2, C(=O)Ar, C(=O)R d , P(=O)(Ar)2, P(=O)(R d )2, P(Ar)2, P(R d )2, S(=O)Ar, S(=O)R d, S(=O)2Ar, S(=O)2R d , OSO2Ar, OSO2R d , a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is in each case independently selected from one or more R d groups, and one or more non-adjacent CH groups may be substituted by R d C=CR d , C≡C, Si(R d )2, C=O, C=S, C=Se, C=NR d , -C(=O)O-, -C(=O)NR d -, NR d , P(=O)(R d ), -O-, -S-, SO, or SO2), or having 5 to 60 aromatic ring atoms, in each case one or more R d an aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R d an aryloxy group or a heteroaryloxy group optionally substituted by a group, or a aryloxy group having 5 to 60 aromatic ring atoms and one or more R d an arylthio group or a heteroarylthio group optionally substituted by a group, or a arylthio group having 5 to 60 aromatic ring atoms and one or more R d A diarylamino group, an arylheteroarylamino group, a diheteroarylamino group, or a aryl group having 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl group, which may be substituted by a group, and one or more R d arylalkyl or heteroarylalkyl groups, optionally substituted by a group, and at the same time the R group is selected from the group consisting of a further group, preferably R or R b and / or R may form a ring system. a , R b , Rc , R d At least one of the groups is preferably the same or different in each case and is selected from the group consisting of CN, N(Ar′), N(R 1 )2, C(=O)N(Ar')2, C(=O)N(R 1 )2, C(Ar')3, C(R 1 )3, Si(Ar')3, Si(R 1 )3, B(Ar')2, B(R 1 )2, C(=O)Ar', C(=O)R 1 , P(=O)(Ar')2, P(=O)(R 1 )2, P(Ar')2, P(R 1 )2, S(=O)Ar', S(=O)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1 , a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is in each case independently selected from one or more R 1 groups, and one or more non-adjacent CH groups may be substituted by R 1 C=CR 1 , C≡C, Si(R 1 )2, C=O, C=S, C=Se, C=NR 1 , -C(=O)O-, -C(=O)NR 1 -, NR 1 , P(=O)(R 1 ), -O-, -S-, SO, or SO2), or 5 to 60 aromatic ring atoms, in each case one or more R 1 an aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms, in each case one or more R 1 an aryloxy group or a heteroaryloxy group optionally substituted by a group, a , R b, R c , R d The groups may also form a ring system together with or with further groups. In this context, N(Ar)2 and N(R d ) 2 groups are less preferred compared to the other groups mentioned.

[0020] An aryl group in the context of the present invention comprises 6 to 40 carbon atoms, a heteroaryl group in the context of the present invention comprises 2 to 40 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 is understood here to mean either a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused (annelated) aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatics linked together by a single bond, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0021] An electron-deficient heteroaryl group in the context of the present invention is a heteroaryl group having at least one heteroaromatic 6-membered ring with at least one nitrogen atom.Furthermore, an aromatic or heteroaromatic 5-membered or 6-membered ring may be fused to this 6-membered ring.Examples of electron-deficient heteroaryl groups include pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, or quinoxaline.

[0022] An aromatic ring system in the context of the present invention comprises 6 to 60 carbon atoms in the ring system, preferably 6 to 40 carbon atoms in the ring system. A heteroaromatic ring system in the context of the present invention comprises 2 to 60 carbon atoms in the ring system, preferably 3 to 40 carbon atoms, and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system in the context of the present invention is understood to mean a system which does not necessarily contain only aryl or heteroaryl groups, but in which two or more aryl or heteroaryl groups can also be linked by non-aromatic units such as carbon, nitrogen or oxygen atoms. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, stilbenes, etc. are also considered as aromatic ring systems in the context of the present invention, as are systems in which two or more aryl groups are linked, for example by short alkyl groups. Preferably, the aromatic ring system is selected from fluorene, 9,9'-spirobifluorene, 9,9-diarylamine or a group in which two or more aryl and / or heteroaryl groups are linked together by a single bond.

[0023] In the context of the present invention, an aliphatic hydrocarbon group or an alkyl or alkenyl or alkynyl group, which may contain 1 to 20 carbon atoms and in which individual hydrogen atoms or CH2 groups may be replaced by the abovementioned groups, is preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, , n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl radicals. An alkoxy group having 1 to 40 carbon atoms is preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy.A thioalkyl group having 1 to 40 carbon atoms is understood to mean, in particular, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. In general, an alkyl, alkoxy or thioalkyl group according to the invention may be linear, branched or cyclic, one or more non-adjacent CH groups may be replaced by the above groups, and furthermore one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO, preferably F, Cl or CN, more preferably F or CN, and particularly preferably CN.

[0024] Aromatic or heteroaromatic ring systems having 5 to 60 or 5 to 40 aromatic ring atoms, which in each case may be substituted by the abovementioned groups and which may be linked to the aromatic or heteroaromatic system via any desired position, are in particular benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetra ... cyclohydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo Benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyrimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole , pyridazine, hexaazatriphenylene, 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, 1,2,4-triazole, benzotriazole, 1,2,It is understood to mean groups derived from 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, or groups derived from combinations of these systems.

[0025] In the context of this specification, the phrase that two or more groups may be taken together to form a ring should be understood to mean, in particular, that the two groups are linked to each other by a chemical bond, with the formal removal of two hydrogen atoms. This is illustrated by the following scheme:

[0026] [ka]

[0027] However, it is further understood that the above phrase also means that when one of the two groups is hydrogen, the second group is attached to the position to which the hydrogen atom is attached to form a ring. This is exemplified by the following scheme:

[0028] [ka]

[0029] Preferably, R, R d At least one of the groups may not be H, preferably R, R d At least one of the groups is not H, D, F, Cl, Br, or I.

[0030] Preferably, R c At least one, and preferably both, of the groups R cThe group may be H or D.

[0031] In a preferred configuration, one R group, preferably X b Group or R b The R group adjacent to the R group has 5 to 13 aromatic ring atoms and at least one R d It may be an aromatic or heteroaromatic ring system optionally substituted by groups.

[0032] Furthermore, more preferably, the group attached to the Y group adjacent to the Y group may not have an acidic proton, and when Y is C=O, it is preferred to rule out keto-enol tautomerism. An acidic proton in this context is a proton with a high pKa, preferably the pKa of the proton is at least 21, more preferably at least 22, particularly preferably at least 25.

[0033] In a further preferred embodiment, the compound of the present invention may comprise at least one substructure of formulae (B1-1) to (B1-30): [ka] JPEG2025507608000010.jpg224170 JPEG2025507608000011.jpg248170 JPEG2025507608000012.jpg96170 where symbol C c , W 1 , Y, R, R b , R c , and R d has the definition given above specifically for formula (I), the dotted bond represents the site of condensation of the moiety to A, and further symbols and indices used are as follows: X 1 is the same or different in each case, N or CR d , preferably CR d where X in one ring is 1 Not more than two of the groups are N; Y 1 is the same or different in each case, and C(R d )2, (R d )2C-C(R d )2, (R d )C=C(R d ), N.R. d , NAr', O, S, SO, SO2, Se, P(O)R d , B.R. d , or Si(R d )2, preferably C(R d )2, (R d )2C-C(R d )2, (R d )C=C(R d ), O, or S, more preferably C(R d )2, k is 0 or 1; n is 0, 1, 2 or 3, preferably 0, 1 or 2; m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2; l is 0, 1, 2, 3, 4, or 5, preferably 0, 1, or 2.

[0034] Here, structures of formulae (B1-1) to (B1-18) are preferred, structures of formulae (B1-1) and (B1-3) are particularly preferred, and structures of formulae (B1-2) and (B1-3) are especially preferred.

[0035] In a further preferred embodiment, when the compound comprises the partial structure (B2), the partial structure (B2) may be selected from the structures of the formulae (B2-1) to (B2-30): [ka] JPEG2025507608000014.jpg241170 JPEG2025507608000015.jpg186170 where symbol C b , W 1 , W 2 , Z, R, R b , Rc , and R d has the definition given above in particular for formula (I) and the symbol X 1 , Y 1 and the indices k, n, m, and l have the definitions given above, particularly for formulas (B1-1) through (B1-30), and the dotted bond represents the site of condensation of the moiety to A.

[0036] Here, structures of the formulae (B2-1) to (B2-18) are preferred, structures of the formulae (B2-1) and (B2-3) are particularly preferred, and structures of the formulae (B2-2) and (B2-3) are especially preferred.

[0037] In a preferred embodiment, the compound of the present invention may comprise a structure of formula (II-1) to (II-21), and more preferably, the compound of the present invention may be selected from the compounds of formula (II-1) to (II-21): [ka] JPEG2025507608000017.jpg244170 JPEG2025507608000018.jpg171170 where symbol C b , C c , Y, W 1 , W 2 , Z, R, R a , R b , R c , and R d has the definition given above in particular for formula (I), and the symbol Y 1 has the definition given above for formulae (B1-1) to (B1-30), in particular, with further indices used being: m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2; l is 0, 1, 2, 3, 4, or 5, preferably 0, 1, or 2.

[0038] Preference is given here to structures / compounds of the formulae (II-1) to (II-7), particularly preferred are those of the formulae (II-1) and (II-2) and very particularly preferred are those of the formula (II-1).

[0039] Furthermore, the fused ring C c may be selected from structures of formulae (CCY-1) to (CCY-10): [ka] wherein R has the definition given above, particularly for formula (I), the dotted bond represents the point of attachment of the fused ring to a further group, and further Z 1 , Z 4 is the same or different in each case, and C(R 3 )2, O, S, or Si(R 3 )2, preferably C(R 3 )2, Z 2 is C(R)2, O, S, NR, or C(=O) and two adjacent Z 2 the group is -CR=CR- or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms and optionally substituted by one or more R groups; G is an alkylene group having 1, 2, or 3 carbon atoms and optionally substituted by one or more R groups, -CR=CR-, or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms and optionally substituted by one or more R groups; R 3 is the same or different in each case and is H, D, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R d )2, C(=O)Ar', C(=O)R d , P(=O)(Ar')2, P(Ar')2, B(Ar')2, B(R d )2, C(Ar')3, C(R d )3, Si(Ar')3, Si(R d) 3, a linear alkyl group, an alkoxy group, or a thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl group, an alkoxy group, or a thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be selected from the group consisting of one or more R d groups, and one or more non-adjacent CH groups may be replaced by -R d C=CR d -, -C≡C-, Si(R d )2, C=O, C=S, C=Se, C=NR d , -C(=O)O-, -C(=O)NR d -, NR d , P(=O)(R d ), -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 60 aromatic ring atoms, each of which is one or more R d an aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R d an aryloxy group or a heteroaryloxy group optionally substituted by a group, or a aryloxy group having 5 to 60 aromatic ring atoms and one or more R d aryl or heteroaryl groups, or combinations of these systems, and at the same time, two R 3 The groups may together form an aliphatic or aromatic ring system, thus forming a spiro system, and further, R 3 is preferably adjacent R, R a , R c , or R 3 Ar′ and R may form an aliphatic ring system together with the group. d has the definition given in claim 1, With the proviso that the two heteroatoms in these groups are not directly bonded to each other, and the two C=O groups are not directly bonded to each other.

[0040] In a preferred embodiment of the present invention, R 3 is not H and / or D.

[0041] In a preferred embodiment of the structures of formulae (CCy-1) to (CCy-10), Z 1 , Z 2 , and Z 4 Not more than one of the groups is a heteroatom, particularly O or NR, and the other groups are C(R 3 )2 or C(R)2, or Z 1 and Z 4 is the same or different in each occurrence, is O, Z 2 is C(R). In a particularly preferred embodiment of the present invention, Z 1 and Z 4 is the same or different in each case, and C(R 3 )2, and Z 2 is C(R)2, more preferably C(R 3 )2 or CH2.

[0042] In a preferred embodiment of the present invention, the fused ring C c may be selected from structures of formulae (CRA-1) to (CRA-13): [ka] wherein R has the definition given above, particularly for formula (I), the dotted bond represents the point of attachment of the fused ring to the further group, and the further symbols are defined as follows: Y 2 are the same or different in each occurrence and are C(R), (R)C-C(R), (R)C=C(R), NR, NAr', O, or S, preferably C(R), (R)C-C(R), (R)C=C(R), O, or S; R fare the same or different in each occurrence and are F, a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is in each occurrence selected from the group consisting of one or more R d groups, and one or more non-adjacent CH groups may be substituted by R d C=CR d , C≡C, Si(R d )2, C=O, C=S, C=Se, C=NR d , -C(=O)O-, -C(=O)NR d -, NR d , P(=O)(R d ), -O-, -S-, SO, or SO2), or having 5 to 60 aromatic ring atoms, in each case one or more R d an aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R d an aryloxy group or a heteroaryloxy group optionally substituted by a group, f The groups together or one R f The groups together with the R groups or with further groups can also form a ring system, R d has the definition given in claim 1, r is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, more preferably 0 or 1; s is 0, 1, 2, 3, 4, 5, or 6, preferably 0, 1, 2, 3, or 4, more preferably 0, 1, or 2; 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; v is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, preferably 0, 1, 2, 3, or 4, and more preferably 0, 1, or 2.

[0043] Here, structures of the formulae CRA-1 to CRA-5 are preferred, and structures of the formulae CRA-3 and CRA-4 are particularly preferred.

[0044] More preferably, the fused ring C c may be selected from the structures of formulae (CRA-1a) to (CRA-4f), [ka] wherein the dotted bond represents the point of attachment of the fused ring to a further group, the index m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, and the symbols R, R d , R f and the indices s, t and v have the definitions given above for formula (I) and / or formulae (CRA-1) to (CRA-13), in particular.

[0045] Structures of formulae CRA-3b and CRA-4f are preferred herein.

[0046] In a preferred embodiment, the ring C c However, instead of R, it is a substituent R d In this preferred embodiment, for example, Z 1 ~Z 4 , G., Y. 2 , R 3 , and R f The substituents R and R of the group d are R d and R 1 This applies in particular to formulae (CCy-1) to (CCy-10), (CRA-1 to CRA-13), and (CRA-1a) to (CRA-4f), where, for example, the substituents R and R d are R d and R 1 needs to be replaced by

[0047] In a further preferred embodiment, the ring C b However, the substituent R is not a substituent R 1 In this preferred embodiment, for example, Z 1 ~Z 4 , G., Y. 2 , R 3 , and R f The substituents R and R of the group d are R 1 and R 2 These definitions should be replaced by Z, as detailed below. 5 ~Z 7 , G 1 , Y 4 , and R g The radicals are detailed by way of example and are applicable accordingly. This applies in particular to formulae (CCy-1) to (CCy-10), (CRA-1 to CRA-13) and (CRA-1a) to (CRA-4f), where, for example, the substituents R and R d are R 1 and R 2 needs to be replaced by

[0048] Ring C c is W 1 The effect of this group is that the aromatic or heteroaromatic substituent R which may be derived from this group is in the basic skeleton of the partial structure B, in particular the two X c The inability to form a through-conjugation with the ring bearing the group.

[0049] Furthermore, the fused ring C b may be selected from structures of formulae (BCY-1) to (BCY-10): [ka] in which R has the definition given above, in particular for formula (I), and the symbols G, Z 1 , and Z 2has the definition given above, especially for formulae (CCy-1) to (CCy-10), the dotted bond represents the point of attachment of the fused ring to a further group, and further Z 3 is the same or different in each case, and C(R 3 )2, O, S, or Si(R 3 )2, preferably C(R 3 )2, and R 3 has the definition given above, especially for the formulae (CCy-1) to (CCy-10), With the proviso that the two heteroatoms in these groups are not directly bonded to each other, and the two C=O groups are not directly bonded to each other.

[0050] In a preferred embodiment of the present invention, R 3 is not H and / or D.

[0051] If adjacent groups in the structures of the present invention form an aliphatic ring system, it is preferred that the latter does not have an acidic benzylic proton. A benzylic proton is understood to mean a proton that is bonded to an alkyl carbon atom that is directly bonded to an aryl or heteroaryl group. This can be achieved in that the carbon atom in the aliphatic ring system that is directly bonded to an aryl or heteroaryl group is fully substituted and does not contain bonded hydrogen atoms. The absence of an acidic benzylic proton in formulae (CCy-1) to (CCy-3) and / or (BCy-1) to (BCy-3) therefore means that Z 1 and Z 4 or Z 1 and Z 3 However, these are C(R 3 )2, then R 3is defined as not being hydrogen. Furthermore, this can also be achieved by the carbon atom in the aliphatic ring system directly bonded to the aryl or heteroaryl group being the bridgehead of a bicyclic or polycyclic structure. Due to the spatial structure of the bicyclic or polycyclic structure, the protons attached to the bridgehead carbon atoms are significantly less acidic than the benzylic protons on the unbonded carbon atoms in the bicyclic or polycyclic structure and are considered non-acidic protons in the context of the present invention. Thus, the absence of acidic benzylic protons in formulae (CCy-1) to (CCy-3) and / or (BCy-1) to (BCy-3) is achieved when this is a bicyclic structure, so that R 1 If R is H, it will be much less acidic than the benzylic proton, since the corresponding anion of the bicyclic structure is not mesomerically stabilized. Thus, R in formulae (CCy-1)-(CCy-3) and / or (BCy-1)-(BCy-3) 1 Even if is H, in the context of this application this is a non-acidic proton.

[0052] Preferably, in particular in the formulae (CCy-1) to (CCy-3) and / or (BCy-1) to (BCy-3), R 3 is the same or different in each case and is F, Cl, Br, I, CN, NO2, N(Ar')2, N(R d )2, C(=O)Ar', C(=O)R d , P(=O)(Ar')2, P(Ar')2, B(Ar')2, B(R d )2, C(Ar')3, C(R d )3, Si(Ar')3, Si(R d ) 3, a linear alkyl group, an alkoxy group, or a thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl group, an alkoxy group, or a thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be selected from the group consisting of one or more R d groups, and one or more non-adjacent CH groups may be replaced by -Rd C=CR d -, -C≡C-, Si(R d )2, C=O, C=S, C=Se, C=NR d , -C(=O)O-, -C(=O)NR d -, NR d , P(=O)(R d ), -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 60 aromatic ring atoms, each of which is one or more R d an aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R d an aryloxy group or a heteroaryloxy group optionally substituted by a group, or a aryloxy group having 5 to 60 aromatic ring atoms and one or more R d an aralkyl group or a heteroaralkyl group, optionally substituted by a group, or a combination of these systems, and at the same time, two R 3 The groups may together form an aliphatic or aromatic ring system, thus forming a spiro system, and further, R 3 is preferably adjacent R, R a , R c , or R 3 Ar′ and R may form an aliphatic ring system together with the group. d may have the definition given above for formula (I).

[0053] Preferably, in particular in the formulae (CCy-1) to (CCy-3) and / or (BCy-1) to (BCy-3), R 3 are the same or different in each occurrence and are F, a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 atoms, each of which is represented by one or more R dgroups, and one or more non-adjacent CH groups may be replaced by -R d C=CR d -, -C≡C-, Si(R d )2, C=O, C=S, C=Se, C=NR d , -C(=O)O-, -C(=O)NR d -, NR d , P(=O)(R d ), -O-, -S-, SO, or SO2), or having 5 to 60 aromatic ring atoms, in each case one or more R d an aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R d an aryloxy group or a heteroaryloxy group optionally substituted by a group, 3 The groups together or one R 3 Groups are R and R a , R c It is sometimes also possible, together with the group or together with further groups, to form a ring system, preferably an aliphatic ring system.

[0054] In a preferred embodiment of the structures of formulae (BCy-1) to (BCy-10), Z 1 , Z 2 , and Z 3 Not more than one of the groups is a heteroatom, particularly O or NR, and the other groups are C(R 3 )2 or C(R)2, or Z 1 and Z 3 are the same or different in each occurrence, are O, and Z 2 is C(R). In a particularly preferred embodiment of the present invention, Z 1 and Z 3 is the same or different in each case, and C(R 3 )2, and Z 2 is C(R)2, more preferably C(R 3 )2 or CH2.

[0055] In a preferred embodiment of the present invention, the R groups bonded to the bridgehead atoms, preferably to the bridgehead atoms in the formulae (CCy-4) to (CCy-10) or (BCy-4) to (BCy-10), are in each case the same or different and are selected from H, D, F, having 1 to 10 carbon atoms and one or more R 1 a linear alkyl group, which may be substituted by a group, but is preferably unsubstituted, or a cyclic alkyl group having 3 to 10 carbon atoms and one or more R 1 a branched or cyclic alkyl group, which may be substituted by a group, but is preferably unsubstituted, or a cyclic alkyl group having 5 to 12 aromatic ring atoms, in each case one or more R 1 More preferably, the R groups bonded to the bridgehead atoms of formula (CCy-4) or (BCy-4) are the same or different in each case and are selected from the group consisting of H, F, linear alkyl groups having 1 to 4 carbon atoms, branched alkyl groups having 3 or 4 carbon atoms, and phenyl groups which may be substituted, but preferably unsubstituted, by alkyl groups having 1 to 4 carbon atoms. Most preferably, the R groups are the same or different in each case and are selected from the group consisting of H, methyl, and tert-butyl.

[0056] In a preferred embodiment of the present invention, the fused ring C b may be selected from structures of formulae (BRA-1) to (BRA-12): [ka] in which R has the definition given above, in particular for formula (I), and the symbol Y 2 and R f and the indices r, s, t, and v have the definitions given above, particularly for formulae (CRA-1) to (CRA-13), and the dotted bond represents the point of attachment of the fused ring to further groups.

[0057] Here, structures of the formulae BRA-1 to BRA-4 are preferred, and structures of the formulae BRA-3 and BRA-4 are particularly preferred.

[0058] More preferably, the fused ring C b may be selected from structures of formulae (BRA-1a) to (BRA-3f): [ka] wherein the dotted bond represents the point of attachment of the fused ring to a further group, the index m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, and the symbols R, R d , R f and the indices s, t and v have the definitions given above, in particular for formula (I) and / or formulae (CRA-1) to (CRA-13).

[0059] Here, structures of formula BRA-3f are preferred.

[0060] In a preferred embodiment, the ring C b However, instead of R, it is a substituent R d In this preferred configuration, for example, W 1 , W 2 , Z 1 ~Z 3 , G., Y. 2 , R 3 , and R f The substituents R and R of the group d are R d and R 1 This applies in particular to formulae (BCy-1) to (BCy-10), (BRA-1) to (BRA-12), and (BRA-1a) to (BRA-3f), where, for example, the substituents R and R d are R d and R 1 needs to be replaced by

[0061] In a further preferred embodiment, the ring C b However, the substituent R is not R 1 In this preferred configuration, for example, W 1 , W2 , Z 1 ~Z 3 , G., Y. 2 , R 3 , and R f The substituents R and R of the group d are R 1 and R 2 These definitions should be replaced by Z, as detailed below. 5 ~Z 7 , G 1 , Y 4 , and R g The radicals are detailed by way of example and are applicable accordingly. This applies in particular to formulae (BCy-1) to (BCy-10), (BRA-1) to (BRA-12) and (BRA-1a) to (BRA-3f), where, for example, the substituents R and R d are R 1 and R 2 needs to be replaced by

[0062] Ring C b is W 1 , W 2 The effect of these groups is that the aromatic or heteroaromatic substituent R derived from these groups is in the basic skeleton of the partial structure B, in particular Z or X. c The inability to form a through conjugation with the ring bearing the group.

[0063] In a preferred embodiment of the present invention, at least two R, R a , R b , R c , R d The group is composed of two R, R a , R b , R c , R d The R, R groups form a fused ring together with the further groups to which they are attached, a , R b , R c , R d The group may form at least one structure of the following formulae (Cy-1) to (Cy-10): [ka] In the formula, R 1 has the definition given above, particularly for formula (I), and the dotted bond represents two R, R a , R b , R c , R d represents the site of attachment of the group to the atom to which the group is attached, and further Z 5 , Z 7 is the same or different in each case, and C(R 4 )2, O, S, NR 4 or C(=O), Z 6 is C(R 1 )2, O, S, NR 1 or C(=O) and two adjacent groups Z 2 -CR 1 =CR 1 - or 5 to 14 aromatic ring atoms and one or more R 1 represents an ortho-linked arylene group or heteroarylene group optionally substituted by a group, G 1 has 1, 2, or 3 carbon atoms and one or more R 1 an alkylene group optionally substituted with a -CR 1 =CR 1 - or 5 to 14 aromatic ring atoms and one or more R 1 an ortho-linked arylene or heteroarylene group optionally substituted by a group; R 4 are the same or different in each case and are H, D, F, Cl, Br, I, CN, NO2, N(Ar'')2, N(R 2 )2, C(=O)Ar'', C(=O)R 2 , P(=O)(Ar'')2, P(Ar'')2, B(Ar'')2, B(R 2 )2, C(Ar'')3, C(R 2 )3, Si(Ar'')3, Si(R 2) 3, a linear alkyl group, an alkoxy group, or a thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl group, an alkoxy group, or a thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be selected from the group consisting of one or more R 2 groups, and one or more non-adjacent CH groups may be replaced by -R 2 C=CR 2 -, -C≡C-, Si(R 2 )2, C=O, C=S, C=Se, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 2 ), -O-, -S-, SO, or SO2, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN, or NO2), or having 5 to 60 aromatic ring atoms, each of which is one or more R 2 an aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R 2 an aryloxy group or a heteroaryloxy group optionally substituted by a group, or a aryloxy group having 5 to 60 aromatic ring atoms and one or more R 2 aryl or heteroaryl groups, or combinations of these systems, and at the same time, two R 4 The groups may together form an aliphatic or aromatic ring system, thus forming a spiro system, and further, R 4 is preferably adjacent R, R a , R b , R c , R d , or R 1 may form an aliphatic ring system with a group, and may be represented by the symbol R 1 , R 2 and Ar″ have the definitions given above, in particular for formula (I), With the proviso that the two heteroatoms in these groups are not directly bonded to each other, and the two C=O groups are not directly bonded to each other.

[0064] In a preferred embodiment of the present invention, R 4 is not H and / or D.

[0065] The absence of acidic benzyl protons in formulae (Cy-1) to (Cy-3) is preferably due to Z 5 and Z 7 However, these are C(R 4 )2, then R 4 is defined as not being hydrogen. Moreover, this can also be achieved when the carbon atom in the aliphatic ring system directly bonded to the aryl or heteroaryl group is a bridgehead of a bicyclic or polycyclic structure. Due to the spatial structure of the bicyclic or polycyclic structure, the protons attached to the bridgehead carbon atoms are significantly less acidic than the benzylic protons on the unbonded carbon atoms in the bicyclic or polycyclic structure and are considered non-acidic protons in the context of the present invention. Thus, the absence of acidic benzylic protons in formulas (Cy-4) to (Cy-10) is achieved when this is a bicyclic structure, so that R 1 If R is H, the corresponding anion of the bicyclic structure is not mesomerically stabilized and is therefore much less acidic than the benzylic proton. 1 Even if is H, this is a non-acidic proton in the context of this application.

[0066] Preferably, particularly in formulas (Cy-1) to (Cy-3), R 4 is the same or different in each case and is F, Cl, Br, I, CN, NO2, N(Ar'')2, N(R 2 )2, C(=O)Ar'', C(=O)R 2 , P(=O)(Ar'')2, P(Ar'')2, B(Ar'')2, B(R 2 )2, C(Ar'')3, C(R 2 )3, Si(Ar'')3, Si(R2 ) 3, a linear alkyl group, an alkoxy group, or a thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl group, an alkoxy group, or a thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be selected from the group consisting of one or more R 2 groups, and one or more non-adjacent CH groups may be replaced by -R 2 C=CR 2 -, -C≡C-, Si(R 2 )2, C=O, C=S, C=Se, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 2 ), -O-, -S-, SO, or SO2, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN, or NO2), or having 5 to 60 aromatic ring atoms, each of which is one or more R 2 an aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R 2 an aryloxy group or a heteroaryloxy group optionally substituted by a group, or a aryloxy group having 5 to 60 aromatic ring atoms and one or more R 2 aryl or heteroaryl groups, or combinations of these systems, and at the same time, two R 4 The groups may together form an aliphatic or aromatic ring system, thus forming a spiro system, and further, R 4 is preferably adjacent R, R a , R c , R d , R 1 In some cases, together with the group or further groups, it may form a ring system, preferably an aliphatic ring system.

[0067] Preferably, particularly in formulas (Cy-1) to (Cy-3), R 4are the same or different in each occurrence and are F, a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkyl or alkenyl group having 2 to 40 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 occurrence selected from one or more of R 2 groups, and one or more non-adjacent CH groups may be substituted by R 2 C=CR 2 , C≡C, Si(R 2 )2, C=O, C=S, C=Se, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 1 ), -O-, -S-, SO, or SO2), or having 5 to 60 aromatic ring atoms, in each case one or more R 2 an aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R 2 an aryloxy group or a heteroaryloxy group optionally substituted by a group, 4 The groups together or one R 4 Groups are R and R a , R c , R d , R 1 It is sometimes also possible, together with the group or together with further groups, to form a ring system, preferably an aliphatic ring system.

[0068] In a preferred embodiment of the structures of formulae (Cy-1) to (Cy-10), Z 5 , Z 6 , and Z 7 Not more than one of the groups is a heteroatom, in particular O or NR 4 , or O or NR 1 and the other group is C(R 4 )2 or C(R 1 )2 or Z5 and Z 7 is the same or different in each occurrence, O or NR 4 and Z 6 C(R 1 In a particularly preferred embodiment of the present invention, Z 5 and Z 7 is the same or different in each case, and C(R 4 )2, and Z 6 is C(R 1 )2, more preferably C(R 4 )2 or CH2.

[0069] In a preferred embodiment of the present invention, R bonded to a bridgehead atom, preferably a bridgehead atom in formulas (Cy-4) to (Cy-10) 1 The groups are in each case the same or different and are selected from H, D, F, 1 to 10 carbon atoms, and one or more R 2 a linear alkyl group having 3 to 10 carbon atoms, which may be substituted by a group, but is preferably unsubstituted, and one or more R 2 a branched or cyclic alkyl group, which may be substituted by a group, but is preferably unsubstituted, or a cyclic alkyl group having 5 to 12 aromatic ring atoms, in each case one or more R 2 More preferably, the R bonded to the bridgehead atom of formula (CY-4) is selected from the group consisting of aromatic and heteroaromatic ring systems, each of which may be substituted by a group. 1 The radicals are in each case the same or different and are selected from the group consisting of H, F, linear alkyl radicals having 1 to 4 carbon atoms, branched alkyl radicals having 3 or 4 carbon atoms, and phenyl radicals which may be substituted, but preferably unsubstituted, by alkyl radicals having 1 to 4 carbon atoms. Most preferably, R 1 The groups are the same or different in each occurrence and are selected from the group consisting of H, methyl, and tert-butyl.

[0070] In a preferred development of the invention, at least two R, R a , R b , R c , R dThe group is two R, R a , R b , R c , R d The R, R groups form a fused ring together with the further groups to which they are attached, a , R b , R c , R d The group may form at least one structure of formula (RA-1) to (RA-13): [ka] In the formula, R 1 has the definition given above, and the dotted bond represents two R, R a , R b , R c , R d represents the point of attachment to the atom of the group to which the group is attached, and further symbols have the following definitions: Y 4 is the same or different in each case, and C(R 1 )2, (R 1 )2C-C(R 1 )2, (R 1 )C=C(R 1 ), N.R. 1 , NAr′, O, or S, preferably C(R 1 )2, (R 1 )2C-C(R 1 )2, (R 1 )C=C(R 1 ), O, or S, and R g are the same or different in each occurrence and are F, a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is in each occurrence selected from the group consisting of one or more R 2 groups, and one or more adjacent CH groups may be substituted by R 2 C=CR 2 , C≡C, Si(R 2)2, C=O, C=S, C=Se, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 2 ), -O-, -S-, SO, or SO2), or having 5 to 60 aromatic ring atoms, in each case one or more R 2 Aromatic or heteroaromatic ring system, optionally substituted by a group, or having 5 to 60 aromatic ring atoms and one or more R 2 an aryloxy group or a heteroaryloxy group optionally substituted by a group, g The groups together or one R g Group is R 1 Together with the group or with further groups, R may form a ring system. 2 has the definition given in claim 1, r is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, more preferably 0 or 1; s is 0, 1, 2, 3, 4, 5, or 6, preferably 0, 1, 2, 3, or 4, more preferably 0, 1, or 2; 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; v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 0, 1, 2, 3, or 4, and more preferably 0, 1, or 2.

[0071] Preferred herein are structures of formulae RA-1, RA-3, RA-4 and RA-5, with structures of formulae RA-4 and RA-5 being particularly preferred.

[0072] In a preferred embodiment of the present invention, at least two R, R a , R b , R c , R d The group is composed of two R, R a , R b , R c, R d The R, R group together with the further group to which it is attached forms a fused ring, where the two R, R a , R b , R c , R d The groups form structures of formulae (RA-1a) to (RA-4f): [ka] The dotted bond represents two R, R a , R b , R c , R d represents the bonding site to which the group is attached, the index m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, and the symbol R 1 , R 2 , R g and the indices s and t have the definitions given above in particular for formula (I) and / or formulae (RA-1) to (RA-13).

[0073] Structures of formula RA-4f are preferred here.

[0074] In addition, one R a group and one R d The groups may form a fused ring by forming a structure of formula (Cy-1) to (Cy-10), (RA-1) to (RA-13), and / or (RA-1a) to (RA-4f), where R b Groups and R d The groups are preferably adjacent.

[0075] In addition, two R d The groups may form a fused ring by forming a structure of formula (Cy-1) to (Cy-10), (RA-1) to (RA-13) and / or (RA-1a) to (RA-4f), where R d The groups are preferably adjacent. Furthermore, two R d The groups may be from different rings.

[0076] In a further configuration, one R b Single group R or R dTogether with the groups, they form a structure of formula (Cy-1) to (Cy-10), (RA-1) to (RA-13), and / or (RA-1a) to (RA-4f) to form a fused ring.

[0077] In a more preferred embodiment, at least two R, R a , R b , R c , R d groups, preferably at least two R, R b , R d There are two groups, R and R a , R b , R c , R d Group or two R, R b , R d The R, R group together with the further group to which it is attached forms a fused ring, where the two R, R a , R b , R c , R d groups, preferably two R, R b , R d The group forms a structure of formula (RB): [ka] In the formula, R 1 has the definition given above, particularly for formula (I), and the dotted bond represents two R, R a , R b , R c , R d Group or two R, R b , R d represents the bonding site to which the Y group is attached, the index m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2; 5 is C(R 1 )2, NR 1 , NAr', B.R. 1 , BAr′, O, or S, preferably C(R 1 )2, NAr′ or O, more preferably C(R 1 )2 or O, and Ar' has the definition given above, particularly for formula (I).

[0078] Here, one R b Single group R or R d In addition, two R groups may form a fused ring together to form a structure of the formula (RB). d The groups may form a fused ring, forming a structure of formula (RB), d The groups are preferably adjacent. b group and one R d The groups may form a fused ring, forming a structure of formula (RB), b Groups and R d The groups are preferably adjacent.

[0079] More specifically, in preferred structures / compounds, the sum of the indices r, s, t, v, m, and n is preferably 0, 1, 2, or, more preferably, 1 or 2.

[0080] More preferably, the compound comprises at least one structure of formula (III-1) to (III-20), more preferably, the compound is selected from the compounds of formula (III-1) to (III-20), which have at least one fused ring: [ka] JPEG2025507608000030.jpg239170 JPEG2025507608000031.jpg117170 where symbol C b , C c , Y, W 1 , W 2 , Z, R a , R b , R c , and R d has the definition given above in particular for formula (I), the symbol o represents the fusion site of at least one fused ring, and further indices are defined as follows: m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2; l is 0, 1, 2, 3, 4, or 5, preferably 0, 1, or 2.

[0081] Preferably, the compound has at least two fused rings, at least one fused ring being formed by a structure of formulae (RA-1) to (RA-13) and / or (RA-1a) to (RA-4f), and further rings may be formed by a structure of formulae (RA-1) to (RA-13), (RA-1a) to (RA-4f) or (RB).

[0082] More preferably, the compound comprises at least one structure of formula (IV-1) to (IV-3), more preferably, the compound is selected from the compounds of formula (IV-1) to (IV-3), which have at least two fused rings: [ka] In the formula, the symbol C c , W 1 , Y, R a , R b , and R c has the definition given above specifically for formula (I), and the symbol o represents the fusion site of at least two fused rings.

[0083] Preferably, at least one of the fused rings, particularly in formulas (IV-1) to (IV-3), more preferably both fused rings, contains at least two R, R a , R b , R c , R d group, and two R, R a , R b , R c , R d The group is formed by further groups to which it is attached, where at least two R, R a , R b , R c , R d The groups form structures of formulae (RA-1) to (RA-12) and / or (RB), preferably structures of formulae (RA-1) to (RA-12).

[0084] Furthermore, the substituents R, R according to the above formula a , R b , Rc , R d , R f , R g , R 1 , R 2 , R 3 , and R 4 are the substituents R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 , and R 4 may not form a fused aromatic or heteroaromatic ring system together with the ring atoms of the ring system to which it is attached. This includes the substituents R, R a , R b , R c , R d , R f , R g , R 1 , R 3 , and R 4 The possible substituent R which may be attached to d , R 1 , and R 2 This includes the formation of fused aromatic or heteroaromatic ring systems with

[0085] The compounds of the present invention are aromatic or heteroaromatic R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 , or R 4When substituted by groups, it is preferred that they do not have aryl or heteroaryl groups with three or more aromatic six-membered rings directly fused to each other.More preferably, the substituents do not have aryl or heteroaryl groups with six-membered rings directly fused to each other.The reason for this preference is that the triplet energy of such structures is low.The fused aryl groups that have three or more aromatic six-membered rings directly fused to each other but are still suitable according to the present invention are phenanthrene and triphenylene, because they also have high triplet levels.

[0086] Thus, preferably, the R group may not have a through-conjugated anthracene group, and preferably, R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 , and R 4 None of the groups contain a through-conjugated anthracene group.

[0087] When a direct bond is formed between the anthracene group, which is the basic skeleton of the present invention shown in formula (I), and an optional aromatic or heteroaromatic linking group, a through-conjugation of the anthracene group is formed. Further bonds between the aforementioned 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, the two aromatic rings are directly bonded, and the 9-position sp 3 The hybridized carbon atom does not prevent the fusion of these rings, but the sp 3Conjugation is possible because the hybridized carbon atom is not necessarily between the groups connected via the connecting group. In contrast, in the case of a spirobifluorene structure, through conjugation can be formed when the bonds between the groups connected via the spirobifluorene group are 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 are in the same plane. When the bonds between the groups connected via the spirobifluorene group are sp at the 9-position, the bond between the groups connected via the spirobifluorene group is sp 3 Conjugation is interrupted when through a different phenyl group in a second spirobifluorene structure attached via a hybridized carbon atom.

[0088] More preferably, the R group may not contain an anthracene group, and preferably, R, R a , R b , R c , and R d Any of the groups is more preferably R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 , and R 4 None of the groups contain anthracene groups.

[0089] Very particularly preferably, the R group may furthermore not comprise an aromatic or heteroaromatic ring system having three linearly fused aromatic 6-membered rings, preferably R, R a , R b , R c , and R d Any of the groups is more preferably R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 , and R 4None of the groups include aromatic or heteroaromatic ring systems having three aromatic six-membered rings fused in a linear chain.

[0090] R, R a , R b , R c , and R d Any of the groups is more preferably R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 , and R 4 None of the groups may contain or form a fluorenone group. This includes R, R a , R b , R c , R d The substituents bonded to the fluorenone group include those bonded to a 5-membered ring having a CO group fused to two 6-membered aromatic rings.

[0091] Especially R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 , and R 4 When two groups selected from form together a ring system, the ring system may be monocyclic or polycyclic aliphatic, heteroaliphatic, aromatic, or heteroaromatic. In this case, the groups that together form the ring system may be adjacent, which means that they may be attached to the same carbon atom or to carbon atoms directly bonded to each other, or they may be further removed from each other. Furthermore, the substituents R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3, and / or R 4 Ring systems endowed with may be linked to each other via a bond, such that ring closure can be effected. In this case, each of the corresponding linking sites is preferably a substituent R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 , and / or R 4 is provided using

[0092] Preferably, the structure / compound may be symmetrical about the substructure B.

[0093] "Symmetrical with respect to partial structure B" refers more specifically to the corresponding R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 , and R 4 This means that the groups are the same and there are no differences.

[0094] Structures / compounds in which the substructure B is symmetrical are notable for a surprisingly high color purity, which is particularly reflected in the narrow emission spectra.

[0095] In a further configuration, the structure / compound may be asymmetric with respect to the compound with respect to the moiety B.

[0096] Furthermore, the R group, preferably X b Group or R b The R group adjacent to the group is C(Ar), C(R d )3, Si(Ar)3, Si(R d )3, B(R d )2, preferably C(Ar)3, C(R d)3, Si(Ar)3, Si(R d ) 3, more preferably one or more R d represents a fluorene group optionally substituted by a group, or R b It may be formed together with a group.

[0097] R b and / or R d The groups are C(Ar'), C(R 1 )3, Si(Ar')3, Si(R 1 )3, B(R 1 )2, preferably C(Ar')3, C(R 1 )3, Si(Ar')3, Si(R 1 ) at least one group selected from 3, preferably one or more R 1 R b Or R d It may be formed together with a radical.

[0098] C(Ar)3, C(R d )3, Si(Ar)3, Si(R d )3, B(R d )2, or C(Ar')3, C(R 1 )3, Si(Ar')3, Si(R 1 )3, B(R 1 ) 2, more preferably structures / compounds having one of the above groups selected from fluorene groups, are notable for their surprisingly high efficiency.

[0099] In a preferred embodiment, the compound of the present invention can be represented by at least one of the structures of formula (I) and / or formulae (I-1) to (I-4). Preferably, the compound of the present invention, which preferably comprises the structure of formula (I) and / or formulae (I-1) to (I-4), has a molecular weight of 5000 g / mol or less, preferably 4000 g / mol or less, particularly preferably 3000 g / mol or less, particularly preferably 2000 g / mol or less, most preferably 1200 g / mol or less.

[0100] A further feature of the preferred compounds of the invention is that they are sublimable. These compounds generally have a molar mass of less than about 1200 g / mol.

[0101] Preferred aromatic or heteroaromatic ring systems Ar, R, R a , R b , R c , R d , R f , R g , R 3 , R 4 and / or Ar′ is phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta- or para-terphenyl or branched terphenyl, quaterphenyl, in particular ortho-, meta- or para-quaterphenyl or branched quaterphenyl, fluorene which may be bonded via the 1-, 2-, 3- or 4-position, spirobifluorene which may be bonded via the 1-, 2-, 3- or 4-position, naphthalene, in particular 1- or 2-linked naphthalene, indole, benzofuran, benzothiophene, carbazole optionally linked through the 1, 2, 3, 4, or 9 positions, dibenzothiophene optionally linked through the 1, 2, 3, or 4 positions, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or triphenylene, each of which is selected from one or more R d , R 1 , or R 2 It may be substituted by a group.

[0102] Preferably, at least one of the substituents R, R a , R b , R c , R dare in each case the same or different and are selected from the group consisting of H, D, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group or a thioalkoxy group, or an aromatic or heteroaromatic ring system selected from the group of the following formulae Ar-1 to Ar-75. a , R b , R c , R d forms a condensed ring, preferably a condensed ring having the structure of formula (RA-1) to (RA-13) or (RB), or is substituted with substituents R, R a , R b , R c , R d is the same or different in each case and is selected from the group consisting of H, D or an aromatic or heteroaromatic ring system selected from the group of the following formulae Ar-1 to Ar-75, and / or the Ar′ group is the same or different in each case and is selected from the group of the following formulae Ar-1 to Ar-75: [ka] JPEG2025507608000034.jpg236170 JPEG2025507608000035.jpg249163 JPEG2025507608000036.jpg232170 JPEG2025507608000037.jpg78170In formula, R 1 has the definition given above, the dotted bonds represent the points of attachment to the corresponding groups, and further Ar 1 are the same or different in each occurrence and have 6 to 18 aromatic ring atoms, and in each occurrence one or more R 1 a divalent aromatic or heteroaromatic ring system optionally substituted by a group, A is the same or different in each case, and C(R 1 )2, NR 1 , O, or S; p is 0 or 1, where p=0 is Ar 1means that the corresponding aromatic or heteroaromatic group is directly bonded to the corresponding group; q is 0 or 1, where q=0 means that no A group is attached to this position and instead R 1 This means that the group is attached to the corresponding carbon atom.

[0103] In this case, structures of the formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-40), (Ar-41), (Ar-42), (Ar-43), (Ar-44), (Ar-45), (Ar-46), (Ar-69), (Ar-70), and (Ar-75) are preferred, and structures of the formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16) are particularly preferred.

[0104] When the above Ar group has more than one A group, the possible options for these include all combinations from the definition of A. In that case, a preferred embodiment is when one A group is NR 1 and the other A group is C(R 1 )2 or both A groups are NR 1 or both A groups are O.

[0105] A is NR 1 When the substituent R 1 preferably has 5 to 24 aromatic ring atoms and one or more R 2 In a particularly preferred embodiment, R is an aromatic or heteroaromatic ring system optionally substituted by a group. 1 The substituents are in each case the same or different and have 6 to 24 aromatic ring atoms, in particular 6 to 18 aromatic ring atoms, no fused aryl groups, no fused heteroaryl groups in which two or more aromatic or heteroaromatic 6-membered ring groups are directly fused to each other, and in each case one or more R 2Ar-1 through Ar-11 are preferably aromatic or heteroaromatic ring systems, each of which may be substituted by a group. Phenyl, biphenyl, terphenyl, and quaterphenyl are preferred, having the bonding patterns listed above for Ar-1 through Ar-11, and these structures are preferably R 1 Not by one or more R 2 Ar-47 to Ar-50, Ar-57, and Ar-58 are preferably triazines, pyrimidines, and quinazolines, whose structures are represented by R 1 Not by one or more R 2 It may be substituted by a group.

[0106] Preferred substituents R, R a , R b , R c , R d , R f , and R g This article describes the following.

[0107] In a preferred embodiment of the present invention, R, R a , R b , R c , R d is the same or different in each case and is H, D, F, CN, NO2, Si(R 1 )3, B(OR 1 2. a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group is in each case one or more R 1 group), or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, in each case one or more R 1 The ring system is selected from the group consisting of an aromatic or heteroaromatic ring system optionally substituted by a group.

[0108] In a further preferred embodiment of the present invention, the substituents R, R a , R b , R c , R dare in each occurrence the same or different and are H, D, F, a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group is in each occurrence one or more of R 1 group), or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, in each case one or more R 1 The ring system is selected from the group consisting of an aromatic or heteroaromatic ring system optionally substituted by groups.

[0109] In addition, at least one substituent R, R a , R b , R c , R d are the same or different in each occurrence and are H, D, 6 to 30 aromatic ring atoms, and one or more R 1 In a further preferred embodiment of the present invention, the substituents R, R a , R b , R c , R d forms a ring having the structure of formula (RA-1) to (RA-13), (RA-1a) to (RA-4f) or (RB), or R, R a , R b , R c , R d are the same or different in each occurrence and are H, D, 6 to 30 aromatic ring atoms, and one or more R 1 More preferably, the substituents R, R are selected from the group consisting of aromatic and heteroaromatic ring systems, which may be substituted by groups. a , R b , R c , R d are the same or different in each occurrence and are H, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, and more preferably 6 to 13 aromatic ring atoms, each of which may be represented by one or more R 1 wherein the aryl group is substituted with an alkyl group.

[0110] In a preferred embodiment of the present invention, R f or R g are in each occurrence the same or different and are linear alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, where the alkyl group is in each occurrence one or more of R d or R 2 group), or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, in each case one or more R d Or R 2 The ring system is selected from the group consisting of an aromatic or heteroaromatic ring system optionally substituted by a group.

[0111] In a further preferred embodiment of the present invention, R f or R g are the same or different in each occurrence and are linear alkyl groups having 1 to 10 carbon atoms or branched or cyclic alkyl groups having 3 to 10 carbon atoms, where the alkyl group is in each occurrence one or more R d or R 2 group), or having 6 to 30 aromatic ring atoms and one or more R d or R 2 The ring system is selected from the group consisting of an aromatic or heteroaromatic ring system optionally substituted by a group.

[0112] More preferably, X b Or R b R group adjacent to the group, or R d are the same or different in each occurrence and are a linear alkyl group having 1 to 5 carbon atoms or a branched or cyclic alkyl group having 3 to 5 carbon atoms, where the alkyl group is, in each occurrence, one or more of R d or R 1 group), or having 6 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 R d Or R 1The ring system is selected from the group consisting of an aromatic or heteroaromatic ring system optionally substituted by a group.

[0113] In a preferred embodiment of the present invention, R f or R g are in each occurrence the same or different and are linear alkyl groups having 1 to 6 carbon atoms or cyclic alkyl groups having 3 to 6 carbon atoms, where the alkyl group is in each occurrence one or more R d or R 2 group), or having 6 to 24 aromatic ring atoms, in each case one or more R d Or R 2 and at the same time, two R f or R g The groups may be taken together to form a ring system. More preferably, R f or R g are the same or different in each occurrence and are linear alkyl groups having 1, 2, 3, or 4 carbon atoms or branched or cyclic alkyl groups having 3 to 6 carbon atoms, where the alkyl group is selected from one or more of R d or R 2 group, but preferably unsubstituted), or having 6 to 12 aromatic ring atoms, in particular 6 aromatic ring atoms, in each case one or more, preferably non-aromatic R d or R 2 and at the same time, the two R f or R g The groups may be taken together to form a ring system. Most preferably, R f or R g are the same or different in each occurrence and are selected from linear alkyl groups having 1, 2, 3, or 4 carbon atoms or branched alkyl groups having 3 to 6 carbon atoms. Most preferably, R f or R gis a methyl group or a phenyl group, and two phenyl groups may be joined together to form a ring system, with methyl groups being preferred over phenyl groups.

[0114] Substituent R 3 , R a , R b , R c , R d , R f , R g Preferred aromatic or heteroaromatic ring systems represented by Ar, Ar', or Ar'' are phenyl, biphenyl, in particular ortho-, meta-, or para-biphenyl, terphenyl, in particular ortho-, meta-, or para-terphenyl or branched terphenyl, quaterphenyl, in particular ortho-, meta-, or para-quaterphenyl or branched quaterphenyl, fluorene, which may be bonded via the 1-, 2-, 3-, or 4-position, spirobifluorene, which may be bonded via the 1-, 2-, 3-, or 4-position, naphthalene, in particular 1 - or 2-bonded naphthalene, indole, benzofuran, benzothiophene, carbazole optionally bonded through the 1, 2, 3, or 4 positions, dibenzofuran optionally bonded through the 1, 2, 3, or 4 positions, dibenzothiophene optionally bonded through the 1, 2, 3, or 4 positions, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or triphenylene, each of which is selected from one or more R d , R 1 , or R 2Group may be substituted. Particularly preferred are the structures Ar-1 to Ar-75 shown above, with the structures of formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-40), (Ar-41), (Ar-42), (Ar-43), (Ar-44), (Ar-45), (Ar-46), (Ar-69), (Ar-70), and (Ar-75) being preferred, and the structures of formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16) being particularly preferred. Regarding the structures Ar-1 to Ar-75, these are the structures of the substituent R 1 It is necessary to state that the ring system R, R 3 , R f , or in the case of Ar, these substituents R 1 is R d Ar'', R g In the case of these substituents R 1 is R 2 needs to be replaced by

[0115] Further suitable R, R a , R b , R c , R d The group has the formula -Ar 4 -N(Ar 2 )(Ar 3 ) group, wherein Ar 2 , Ar 3 , and Ar 4 are the same or different in each occurrence and have 5 to 24 aromatic ring atoms, and in each occurrence one or more R 1 Ar is an aromatic or heteroaromatic ring system optionally substituted by a group. 2 , Ar 3 , and Ar 4 The total number of aromatic ring atoms in the formula -Ar is 60 or less, preferably 40 or less. 4 -N(Ar 2 )(Ar 3 ) are not preferred.

[0116] Here, Ar 4 and Ar 2 may be bonded to each other, and / or Ar 2 and Ar 3 is C(R 1 )2, NR 1 , O, and S. Preferably, Ar 4 and Ar 2 are bonded to each other, and Ar 2 and Ar 3 are attached to each other at ortho positions relative to the bond to the nitrogen atom. 2 , Ar 3 , and Ar 4 None of the groups are bonded to each other.

[0117] Preferably, Ar 4 has 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms, and in each case one or more R 1 Ar is an aromatic or heteroaromatic ring system optionally substituted by a group. 4 is selected from the group consisting of ortho-, meta-, or para-phenylene, or ortho-, meta-, or para-biphenyl, each of which is selected from the group consisting of one or more R 1 It may be substituted by a group, but is preferably unsubstituted. Most preferably, Ar 4 is an unsubstituted phenylene group.

[0118] Preferably, Ar 2 and Ar 3 are the same or different in each occurrence and have 6 to 24 aromatic ring atoms, and in each occurrence one or more R 1 Ar is an aromatic or heteroaromatic ring system optionally substituted by a group. 2 and Ar 3The groups are in each occurrence the same or different and are benzene, ortho-, meta-, or para-biphenyl, ortho-, meta-, or para-terphenyl or branched terphenyl, ortho-, meta-, or para-quaterphenyl or branched quaterphenyl, 1-, 2-, 3-, or 4-fluorenyl, 1-, 2-, 3-, or 4-spirobifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-, 3-, or 4-carbazole, 1-, 2-, 3-, or 4-dibenzofuran, 1-, 2-, 3-, or 4-dibenzothiophene, indenocarbazole, indolocarbazole, 2-, 3-, or 4-pyridine, 2-, 4-, or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene, or triphenylene, each of which may be selected from the group consisting of one or more R 1 It may be substituted by a group. Most preferably, it is 2 and Ar 3 are in each case the same or different and are selected from the group consisting of benzene, biphenyl, in particular ortho-, meta-, or para-biphenyl, terphenyl, in particular ortho-, meta-, or para-terphenyl or branched terphenyl, quaterphenyl, in particular ortho-, meta-, or para-quaterphenyl or branched quaterphenyl, fluorene, in particular 1-, 2-, 3-, or 4-fluorene, or spirobifluorene, in particular 1-, 2-, 3-, or 4-spirobifluorene.

[0119] In a further preferred embodiment of the present invention, R 1 are in each occurrence the same or different and are H, D, F, CN, a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the alkyl group is in each occurrence one or more of R 2 group), or having 6 to 24 aromatic ring atoms, in each case one or more R 2 In a particularly preferred embodiment of the present invention, R1 are in each case the same or different and are H, a linear alkyl group having 1 to 6 carbon atoms, in particular 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, where the alkyl group is selected from one or more R 2 group, but is preferably unsubstituted), or having 6 to 13 aromatic ring atoms, in each case one or more R 2 The ring system is selected from the group consisting of an aromatic or heteroaromatic ring system which may be substituted, but is preferably unsubstituted, by groups.

[0120] In a further preferred embodiment of the present invention, R 2 is the same or different in each occurrence and is H, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, which may be substituted by an alkyl group having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0121] At the same time, in compounds of the invention processed by vacuum evaporation, the alkyl groups preferably have 5 carbon atoms or less, more preferably 4 carbon atoms or less, and most preferably 1 carbon atom or less. In the case of compounds processed from solution, suitable compounds are also those substituted with alkyl groups having up to 10 carbon atoms, especially branched alkyl groups, or with oligoarylene groups, such as ortho-, meta-, or para-terphenyl or branched terphenyl or quaterphenyl groups.

[0122] Furthermore, the compound may comprise exactly two or exactly three of the structures of formulae (I), (I-1) to (I-4), and / or (II-1) to (II-21), where preferably R, R b , R d or R, R b , R dOne of the aromatic or heteroaromatic ring systems to which the groups are attached is shared by the two structures.

[0123] In a preferred embodiment, the compound is selected from compounds of formula (D-1), (D-2), and (D-3): [ka] In the formula, L 1 The radical is a connecting group, preferably a bond, or an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, aromatic ring atoms, optionally substituted by one or more R groups, and the further symbols used have the definitions given above, in particular for formula (I).

[0124] 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, optionally substituted by one or more R groups, but preferably unsubstituted, where R may have the definition given above, especially for formula (I). 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 1 R may be substituted by a group, but is preferably unsubstituted. 1 may have the definition given above especially for formula (I).

[0125] More preferably, the symbol L 1 are in each case the same or different and are a bond or an aryl or heteroaryl group having 5 to 24 ring atoms, preferably 6 to 13 ring atoms and more preferably 6 to 10 ring atoms, and the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is directly bonded to the respective atom of the further group, i.e. via an atom of the aromatic or heteroaromatic group.

[0126] Furthermore, L shown in formula (D3) 1 The group comprises an aromatic ring system having up to two fused aromatic and / or heteroaromatic six-membered rings, and preferably does not contain a fused aromatic or heteroaromatic ring system. Thus, naphthyl structures are preferred over anthracene structures. Furthermore, fluorenyl, spirobifluorenyl, dibenzofuranyl, and / or dibenzothienyl structures are preferred over naphthyl structures.

[0127] Non-fused structures, such as phenyl, biphenyl, terphenyl, and / or quaterphenyl structures, are particularly preferred.

[0128] 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, particularly branched terphenylene, quaterphenylene, particularly 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 by groups, but is preferably unsubstituted.

[0129] The above preferred embodiments may be combined with one another as desired within the limits defined in claim 1. In particularly preferred embodiments of the invention the above preferences occur simultaneously.

[0130] In a further aspect of the invention, there is provided a compound comprising the structure of formula (I), preferably a compound of formula (I), wherein at least one ring C c has the following properties: [Table 1]

[0131] In a further aspect of the invention, there is provided a compound comprising the structure of formula (I), preferably a compound of formula (I), wherein at least one ring Cc has the following properties: [Table 2] JPEG2025507608000041.jpg169170

[0132] In a further aspect of the present invention, compounds comprising the structure of formula (II-1) are preferred, preferably compounds of formula (II-1), in which ring C c And R a , R b , R c , and R d The radicals, which are the same or different in each case, have the following definitions: [Table 3] JPEG2025507608000043.jpg220170 JPEG2025507608000044.jpg214170 JPEG2025507608000045.jpg219170

[0133] In a further aspect of the invention, compounds comprising the structure of formula (II-2) are preferred, preferably compounds of formula (II-2), in which the index l is preferably in each case less than or equal to 3, more preferably in each case 0, 1 or 2, particularly preferably in each case 0 or 1, and the ring C c And R a , R b , R c , and R d The radicals, which are the same or different in each case, have the following definitions:

[0134] [Table 4] JPEG2025507608000047.jpg246170 JPEG2025507608000048.jpg186170

[0135] In the above table, R d The groups specified in the row below the group are similar to those previously described for R b Substituents on the phenyl ring of the base skeleton which are substituted by groups (see, for example, formula (II-1)), or similarly R b A substituent on the phenyl ring attached to the phenyl ring of the base skeleton that is substituted by a group (see, for example, formula (II-2)). Most preferably, R d is a methyl or phenyl group. In this case, R d The groups may be taken together to form a ring system, thus giving a spiro system.

[0136] The expression "alkyl" in the above table especially includes straight-chain alkyl groups or branched or cyclic alkyl groups according to the definition given above for the respective radical.

[0137] The expressions "aryl, heteroaryl" in the above table include in particular aryl or heteroaryl groups having 5 to 40 aromatic ring atoms according to the definition given above for the respective groups, aryl groups preferably having 6 to 12, more preferably 6 ring atoms, heteroaryl groups preferably having 5 to 13, more preferably 5 ring atoms. More preferably, heteroaryl groups comprise 1 or 2 heteroatoms, preferably N, O or S.

[0138] The designations "CRA-3", "CRA-4", "CRA-4f", "CRA-5", "Ar-1", and "Ar-75" refer to the structural formulae shown above and below.

[0139] To form a ring with a group means that two groups taken together form, in each case, an R 1 Typically, this means forming a phenyl ring which may be substituted by a nitrogen atom. b and R or R dWith a phenyl group substituted by a group, a naphthyl group is formed. The same applies to the further definition of the ring formation.

[0140] In particular, the preferred R b The word "and" in a group description means that the two groups are different, where R b One of the groups is according to the first definition and the second R b The R group is defined as follows: d and together with R form an aryl, heteroaryl, or phenyl ring. b One of the groups is an aryl or heteroaryl group and the second R b Group is R d and form a phenyl ring. If a field does not contain the word "and", then all groups represent the corresponding groups. R d The expression "Ar-1 to Ar-75" for the groups refers to both R b It means that the group is an aryl or heteroaryl group according to the above or below formulae Ar-1 to Ar-75.

[0141] The same applies to further uses of the word "and" in the table above.

[0142] Ring C shown in formula (II-1) and (II-2) b and various substituents R a , R b , R c , and R d Of course, the preferences regarding the above also apply to the other formulae (II-3) to (II-20) shown above.

[0143] Examples of preferred compounds according to the embodiments detailed above are those shown in the table below: [ka] JPEG2025507608000050.jpg241170 JPEG2025507608000051.jpg208170 JPEG2025507608000052.jpg246170 JPEG2025507608000053.jpg243170 JPEG2025507608000054.jpg252170 JPEG2025507608000055.jpg245170 JPEG2025507608000056.jpg253170 JPEG2025507608000057.jpg250170 JPEG2025507608000058.jpg235170 JPEG2025507608000059.jpg249170 JPEG2025507608000060.jpg241170 JPEG2025507608000061.jpg235170 JPEG2025507608000062.jpg249170 JPEG2025507608000063.jpg247170 JPEG2025507608000064.jpg242170 JPEG2025507608000065.jpg238170 JPEG2025507608000066.jpg241170 JPEG2025507608000067.jpg252170 JPEG2025507608000068.jpg232170 JPEG2025507608000069.jpg248170 JPEG2025507608000070.jpg241170 JPEG2025507608000071.jpg194170

[0144] Preferred embodiments of the compounds of the present invention are detailed in the examples, and these compounds can be used alone or in combination with further compounds for any purpose of the present invention.

[0145] The preferred embodiments described above can be combined with one another if desired, provided that the conditions specified in claim 1 are fulfilled. In particularly preferred embodiments of the invention, the preferred embodiments described above are applied simultaneously.

[0146] 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.

[0147] Therefore, the present invention further provides a method for preparing the compounds of the present invention, which comprises synthesizing a base skeleton bearing an aromatic amino group and introducing at least one aromatic or heteroaromatic group, preferably by a nucleophilic aromatic substitution reaction or a coupling reaction.

[0148] Suitable compounds comprising a base skeleton bearing an aromatic amino group are often commercially available and the starting compounds detailed in the examples can be obtained by known methods and therefore reference is made thereto.

[0149] These compounds can be reacted with further compounds by known coupling reactions, the conditions necessary for this purpose being known to those skilled in the art, and the detailed specification of the examples will assist them in carrying out these reactions.

[0150] Particularly suitable and preferred coupling reactions, all resulting in CC bond formation and / or CN bond formation, are those due to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA, and HIYAMA. These reactions are well known and the examples provide further guidance to the skilled artisan.

[0151] Compounds of the invention can be synthesized by methods including those according to Schemes 1, 2, and / or 3 below.

[0152] For example, the synthesis can be carried out in three steps as shown in Scheme 1. First, a bishalogen-functionalized (Br, I) or bistriflate-functionalized starting material BS may be used to prepare a secondary o-chloroarylamine by reaction with a primary arylamine in a palladium / phosphine-catalyzed Hartwig-Buchwald-type CN coupling (first step). Exemplary starting materials BS are cited in the Examples, to which reference is made here in a general manner. The product of the first step can be cyclized in a palladium / phosphine-catalyzed CC coupling in a second step to give a carbazole. The carbazole thus obtained can then be reacted with a 1,4-dichloro-2,5-difluoro aromatic compound and S N 2 Ar (see step 1 of the third stage), and the coupling product can be cyclized in situ in a palladium / phosphine catalyzed CC coupling by adding a Pd source and a phosphine to give the compound of the invention (see step 2 of the third stage). When two different carbazoles are used in the third stage, either as a mixture or by sequential addition, functionalized compounds of the invention with mixed functionalization can be obtained. This is true both in the case of using two carbonyl-functionalized carbazoles as well as in the case of using one carbonyl-functionalized carbazole and one differently functionalized carbazole.

[0153] [ka]

[0154] Alternatively, compounds of the invention can be prepared in four steps from carbazoles (see Scheme 2).

[0155] First, a carbazole bearing a substituent R' o to the C=O (see experimental for synthesis) can be subjected to a regioselective NBS bromination at the o position of the carbazole nitrogen atom (step 1). The bromine function can be reacted with B2Pin2 via palladium / phosphine catalyzed borylation to give the B-Pin ester (step 2). The central ring unit is then coupled in a palladium / phosphine catalyzed Suzuki-type C-C coupling (step 3). Finally, cyclization is performed via palladium / phosphine catalyzed C-C coupling to give the compounds of the invention (step 4).

[0156] [ka]

[0157] Alternatively, the compounds of the invention can be prepared in three steps from the starting material BS (see Scheme 3). First, the starting material BS (see experimental for synthesis) can be used to prepare secondary o-bischloroarylamines by reacting with primary o-chloroarylamines in a palladium / phosphine-catalyzed Hartwig-Buchwald-type CN coupling (step 1). The latter can be cyclized in a palladium / phosphine-catalyzed CC coupling in a second step to give o-chlorocarbazoles. The carbazoles can then be cyclized in a palladium / phosphine-catalyzed CN coupling followed by CC coupling to give the compounds of the invention (see step 3). The CN or CC couplings can be carried out sequentially or in a one-pot reaction. When two different carbazoles are used in the third step as a mixture or by sequential addition, functionalized compounds of the invention with mixed functionalization can be obtained.

[0158] This procedure has the advantage of being regioselective towards the carbazole with respect to the coupling and cyclization of the central unit in the third step.

[0159] [ka]

[0160] The definitions of the symbols used in schemes 1, 2, and 3 are essentially the same as those defined in formula (I) or preferred embodiments of these structures, and for clarity, the numbering and full designation of all symbols are omitted. In addition, the symbols X, X in formulas (I-1) to (I-4) are particularly a , X b , and X c For the sake of clarity, the use of symbols to represent possible nitrogen atoms in heteroaromatic rings has in many cases been omitted, as shown by X, X, etc. These details must therefore be understood as illustrative, and the skilled artisan will be able to carry out the syntheses given above and below, especially in the examples, with the symbols X, X a , X b , and X c is applicable to compounds in which one or more of the groups is nitrogen.

[0161] 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 for the preparation of the compounds of the invention. Further information can be found in the examples.

[0162] By these methods, and optionally subsequent purification such as recrystallization or sublimation, the compounds of the present invention can be obtained in high purity (preferably 99% or more). 1 1 H NMR and / or HPLC).

[0163] The compounds of the present invention may also be mixed with polymers. Likewise, these compounds may be covalently incorporated into polymers. This is possible, in particular, with compounds substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic ester, or reactive polymerizable groups such as olefins or oxetanes. They may be used as monomers to generate the corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably carried out via halogen or boronic acid functional groups or via polymerizable groups. Furthermore, it is possible to crosslink the polymers via groups of this kind. The compounds and polymers of the present invention may be used in the form of crosslinked or non-crosslinked layers.

[0164] Thus, the present invention further provides an oligomer, polymer or dendrimer comprising one or more of the structures of formula (I) and preferred embodiments of this formula or compounds of the present invention detailed above, and there is a bond of one or more of the compounds of the present invention or the structures of formula (I) and preferred embodiments of this formula to the polymer, oligomer or dendrimer. Thus, according to the bond of the structures of formula (I) and preferred embodiments of this formula or compounds, they form side chains of the oligomer or polymer or are bonded within the main chain. The polymers, oligomers or dendrimers may be bonded, partially bonded or unbonded. The oligomers or polymers may be linear, branched or dendritic. For the repeating units of the compounds of the present invention in oligomers, dendrimers and polymers, the same preferences as described above apply.

[0165] To prepare oligomers or polymers, the monomers of the invention are homopolymerized or copolymerized with further monomers. Copolymers are preferred in which the units of formula (I) or the preferred embodiments described above and 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 and preferred comonomers forming the polymer backbone are fluorenes (for example according to EP 842208 or WO 2000 / 022026), spirobifluorenes (for example according to EP 707020, EP 894107 or WO 2006 / 061181), paraphenylenes (for example according to WO 92 / 18552), carbazoles (for example according to WO 2004 / 070772 or WO 2004 / 113468), thiophenes, etc. (for example according to EP 1028136), dihydrophenanthrenes (for example according to WO 2005 / 014689), cis and trans indenofluorenes (for example according to WO 2004 / 041901 or WO 2004 / 113412), ketones (for example according to WO 2005 / 040302), phenanthrenes (for example according to WO 2005 / 104264 or WO 2007 / 017066), or else a plurality of these units. The polymers, oligomers and dendrimers may still contain further units, for example transport units (especially those based on triarylamines) and / or electron transport units.

[0166] Furthermore, 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 comprising the structure of formula (I) or the preferred embodiments described above and below 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, determined according to DIN 51005 (2005-08 version).

[0167] For processing the compounds of the present invention from liquid phase, for example by spin coating or printing, formulations of the compounds of the present invention are required.These formulations can be, for example, solutions, dispersions or emulsions.For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and 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, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, Indane, 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, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate, or mixtures of these solvents.

[0168] Thus, the present invention further provides a formulation or composition comprising at least one 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 aforementioned solvents, or a mixture of these solvents. If the further compound comprises a solvent, this mixture is referred to herein as a formulation. Alternatively, the further compound may be at least one further organic or inorganic compound that is also used in electronic devices, such as emitters and / or matrix materials, which are different from the compounds of the present invention. Suitable emitters and matrix materials are listed below in connection with organic electroluminescent devices. The further compound may be a polymer.

[0169] 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 shows TADF (thermally activated delayed fluorescence), host material, electron transport material, electron injection material, hole conducting material, hole injection material, electron blocker material, hole blocking material, wide band gap material and n-dopant, and is preferably a host material.

[0170] The present invention further provides the use of the compounds of the present invention as emitters, more preferably as green, red or blue emitters, particularly preferably as blue emitters, in electronic devices, in particular organic electroluminescent devices, in which case the compounds of the present invention preferably exhibit fluorescent properties and therefore provide preferentially fluorescent emitters.

[0171] The present invention further provides an electronic device comprising at least one compound of the present invention.An electronic device in the context of the present invention is a device comprising at least one layer comprising at least one organic compound.This component may also comprise other layers made of inorganic materials or entirely inorganic materials.

[0172] The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs, sOLEDs, PLEDs, LECs, etc.), preferably organic light-emitting diodes (OLEDs), small molecule based organic light-emitting diodes (sOLEDs), polymer based organic light-emitting diodes (PLEDs), light-emitting mechanical cells (LECs), organic laser diodes (O-lasers), organic plasmonic light-emitting devices (DM Koller et al., Nature Photonics 2008, 1-4), 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-quench devices (O-FQDs), and organic electrical sensors, preferably organic electroluminescent devices, more preferably organic light-emitting diodes (OLEDs), small molecule based organic light-emitting diodes (sOLEDs), polymer based organic light-emitting diodes (PLEDs), in particular phosphorescent OLEDs.

[0173] The organic electroluminescent element comprises a cathode, an anode and at least one light-emitting layer. Apart from these layers, it may also comprise further layers, for example in each case one or more injection layers, transport layers, blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers and / or charge generating layers. Similarly, an intermediate layer with exciton blocking function can be introduced, for example, between two light-emitting layers. However, it should be noted that not all of these layers necessarily have to be present. In this case, the organic electroluminescent element can comprise a light-emitting layer or can comprise a plurality of light-emitting layers. If a plurality of light-emitting layers are present, these preferably have several emission maxima over the entire range from 380 nm to 750 nm, so that the overall result is a white emission. In other words, various light-emitting compounds capable of emitting fluorescence or phosphorescence are used in the light-emitting layers. Particularly preferred are systems with three light-emitting layers, in which the three layers exhibit blue, green and orange or red emission. The organic electroluminescent element of the present invention may also be a tandem electroluminescent element, in particular for white-emitting OLEDs.

[0174] The compounds of the present invention may be used in different layers according to the exact structure. Preferred is an organic electroluminescent device comprising a compound of formula (I) or the preferred embodiments detailed above as emitter, preferably a red, green or blue emitter, more preferably a blue emitter, in the light-emitting layer.

[0175] When the compounds of the present invention are used as light emitters in a light-emitting layer, it is preferable to use suitable matrix materials known as such.

[0176] Preferred mixtures of the compounds of the invention and matrix material comprise 99% to 1% by volume, preferably 98% to 10% by volume, more preferably 97% to 60% by volume, in particular 95% to 80% by volume of matrix material, based on the entire mixture of phosphor and matrix material. Correspondingly, the mixture comprises 1% to 99% by volume, preferably 2% to 90% by volume, more preferably 3% to 40% by volume, in particular 5% to 20% by volume of phosphor, based on the entire mixture of phosphor and matrix material.

[0177] Suitable matrix materials which can be used in combination with the compounds of the invention include aromatic ketones, aromatic phosphine oxides, or aromatic sulfoxides or sulfones (e.g. according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627, or WO 2010 / 006680), triarylamines, carbazole derivatives, e.g. CBP (N,N-biscarbazolylbiphenyl) or those described in WO 2005 / 039246, U.S. Patent Application Publication No. 2005 / 006627, U.S. Patent Application Publication No. 2005 / 006680 ... Carbazole derivatives, indolocarbazole derivatives (for example according to WO 2007 / 063754 or WO 2008 / 056746), indenocarbazole derivatives (for example according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056746), as disclosed in WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056746, 6776), azacarbazole derivatives (for example according to EP 1 617 710, EP 1 617 711, EP 1 731 584, JP 2005 / 347160), bipolar matrix materials (for example according to WO 2007 / 137725), silanes (for example according to WO 2005 / 111172), azaboroles or boronic esters (for example according to WO 2006 / 117052), triazine derivatives (for example according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877), zinc complexes (for example according to EP 652273 or WO 2009 / 062578), diazasilol or tetraazasilol derivatives (for example according to WO 2010 / 054729), diazaphosphole derivatives (for example according to WO 2010 / 054730), bridged carbazole derivatives (for exampleAccording to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877, and WO 2012 / 143080), triphenylene derivatives (for example according to WO 2012 / 048781), dibenzofuran derivatives (for example according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564, or WO 2017 / 148565), or biscarbazoles (for example according to Patent No. 3139321).

[0178] Furthermore, the co-host used can be a compound that is preferably not involved in charge transport, as described, for example, in WO 2010 / 108579.Particularly suitable for combination with the compound of the present invention as co-matrix material are compounds that have a large band gap and are themselves involved in the charge transport of the light-emitting layer, at least to an insignificant extent, if at all.Such materials are preferably purely hydrocarbons.Examples of such materials can be found, for example, in WO 2009 / 124627 or WO 2010 / 006680.

[0179] In a preferred configuration, the compounds of the invention used as emitters are preferably used in combination with one or more phosphorescent materials (triplet emitters) and / or compounds which are TADF (thermally activated delayed fluorescence) host materials, preferably forming hyperfluorescent and / or hyperphosphorescent systems.

[0180] WO2015 / 091716 and WO2016 / 193243 disclose OLEDs that contain both phosphorescent compounds and fluorescent emitters in the emitting layer, where energy is transferred from the phosphorescent compound to the fluorescent emitter (hyperphosphorescence).Therefore, in this context, the phosphorescent compound behaves as a host material.As known to those skilled in the art, in order to transfer the energy from the host material to the emitter with maximum efficiency, the host material has higher singlet energy and triplet energy compared to the emitter.The systems disclosed in the prior art have exactly such an energy relationship.

[0181] Phosphorescence in the context of the present invention is understood to mean emission from excited states of higher spin multiplicity, i.e. spin state greater than 1, in particular emission from excited triplet states. In the context of the present application, luminescent complexes with transition metals or lanthanides, in particular with iridium, platinum and copper, are considered as phosphorescent compounds.

[0182] Suitable phosphorescent compounds (=triplet emitters) are in particular compounds which, when suitably excited, preferably emit light in the visible range and further comprise at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, in particular a metal with this atomic number. Preferred phosphorescent emitters used are compounds which comprise copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds which comprise iridium or platinum.

[0183] Examples of the above mentioned phosphors are disclosed in the applications WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US Patent Application Publication No. 2005 / 0258742, WO 2009 / 146770, WO 2010 / 0 15307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626, WO 2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 02 3377, WO 2014 / 094961, WO 2014 / 094960, WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439, WO 2018 / 011186, WO 2018 / 001990, WO 2018 / 019687, WO 2018 / 01 9688, WO 2018 / 041769, WO 2018 / 054798, WO 2018 / 069196, WO 2018 / 069197, WO 2018 / 069273, WO 2018 / 178001, WO 2018 / 177981, WO 2019 / 020538, WO 2019 / 115423, WO 2019 / 158453 and WO 2019 / 179909. In general, all phosphorescent complexes used in phosphorescent electroluminescent elements 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 exerting his inventive skills.

[0184] The compounds of the present invention may preferably be used in combination with the above-mentioned TADF host materials and / or TADF emitters.

[0185] The process called thermally activated delayed fluorescence (TADF) is described, for example, in BH Uoyama et al., Nature 2012, Vol. 492, 234. To enable this process, for example, -1 A relatively small singlet-triplet difference ΔE(S1-T1) of less than 0.05 is required for the emitter. In order to be able to access the in principle spin-forbidden T1->S1 transition and the emitter, it is possible to provide further compounds with strong spin-orbit coupling in the matrix, so that intersystem crossing is possible via spatial proximity and thus possible interactions between the molecules, or the spin-orbit coupling occurs via metal atoms present in the emitter.

[0186] Further useful sources of information on hyperfluorescent systems include WO 2012 / 133188 (Idemitsu), WO 2015 / 022974 (Kyushu Univ.), WO 2015 / 098975 (Idemitsu), WO 2020 / 053150 (Merck), and DE 202019005189 A1 (Merck).

[0187] Further useful sources of information regarding superphosphorescent systems include WO 2015 / 091716, WO 2016 / 193243 (BASF), WO 01 / 08230 (Princeton Univ. (Mark Thompson)), U.S. Patent Application Publication No. 2005 / 0214575 (Fuji), WO 2012 / 079673 (Merck), WO 2020 / 053314 (Merck), and WO 2020 / 053315 (Merck).

[0188] In a further embodiment of the present invention, the organic electroluminescent device of the present invention does not comprise a separate injection layer and / or transport layer and / or blocking layer and / or electron transport layer, which means that the light-emitting layer is directly adjacent to the injection layer or the anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051.Furthermore, it is also possible to use a metal complex identical or similar to the metal complex in the light-emitting layer as a transport or hole injection material directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0189] The further layer of the organic electroluminescent device of the present invention can use any material that is typically used in the prior art.Therefore, those skilled in the art can use any material that is known for organic electroluminescent device in combination with the compound of formula (I) of the present invention or above preferred embodiment without exerting creative skill.

[0190] Further preferred is an organic electroluminescent device characterized in that one or more layers are coated by a sublimation process. In this case, the material is deposited at 10 -5 Less than millibars, preferably 10 -6 It is applied by vapor deposition at an initial pressure of less than millibar. However, it is also possible to apply it at a lower initial pressure, e.g. 10 -7 It can also be less than millibar.

[0191] Likewise preferred are organic electroluminescent devices, characterized in that one or more layers are coated with the aid of the OVPD (organic vapor phase deposition) method or carrier gas sublimation. In this case, the materials are preferably 10 -5It 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 and structured directly by a nozzle.

[0192] Furthermore, 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, for example screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, Thermal Transfer Printing), inkjet printing or nozzle printing. For this purpose, soluble compounds are required, which can be obtained, for example, by suitable substitution.

[0193] The formulation for applying the compound of formula (I) or the preferred embodiments thereof detailed above is novel.Thus, the present invention further provides a formulation comprising at least one solvent and the compound of formula (I) or the preferred embodiments thereof detailed above.

[0194] Additionally, hybrid processes are possible, for example where one or more layers are applied from solution and one or more further layers are applied by vapor deposition.

[0195] A person skilled in the art is generally aware of these methods and can apply them, without exerting any inventive skill, to an organic electroluminescent device comprising a compound of the present invention.

[0196] The compounds of the present invention and the organic electroluminescent device of the present invention have the particular characteristics of improved lifetime and high color purity compared to the prior art.At the same time, the further electronic properties of the electroluminescent device, such as efficiency or operating voltage, are at least equally good.In yet another variant, the compounds of the present invention and the organic electroluminescent device of the present invention are particularly characterized by improved efficiency and / or operating voltage and long lifetime compared to the prior art.

[0197] The electronic devices, and in particular the organic electroluminescent devices, of the present invention are notable in that they provide one or more of the following surprising advantages over the prior art:

[0198] 1. Electronic devices, particularly organic electroluminescent devices, comprising the compound of formula (I) or the preferred embodiments described above and below as emitters, have very narrow emission bands with very low FWHM (Full Width Half Maximum) values, resulting in particularly pure color emission, which can be recognized by low CIE y values.What is particularly surprising here is that both blue emitters with low FWHM values ​​and emitters with low FWHM that emit in the green, yellow or red region of the color spectrum are provided.

[0199] The emission bands in the long-wave emission flank often have shoulders or secondary maxima that are less than 40% and 30% of the intensity of the main maximum, respectively. This results in a favorable low viewing angle dependence of the color impression compared to prior art narrowband boron-containing emitters, which often do not have such shoulders and secondary maxima in top-emitting OLED components and have a larger viewing angle dependence of the color impression.

[0200] 2. The electronic device, especially the organic electroluminescent device, that comprises the compound of formula (I) or the preferred embodiments described above and below as emitter has a very good life span.In this context, these compounds cause a low roll-off, i.e. a small decrease in the power efficiency of the device, especially at high brightness.

[0201] 3. The electronic device, particularly the organic electroluminescent device, that comprises the compound of formula (I) or the preferred embodiment described above and below as emitter has excellent efficiency.In this context, the compound of the present invention that has the structure of formula (I) or the preferred embodiment described above and below when used in electronic device brings about low operating voltage.

[0202] 4. The compounds of formula (I) or the preferred embodiments described above and below exhibit very high stability and longevity.

[0203] 5. By using the compound of formula (I) or the preferred embodiments described above and below, it is possible to avoid the formation of light loss channels in electronic devices, especially in organic electroluminescent devices.As a result, these devices are characterized by high PL efficiency of the emitter, therefore high EL efficiency, and excellent energy transfer from the matrix to the dopant.

[0204] Excitonic energy is transferred from the host of the matrix or the emitting layer to the emitter via what is typically called Dexter transfer or Förster transfer.Förster energy transfer (FRET) from the host or matrix to the emitter of the present invention is particularly preferred here, because it is particularly efficient and results in electronic devices with particularly good performance data (e.g. efficiency, voltage and life).It is found that energy is preferably transferred from the host or matrix to the compound of the present invention via Förster transfer.

[0205] 6. The compounds of formula (I) or the preferred embodiments described above and below have excellent glass film forming properties.

[0206] 7. Compounds of formula (I) or the preferred embodiments described above and below form very good films from solution and exhibit excellent solubility.

[0207] These above mentioned advantages are not accompanied by an excessively high degradation of the further electronic properties.

[0208] It should be noted that variations of the embodiments described in the present invention are included in the scope of the present invention. Any feature disclosed in the present invention may be replaced with an alternative feature serving the same purpose or an equivalent or similar purpose, unless this is 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.

[0209] 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 separately (not in combination).

[0210] It should also be pointed out that many of the features, particularly those of the preferred embodiments of the present invention, are to be considered inventive in their own right and not merely as part of the embodiments of the present invention: they may seek independent protection in addition to or as an alternative to the invention as claimed.

[0211] The technical teachings disclosed in the present invention may be conceptualized and combined with other examples.

[0212] The present invention is illustrated in detail by the following examples, which are not intended to limit the present invention. Those skilled in the art can use the information provided to practice the present invention to the full extent of the disclosure, and can prepare further compounds of the present invention and use them in electronic devices or use the processes of the present invention without exerting creative skills. EXAMPLES

[0213] The following syntheses are carried out in dry solvents under a protective gas atmosphere unless otherwise stated. Solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The numbers in brackets or the respective numbers cited for individual compounds relate to the CAS numbers of the compounds known from the literature. In the case of compounds that can exhibit multiple conformers, enantiomers, diastereomers or tautomers, one form is shown in a representative manner. The following abbreviations are used for solvents and reagents: DCM-dichloromethane, EA-ethyl acetate, THF-tetrahydrofuran, EtOH-ethanol, NCS-N-chlorosuccinimide, NBS-N-bromosuccinimide, NIS, N-iodosuccinimide.

[0214] 1) Preparation of synthons 1.1) Bicyclic ketones: Example S1: [ka]

[0215] A) By Grignard route: [ka]

[0216] S1 can be prepared in 34% yield from the above reactants via the Grignard route described above, according to the following literature: Phases 1-4: BM Fox et al., J. Med. Chem., 2014, 52, 3464. Phase 5: I. Dragutan et al., Org. Prep.Proced., Int., 1975, 7, 2, 75.

[0217] Purification, especially the removal of the regioisomer resulting from the cyclization in the fifth step, is achieved by flash chromatography on an automated column system (Combi-Flash Torrent, Axel Semrau).

[0218] B) By Suzuki route: [ka]

[0219] S50 can also be prepared in 41% yield from the above reactants via the Suzuki route described above, according to the following literature: Stages 1-3: C. Dolente et al., WO 2011 / 120877. Stage 4: I. Dragutan et al., Org. Prep.Proced., Int., 1975, 7, 2, 75.

[0220] Purification, especially the removal of the regioisomer resulting from the cyclization in the fourth step, is achieved by flash chromatography on an automated column system (Combi-Flash Torrent, Axel Semrau).

[0221] Example S2: [ka]

[0222] C) By Friedel-Crafts alkylation and acylation: [ka]

[0223] S2 can be prepared in 28% yield via the Friedel-Crafts route described above, following literature data, except using 2-chloroanisole rather than anisole. First stage: Ismailov, AG et al., Nauch.Tr.Azerb.Un-t. Ser.Khim.N, 1979, (4),47. Second stage: Ismailov, AG et al., Zhurnal Organicheskoi Khimii, 1978, 14(4), 811. Stages 3 and 4: M. L. Maddess et al., Org. Process Res. Dev. 2014, 18, 528-538.

[0224] Purification, especially the removal of the regioisomer resulting from the cyclization in the second step, is achieved by flash chromatography on an automated column system (Combi-Flash Torrent, Axel Semrau).

[0225] The following synthons can be prepared similarly:

[0226] [Table 5] JPEG2025507608000081.jpg54170

[0227] Example S9: [ka]

[0228] S9 can be prepared in 55% yield by the Grignard route A) described above according to the literature cited above, using 1-bromo-2-chloro-4-iodobenzene instead of 1-bromo-2-fluoro-4-iodobenzene, or by the Grignard route described in GM Castanedo et al., J. Med. Chem., 2017, 60, 627.

[0229] 1.2) Nitrile: Example S100 [ka]

[0230] S100 can be prepared in 69% yield by the above route according to the following literature: Stages 1 and 2: W.S. Tan et al., J. Chin. Chem. Soc., 2012, 59, 399. Phase 3: JM Herbert et al., J. Label.Compd.Radiopharm., 2007, 50, 440.

[0231] Purification is carried out by flash chromatography using an automated column system (Combi-Flash Torrent from Axel Semrau).

[0232] The following synthons can be prepared similarly:

[0233] [Table 6]

[0234] Alternative preparation formats: Alternatively, S100-S103 can be prepared in improved yields by the following route: [ka]

[0235] Steps 1 and 3: As in WS Tan et al., J. Chin.Chem. Soc., 2012, 59, 399. The yield of step 1 is about 95%, and the yield of step 3 is quantitative. Step 2: Iodination with N-iodosuccinimide in trifluoroethanol (TFE) or hexafluoroisopropanol as in R.-J. Tang et al. J. Org. Chem., 2018, 83, 930. Yield 93%.

[0236] Example S100b:

[0237] [ka]

[0238] Similarly, the corresponding bromotriflate can be obtained by using N-bromosuccinimide. 87% yield over three steps.

[0239] Example S100c: [ka]

[0240] Similarly, the corresponding chlorotriflate can be obtained by using N-chlorosuccinimide. Yield 69% over three steps.

[0241] Example S110: [ka]

[0242] Similar procedure to WS Tan et al., J. Chin.Chem. Soc., 2012, 59, 399. Dimethylacetamide (DMAC) was used instead of DMF, which improves the yield. Yield 66%.

[0243] Analogously to S110 (alternative preparation mode), the following synthons can be prepared:

[0244] [Table 7]

[0245] Alternatively, step S110 can be prepared as follows: [ka]

[0246] Step 1: As in MA Zolfigol et al., Molecules 2001, 6, 614. Yield: 93%. Step 2: Ralf et al. Journal für Praktische Chemie 1987, 329(6), 945. Yield 89%. Third stage: As in S. Chandrappa et al., Synlett 2010, 3019. Yield: 87%. Stage 4: EA Krasnokutskaya, Synthesis 2007, (1), 81. Yield 70%

[0247] Optimized synthesis of S110: Phase 1: To a solution of 29.5 g (100 mmol) of 1-cyano-4-hydroxytriptycene cooled to 0° C., a mixture of 19.0 g of 65% by weight nitric acid and 20.0 g of 96% by weight nitric acid is added dropwise over 1 h. The mixture is stirred for another 30 min and then carefully poured into a mixture of 37.8 g (450 mmol) of sodium bicarbonate and 3 l of ice water with very good stirring (bubbles!). The organic phase is separated, the aqueous phase is extracted three times with 200 ml of DCM each time and the combined organic phases are dried over saturated sodium chloride solution and magnesium sulfate. The drying agent is filtered off, the DCM is removed under reduced pressure and the residue is subjected to chromatography (silica gel, n-heptane / EA 5:1). Yield: 31.5 g (93 mmol), 93%; purity: 1 Approximately 98% by H NMR.

[0248] Phase 2: To a well-stirred mixture of 34.0 g (100 mmol) 1-cyano-3-nitro-4-hydroxytriptycene and 93.5 ml (1 mol) phosphoryl chloride, 21.0 ml (120 mmol) diisopropylethylamine (DIPEA) is added and the mixture is stirred at reflux for 4 h. The reaction mixture is poured slowly into 2 l ice water with very good stirring (exothermic, induction period!) and stirred for another 30 min. The aqueous phase is extracted 5 times with 200 ml DCM each time and the combined organic phases are dried over saturated sodium chloride solution and magnesium sulfate. The drying agent is filtered off, the DCM is removed under reduced pressure and the residue is subjected to chromatography (silica gel, n-heptane / EA 5:1). Yield: 40.1 g (89 mmol), 89%; purity: 1 Approximately 97% by H NMR.

[0249] Phase 3: To a well-stirred suspension of 35.9 g (100 mmol) of 1-cyano-3-nitro-4-chlorotriptycene and 25.1 g (450 mmol) of iron powder in 700 ml of EtOH, 75.0 ml of 37% by weight aqueous hydrochloric acid is added dropwise over 30 min under reflux (Caution: Hydrogen evolution!). The mixture is stirred under reflux for a further 3 h, diluted with 2 l of water and 2 l of DCM and alkalized by careful addition (foaming!) of solid sodium carbonate (pH about 9). The mixture is filtered with suction through Celite, the organic phase of the filtrate is separated, the aqueous phase is extracted 5 times with 100 ml of DCM each time and the combined organic phases are washed twice with 300 ml of saturated sodium chloride solution each time and dried over magnesium sulfate. The drying agent is filtered off, the DCM is removed under reduced pressure and the crude product is subjected to Isolute and chromatography (silica gel, n-heptane / DCM 1:1>1:2). If necessary, perform additional chromatography steps until the product turns from white to pale beige. Yield: 28.5 g (87 mmol), 87%; Purity: 1 Approximately 98% by H NMR.

[0250] Phase 4: To a solution of 32.9 g (100 mmol) of 1-cyano-3-amino-4-chlorotriptycene in 500 ml of acetonitrile (4 l four-neck flask, internal thermometer, dropping funnel, precision glass stirrer, argon blanketing), 57.1 g (300 mmol) of p-toluenesulfonic acid monohydrate [6192-52-5] is added in portions and then cooled to 10° C. in an ice bath. To the suspension, with good stirring and ice cooling, is added dropwise a solution of 13.9 g (200 mmol) of sodium nitrite and 37.5 g (250 mmol) of potassium iodide in 60 ml of water and the mixture is stirred for 15 min at 10° C. (Caution: Nitrogen evolution - bubbling). The mixture is then warmed to room temperature and stirred for another 70 min. The mixture is then diluted with 1500 ml of water, adjusted to pH 9.5 by adding saturated sodium bicarbonate solution and mixed with 200 ml of 2M sodium hydrogen sulfite solution. The precipitated crude product is filtered off by suction filtration, washed twice with 50 ml of water each time and briefly dried by suction. The crude product is dissolved in 500 ml of DCM, the solution is dried over sodium sulfate, the drying agent is filtered off and the crude product is subjected to Isolute. Purification is carried out by flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 31.1 g (70 mmol), 70%; Purity: 1 Approximately 97% by H NMR.

[0251] Compounds S111-S115 can be prepared similarly:

[0252] 1.3) Synthesis of substituted iodochloropyridines Synthesis scheme using the example of homoadamantane enamine: [ka]

[0253] Steps 1 to 5 are carried out similarly to syntheses known from the literature. Steps 1 to 4: M. Adachi et al., Tetrahedron Letters, 37 (49), 8871, 1996; European Patent No. 0556008. Stage 5: JD Eckelbarger et al., U.S. Pat. No. 8,835,409; EA Krasnokutskaya et al., Synthesis, 2007,1, 81.

[0254] A) Synthesis of enamines: The enamines can be prepared in about 60-80% yield from the indicated ketones and morpholines by the methods detailed on page 108 of WO 2020 / 064662.

[0255] [Table 8] JPEG2025507608000093.jpg222170

[0256] B) Synthesis of substituted pyridines: Example S200 Phase 1: S200b [ka]

[0257] A mixture of 23.3 g (100 mmol) of S200a (similarly for the other 6- and 7-membered ring enamines), 22.6 g (120 mmol) of 4-(aminomethylene)-2-phenyl-5(4H)-oxazolone [3674-51-9], 47.3 ml (500 mmol) of acetic anhydride [108-24-7] and 150 ml of toluene is stirred at 100 ° C for 4 h (the 5-membered ring enamine is converted in o-xylene in an autoclave at 130 ° C / 4 h). The mixture is completely concentrated under reduced pressure, 70 ml of methanol are added to the oil, the mixture is stirred for another 3 h, the crystallized product is filtered off by suction filtration, washed once with 25 ml of ice-cold methanol and dried under reduced pressure. The crude product thus obtained is further converted without purification. Yield: 26.2 g (78 mmol), 78% E,Z isomer mixture; Purity: 1 Approximately 95% by H NMR.

[0258] Second stage: S200c [ka]

[0259] A mixture of 33.4 g (100 mmol) of S200b and 200 ml of 1-methyl-2-pyrrolidinone (NMP) is stirred at 200-205 °C for 1.5 h. The mixture is cooled to about 100 °C, the NMP is largely removed, the pressure is reduced, the glassy viscous residue is dissolved in 100 ml of warm acetonitrile, stirred at room temperature for another 12 h, the crystalline product is filtered off and dried under reduced pressure. Yield: 25.1 g (75 mmol), 75%; Purity: 1 Approximately 95% by H NMR.

[0260] Phase 3: S200d [ka]

[0261] To a suspension of 33.4 g (100 mmol) of S200c in a mixture of 150 ml of N,N-dimethylformamide (DMF) under ice-salt cooling (approximately -10 °C), 14.0 ml (150 mmol) of phosphoryl chloride in 50 ml of DMF is added dropwise, then the mixture is stirred at room temperature for another 16 h. The reaction mixture is carefully poured into 1000 ml of ice water, stirred for another 10 min, 200 ml of dichloromethane (DCM) is added, the mixture is stirred for another 10 min, and the organic phase is removed. The aqueous phase is made basic (pH 8-9) by careful addition of concentrated ammonia solution, the aqueous phase is extracted three times with 200 ml of ethyl acetate each time, the combined ethyl acetate extracts are washed twice with 200 ml of ice water each time, once with 200 ml of saturated sodium bicarbonate solution and twice with 100 ml of saturated sodium chloride solution each time. The mixture is dried over a mixture of magnesium sulfate and sodium carbonate, the drying agent is filtered off, the organic phase is concentrated under reduced pressure, ethyl acetate (EA) is added and the residue is recrystallized once from acetonitrile. Yield: 24.7 g (81 mmol), 81%; Purity: 1 Approximately 95% by H NMR.

[0262] Phase 4: S200e [ka]

[0263] A mixture of 30.4 g (100 mmol) of S200d, 100 ml of 3N sulfuric acid and 200 ml of dioxane is stirred at 100° C. for 1.5 h. After cooling, the reaction mixture is diluted with 1000 ml of ice water and then the pH is adjusted to about 7.5 with 3N NaOH while cooling with ice. The aqueous phase is extracted three times with 200 ml of DCM each time and the combined organic phases are washed twice with 200 ml of water and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The drying agent is filtered off, the filtrate is concentrated to dryness and the solid is recrystallized from methanol. Yield: 23.1 g (93 mmol), 93%; purity: 1 Approximately 95% by H NMR.

[0264] Phase 5: S200 [ka]

[0265] Variation 1: 24.9 g (100 mmol) of S200e are placed in 500 ml of concentrated hydrochloric acid cooled to 3-5 ° C with good stirring. A cold solution of 10.4 g (150 mmol) of sodium nitrite in 50 ml of water is added dropwise to this suspension with good stirring over 15 minutes, then the mixture is stirred at 5 ° C for about another 20 minutes. The diazonium solution thus obtained is poured into a solution of 90.0 g (600 mmol) of potassium iodide in 5000 ml of water (to which 1000 ml of DCM has been added) cooled to 5 ° C and well stirred (Caution: foaming!). After the evolution of nitrogen has ceased (about 25 minutes), sodium bisulfite solution is added until decolorization and the pH is carefully adjusted to about 0.5 with 5N NaOH while cooling well enough. The mixture is further diluted with 1500 ml of DCM, the organic phase is removed, the aqueous phase is re-extracted twice with 500 ml of DCM each time, the combined organic phases are washed twice with 500 ml of water each time and twice with 500 ml of saturated sodium chloride solution each time and then dried over magnesium sulfate. After removal of the DCM under reduced pressure, the residue is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 22.9 g (63 mmol), 63%; Purity: 1 Approximately 97% by H NMR.

[0266] Variation 2: To a solution of 24.9 g (100 mmol) of S500 in 500 ml of acetonitrile, 57.1 g (300 mmol) of p-toluenesulfonic acid monohydrate [6192-52-5] are added in portions, and the mixture is then cooled to 10 ° C in an ice bath. To the suspension, with good stirring and ice cooling, a solution of 13.9 g (200 mmol) of sodium nitrite and 37.5 g (250 mmol) of potassium iodide in 60 ml of water is added in portions, and the mixture is stirred at 10 ° C for 15 minutes. The mixture is then warmed to room temperature and stirred for another 70 minutes. The mixture is then diluted with 1500 ml of water, adjusted to pH 9.5 by addition of saturated sodium bicarbonate solution and mixed with 200 ml of 2 M sodium sulfite solution. The precipitated crude product is filtered off by suction filtration, washed twice with 50 ml of water each time and briefly dried by suction. The crude product is dissolved in 500 ml of DCM, the solution is dried over sodium sulfate, the drying agent is filtered off and the crude product is subjected to Isolute. Purification is carried out by flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 25.0 g (72 mmol), 72%; Purity: 1 Approximately 97% by H NMR.

[0267] The following pyridines can be obtained analogously to steps 1-5. Yields for the five steps (steps 1-5):

[0268] [Table 9] JPEG2025507608000100.jpg215170

[0269] 1.4) Synthesis of substituted iodochlorobenzenes Example S300: Preparation similar to "Optimized synthesis of S110" [ka]

[0270] Step 1: As in MA Zolfigol et al., Molecules 2001, 6, 614. Yield: 96%. Step 2: Ralf et al. Journal für Praktische Chemie 1987, 329(6), 945. Yield 91%. Third step: As in S. Chandrappa et al., Synlett 2010, 3019. Yield: 90%. Stage 4: EA Krasnokutskaya, Synthesis 2007, (1), 81. Yield: 78%.

[0271] The following compounds can be prepared similarly; yields in four steps:

[0272] [Table 10]

[0273] Example S400: [ka]

[0274] Suzuki coupling: Starting mixture: 21.7 g (50 mmol) 1,4-chloro-2,5-difluoro-3,6-diiodobenzene [2410043-16-0], 13.4 g (110 mmol) phenylboronic acid, 31.8 g (300 mmol) sodium carbonate, 702 mg (1 mmol) bis(triphenylphosphino)palladium(II) chloride, 250 ml acetonitrile, 250 ml methanol, 60° C., 12 h. Work-up: The residue is worked up by filtering off the salts, concentrating the filtrate and extracting with DCM:water. Purification by flash chromatography. Yield: 12.9 g (38 mmol), 76%; Purity: 1 Approximately 97% by H NMR.

[0275] The following compounds can be prepared similarly:

[0276] [Table 11]

[0277] 2. Synthesis of Carbazole C: Example C1: Phase 1: [ka]

[0278] A well-stirred mixture of 30.0 g (100 mmol) of S1, 9.8 g (105 mmol) of aniline, 28.8 g (300 mmol) of sodium tert-butoxide, 1.11 g (2 mmol) of dppf, 225 mg (1 mmol) of palladium(II) acetate in 500 ml of toluene is heated to reflux for 1 h. The mixture is cooled to 70 ° C, 500 ml of water is added, the mixture is stirred for another 10 min, the organic phase is separated, washed twice with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a celite bed in the form of a toluene slurry, the filtrate is concentrated under reduced pressure, the residue is dissolved in 300 ml of DCM and the latter is replaced with the distilled off DCM by removing the DCM under reduced pressure and simultaneously adding EtOH. The crystallized product is filtered off by suction filtration, washed 3 times with 50 ml of EtOH each time and dried under reduced pressure. Yield: 27.7 g (89 mmol), 89%. Purity: 1 About 98% by H NMR. If triflate is used, gradually meter out the triflate: see J. Louie et al., Journal of Organic Chemistry 1997, 62(5), 1268.

[0279] Phase 2: [ka]

[0280] A well-stirred mixture of 31.2 g (100 mmol) of the amine from the first stage, 69.1 g (500 mmol) of potassium carbonate, 3.1 g (30 mmol) of pivalic acid, 1.16 g (4 mmol) of tri-tert-butylphosphonium tetrafluoroborate, 449 mg (2 mmol) of palladium(II) acetate, 100 g of glass beads (diameter 3 mm) and 1000 ml of dimethylacetamide (DMAC) is stirred at 150 ° C for 1 h. The mixture is filtered hot through a Celite bed in the form of a DMAC slurry, the filtrate is concentrated to dryness, the residue is dissolved in 500 ml of DCM, the latter is removed under reduced pressure and replaced by the simultaneous addition of 300 ml of EtOH with the distilled off DCM. The crystallized product is filtered off by suction filtration, washed three times with 50 ml of EtOH each time and dried under reduced pressure. Yield: 22.5g (81mmol), 81%; Purity: 1 Approximately 98% by H NMR.

[0281] The following compounds can be prepared similarly; yields in two steps:

[0282] [Table 12] JPEG2025507608000108.jpg234170 JPEG2025507608000109.jpg229170 JPEG2025507608000110.jpg247170 JPEG2025507608000111.jpg224170 JPEG2025507608000112.jpg246170 JPEG2025507608000113.jpg229170 JPEG2025507608000114.jpg229170 JPEG2025507608000115.jpg238170 JPEG2025507608000116.jpg230170 JPEG2025507608000117.jpg220170 JPEG2025507608000118.jpg245170 JPEG2025507608000119.jpg216170 JPEG2025507608000120.jpg213170 JPEG2025507608000121.jpg231170 JPEG2025507608000122.jpg210170 JPEG2025507608000123.jpg99170

[0283] Example C600: Phase 1: [ka]

[0284] To a well-stirred solution of 42.5 g (100 mmol) of C100 in 1000 ml of DCM, 19.8 g (100 mmol) of N-bromosuccinimide (NBS) are added in portions, and the mixture is then stirred at room temperature for 5 h. The DCM is removed under reduced pressure and replaced by simultaneous addition of MeOH (final volume about 300 ml). The crystallized product is filtered off by suction filtration, washed twice with 50 ml of MeOH each time and dried under reduced pressure. Yield: 48.0 g (95 mmol), 95%; Purity: 1 Approximately 98% by H NMR.

[0285] Phase 2: [ka]

[0286] A well-stirred mixture of 44.7 g (100 mmol) of Br-carbazole, 7.0 ml (50 mmol) of trimethylboroxine [823-96-1], 41.5 g (300 mmol) of potassium carbonate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 449 mg (2 mmol) of palladium(II) acetate, 100 g of glass beads (diameter 3 mm) and 800 ml of dimethylacetamide (DMAC) is stirred at 120 ° C for 12 hours. The mixture is filtered hot through a Celite bed in the form of a DMAC slurry, the filtrate is concentrated to dryness, the residue is dissolved in 500 ml of DCM, the latter is removed under reduced pressure and replaced by the simultaneous addition of 300 ml of EtOH with the distilled off DCM. The crystallized product is filtered off by suction filtration, washed three times with 50 ml of EtOH each time and dried under reduced pressure. Yield: 31.7g (83mmol), 83%; Purity: 1 Approximately 98% by H-NMR.

[0287] The following compounds can be prepared similarly; yields in two steps:

[0288] [Table 13] JPEG2025507608000127.jpg211170 JPEG2025507608000128.jpg102170

[0289] 3. Compounds of the invention: Example D1: [ka]

[0290] A well-stirred mixture of 41.0 g (100 mmol) of carbazole C1, 9.1 g (50 mmol) of 1,4-dichloro-2,5-difluorobenzene [400-05-5], 69.1 g (500 mmol) of potassium carbonate, 100 g of glass beads (diameter 3 mm), and 1000 ml of dimethylacetamide (DMAC) is stirred for 3 h at 150 °C. The mixture is allowed to cool to 80 °C, 3.1 g (30 mmol) of pivalic acid, 1.16 g (4 mmol) of tri-tert-butylphosphonium tetrafluoroborate, and 449 mg (2 mmol) of palladium(II) acetate are added, and the mixture is stirred for another 2 h at 140 °C. The mixture is left to cool to 80 ° C, 2000 ml of water are added dropwise, the precipitated crude product is filtered off by suction filtration, washed three times with 200 ml of water each time and three times with 200 ml of ethanol each time and dried under reduced pressure. The crude product is dissolved in 500-1000 ml of DCM (in the case of pyridine, 10% by weight of ethyl acetate is added), the mixture is filtered in the form of a DCM slurry through a silica gel bed, the DCM is removed under reduced pressure and towards the end is replaced by the simultaneous addition of 300 ml of EtOH. The crystallized product is filtered off by suction filtration, washed three times with 50 ml of EtOH each time and dried under reduced pressure. Further purification can be achieved by successive hot extractions (with standard organic solvents or combinations thereof, preferably DCM or acetonitrile / DCM 3:1 to 1:3) or flash chromatography (CombiFlash Torrent automated column system from A. Semrau, silica gel, RP silica gel, aluminum oxide, eluents: toluene / n-heptane / triethylamine, acetonitrile / THF or DCM) and finally fractional sublimation or thermal treatment under high vacuum (typically at temperatures of about 200-400 °C, for about 10 min). -5 ~10 -6 1000 sq. mbar pressure). Yield: 24.8 g (28 mmol), 56%; Purity: about 99.9% by HPLC.

[0291] When two different carbazoles C are used as a mixture or preferably by sequential addition (i.e. first 50 mmol of the first carbazole and then after a reaction time of about 2 hours 50 mmol of the second carbazole), after chromatographic separation of the possible coupling and cyclization products, compounds of the invention with mixed functionalization can be obtained.

[0292] The following compounds can be prepared similarly:

[0293] [Table 14] JPEG2025507608000131.jpg208170 JPEG2025507608000132.jpg229170 JPEG2025507608000133.jpg229170 JPEG2025507608000134.jpg213170 JPEG2025507608000135.jpg219170 JPEG2025507608000136.jpg218170 JPEG2025507608000137.jpg211170 JPEG2025507608000138.jpg228170 JPEG2025507608000139.jpg214170 JPEG2025507608000140.jpg220170 JPEG2025507608000141.jpg219170 JPEG2025507608000142.jpg202170 JPEG2025507608000143.jpg214170 JPEG2025507608000144.jpg220170 JPEG2025507608000145.jpg219170 JPEG2025507608000146.jpg210170 JPEG2025507608000147.jpg208170 JPEG2025507608000148.jpg198170 JPEG2025507608000149.jpg114170

[0294] Example D200: [ka]

[0295] Step 1: Double Buchwald-Hartwig coupling, procedure similar to intermediate 12 in examples 2-5 of EP 3723149. Bis(chlorocarbazole) is isolated. Yield: 66%. Step 2: Double cyclization, procedure similar to step 2 of Example C1, yield 57%. HP(t-Cy3)BF4 can be used instead of HP(t-Bu3)BF4, and the addition of 30 mol% pivalic acid typically has the effect of improving the yield. Alternatively, cyclization can be performed using NHC-Pd complexes, such as allyl-[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]chloropalladium(II) (e.g., as in T. Kader et al., Chem. Europ. J., 2019, 25(17), 4412 or as in U.S. Pat. No. 9,000,421); typical yield 30-80%.

[0296] The following compounds can be prepared similarly:

[0297] [Table 15] JPEG2025507608000152.jpg233170

[0298] Example D300:

[0299] [ka]

[0300] Steps 1 and 2: Procedures similar to those in Taisei Taniguchi et al., Chem. Lett. 2019, 48, 1160. Yield: 26% D300; 11% F100.

[0301] The following compounds can be prepared similarly:

[0302] [Table 16]

[0303] OLED Component Manufacturing 1) Vacuum Processing Components One use of the compounds of the present invention is as dopants in the emissive layers of fluorescent and perfluorescent OLED components.

[0304] The OLEDs (organic light emitting diodes) of the invention and of the prior art are produced by the general methods according to WO 2004 / 058911 adapted to the conditions described here (variations in layer thickness, materials used).

[0305] In the following examples, results are given for various OLEDs. Cleaned glass plates (Miele laboratory glass washer, cleaned with detergent from Merck Extran) coated with 50 nm thick structured ITO (indium tin oxide) are pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and coated within 30 minutes with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), spun from an aqueous solution, purchased from Heraeus Precious Metals GmbH Deutschland as CLEVIOS™ PVPAI4083) to improve processing, then baked at 180° C. for 10 minutes. These coated glass plates form the substrate on which the OLEDs are applied. After fabrication, the OLEDs are encapsulated for protection against oxygen and water vapor. The exact layer structure of the electroluminescent OLEDs can be found in the examples. The materials required for the fabrication of the OLEDs are given in Table 8.

[0306] OLEDs are characterized in the standard way. For this purpose, the electroluminescence spectrum, current efficiency (measured in cd / A), power efficiency (measured in lm / W), and external quantum efficiency (EQE, measured in percent) are calculated from the current-voltage-luminance characteristic (IUL characteristic) as a function of luminance, assuming a Lambertian emission characteristic. The electroluminescence spectrum is measured at 100 or 1000 cd / m 2 These are used to infer the emission color and the EL-FWHM value (electroluminescence-full width at half maximum-width of the EL emission spectrum at half the peak height (eV)) for ease of comparison across the spectral range.

[0307] Fluorescent OLED components: All materials are applied by thermal evaporation in a vacuum chamber. The light-emitting layer (EML) always consists of at least one matrix material (host material) SMB and a light-emitting dopant (emitter) ES or EAS, which is added to the matrix material in a certain volume percentage by co-evaporation. A specification given in the form SMB:ES or EAS (97:3%) means here that the material SMB is present in the layer in a volume percentage of 97% and the dopant ES or EAS in a percentage of 3%. Similarly, the electron transport layer may also consist of a mixture of two materials, for example here a mixture of ETM1 (50%) and ETM2 (50%) (see Table 1). The materials used in the manufacture of the OLED are given in Table 8. The compound Ref.-D1 is used for comparison (see Table 8).

[0308] Blue fluorescent OLED component BF: An OLED basically has the following layer structure: substrate Injection layer 1 (HIL1) composed of HTM1 doped with -5% NDP-9 (commercially available from Novaled), 20 nm - Transport layer 1 (HTL1) composed of HTM1, 160 nm - Transport Layer 2 (HTL2), see Table 1 -Emitting layer (EML), see Table 1 - Electron transport layer (ETL2), see Table 1 -Electron transport layer (ETL1) composed of ETM1 (50%) and ETM2 (50%), 30 nm electron injection layer (EIL) composed of ETM2, 1 nm - Anode made of aluminum, 100 nm

[0309] [Table 17]

[0310] [Table 18]

[0311] Phosphorescent OLED components: All materials are applied by thermal evaporation in a vacuum chamber. The emissive layer (EML) always consists of at least one matrix material (host material) TMM, a (phosphorescent) sensitizer PS, and a fluorescent emitter ES or EAS. The matrix material (host material) TMM may also consist of two components (premixed host, e.g. TMM2) that are evaporated as a mixture, the composition of which is likewise shown in Table 8. The sensitizer and the fluorescent emitter ES or EAS are added to the host material TMM in a certain volume percentage by co-evaporation. Details given in the form TMM:PS(5%):ES or EAS(3%) etc. mean here that in the layer there are 92% by volume of the materials TMM, 5% by volume of PS, and 3% by volume of ES or EAS.

[0312] Blue superphosphorescent OLED component BH: An OLED basically has the following layer structure: -substrate Injection layer 1 (HIL1) composed of HTM2 doped with -5% NDP-9 (commercially available from Novaled), 20 nm - Transport layer 1 (HTL1) composed of HTM2, 30 nm - Transport Layer 2 (HTL2), see Table 3 -Emitting layer (EML), see Table 3 - Electron transport layer (ETL2), see Table 3 -Electron transport layer (ETL1) composed of ETM1 (50%) and ETM2 (50%), 20 nm -Electron injection layer (EIL) composed of ETM2, 1 nm - Anode made of aluminum, 100 nm

[0313] [Table 19]

[0314] [Table 20]

[0315] Green hyperphosphorescent OLED component GH: An OLED basically has the following layer structure: -substrate Injection layer 1 (HIL1) composed of HTM2 doped with -5% NDP-9 (commercially available from Novaled), 20 nm - Transport layer 1 (HTL1) composed of HTM2, 30 nm - Transport Layer 2 (HTL2), see Table 5 -Emitting layer (EML), see Table 5 - Electron transport layer (ETL2), see Table 5 -Electron transport layer (ETL1) composed of ETM1 (50%) and ETM2 (50%), 30 nm -Electron injection layer (EIL) composed of ETM2, 1 nm - Anode made of aluminum, 100 nm

[0316] [Table 21]

[0317] [Table 22]

[0318] 2) Solution Processing Components: The manufacture of solution-based OLEDs is essentially described in the literature, for example in WO 2004 / 037887 and WO 2010 / 097155. In the following examples, the two manufacturing processes (coating from the gas phase and solution processing) are combined, in which the layers up to and including the emissive layer are processed from solution, and the subsequent layers (blocking layer / electron transport layer) are applied by evaporation under reduced pressure. For this purpose, the general methods described above are combined as follows, adapted to the circumstances described here (layer thickness variations, materials):

[0319] Therefore, the configuration used is the following: -substrate -ITO, 50nm -PEDOT, 20nm - Transport layer consisting of HTM-Sol HIL-Sol, 20 nm -Emitting layer composed of SMB4 (97%) and ES (3%) or EAS (3%), 50 nm -Electron transport layer (ETL1) composed of ETM1 (50%) and ETM2 (50%), 25 nm - Anode made of aluminum, 100 nm

[0320] The substrates used are glass plates coated with a structured ITO (indium tin oxide) with a thickness of 50 nm. For better processing, these are coated with a buffer (PEDOT) Clevios P ​​VP AI 4083 (Heraeus Clevios GmbH, Leverkusen). The PEDOT is on top. Spin coating is carried out from water under air. The layer is then baked at 180 ° C for 10 minutes. The transport layer and the emitting layer are applied to the glass plate thus coated. The transport layer is the polymer HTM-Sol, with the structure shown in table 8, which was synthesized according to WO 2010 / 097155. The polymer is dissolved in toluene, again the solution typically has a solids content of about 5 g / l, and a layer thickness of 20 nm, typical for the device, is achieved by spin coating. The layer is spun in an inert gas atmosphere (argon in this case) and baked at 180 ° C for 60 minutes.

[0321] The emitting layer always consists of at least one matrix material (host material) and a light-emitting dopant (emitter). Details given in the format such as SMB4 (97%) and ES or EAS (3%) mean here that the material SMB4 is present in the emitting layer at 97% by weight and the dopant ES or EAS at 3% by weight. The mixture of the emitting layer is dissolved in toluene or chlorobenzene. The typical solids content of such a solution is about 18 g / l when, as here, a layer thickness of 50 nm typical for the device is achieved by spin coating. The layer is spun in an inert gas atmosphere (argon in this case) and baked at 140-160 ° C for 10 min. The materials used are shown in Table 8.

[0322] The materials of the electron transport layer and the cathode are applied by thermal evaporation in a vacuum chamber. The electron transport layer may, for example, be composed of two or more materials, which are added to each other in a certain volumetric proportion by co-evaporation. Details given in the form ETM1(50%) and ETM2(50%) etc. here mean that the ETM1 and ETM2 materials are present in the layer in a proportion of 50% by volume each. The materials used in this case are given in Table 8.

[0323] [Table 23]

[0324] [Table 24] JPEG2025507608000163.jpg247170 JPEG2025507608000164.jpg65170

[0325] The abbreviations for the compounds of the invention used in the above tables in relation to the OLED components relate to the abbreviations provided in the synthesis examples above.

[0326] Compared with reference, the compounds of the present invention show narrower electroluminescent spectrum, which can be recognized by smaller or equal EL-FWHM value (electroluminescence-full width at half maximum-width of EL emission spectrum at half peak height (eV)). Narrower electroluminescent spectrum improves color purity obviously (lower CIE y value). Moreover, EQE value (External Quantum Efficiency) is obviously higher and operating voltage is lower compared with reference, which improves device power efficiency obviously and therefore consumes less power.

[0327] Fabrication of components for color conversion The compounds of the present invention can be used for color conversion. For this purpose, the compounds are incorporated into compositions, which are then processed by known methods (pin coating, slit coating, screen printing, nozzle printing, inkjet printing, etc.) to obtain pixels or two-dimensional layers. The compositions are typically composed of crosslinkable components (monomers, oligomers, polymers) based on acrylates, acrylamides, polyesters, silicones, etc., and one or more thermally or photochemically activatable starting components. In addition, further components such as organic auxiliaries (antioxidants, stabilizers, levelling aids, viscosity modifiers, etc.) or inorganic fillers (SiO2, TiO2, Al2O3, etc.) can be introduced.

[0328] General procedure for preparing the composition and the derivative layer: 0.5 g of the inventive compound ES or EAS, 0.2 g of titanium dioxide (TiO2ToyoColor from Toyo Ink Group) and 10 g of OE-6550 optical encapsulant (from Dow Corning) are homogenized at 40° C. with very good stirring (magnetic stirrer) under the action of ultrasound (ultrasonic bath). A layer with a layer thickness of about 15 μm is produced by knife coating, then cured by baking (150° C., 1 hour) under nitrogen atmosphere.

[0329] Spectral measurements of layers: The fluorescence spectra and EQE values ​​(external quantum efficiency, EQE = emitted photons / absorbed photons) of the layers are confirmed with a fluorescence spectrometer (C9920, Hamamatsu photonics) equipped with an Ulbricht sphere and optical fibers (excitation wavelengths CWL: 420-440 nm for blue emitters and 450 nm for green emitters, reference measurement at room temperature under air).

[0330] result The results are summarized in Table 9.

[0331] [Table 25]

Claims

1. A compound comprising at least one structure of formula (I): 【Chemistry 1】 wherein A is in each case the same or different and is a moiety of formula (A1) or (A2), 【Chemistry 2】 The partial structure has two partial structures B fused thereto, and is represented by the symbols o and ＊ represents the two condensation sites of each of the partial structures B, one partial structure B is condensed to A via the position labeled o, and one partial structure B is ＊ and at least one of said substructures B is selected from substructures of formula (B1), 【Transformation 3】 The other partial structure B is selected from the partial structure of formula (B1) or the partial structure of formula (B2) shown below: 【Chemistry 4】 wherein the dotted bond represents the point of fusion of said ring structure B to A; Ring C ｃ are the same or different in each occurrence and are fused aliphatic or heteroaliphatic rings having 5 to 60 ring atoms, optionally substituted by one or more R groups; Ring C ｂ are the same or different in each occurrence and are fused aliphatic or heteroaliphatic rings having 5 to 60 ring atoms, optionally substituted by one or more R groups; Further symbols are as follows: Z is the same or different in each occurrence and is N, C—CN, or CR ｃ and Y is the same or different in each occurrence and is CO, P(=O)R ｃ , SO, SO ２ , C(O)O, C(S)O, C(O)S, C(=O)NR ｃ , C(═O)NAr′, W １ , W ２ are the same or different in each case, and C(R) ２ , O, S, Si(R) ２ and X is the same or different in each occurrence and is N or CR, provided that X, X in one ring ｂ no more than two of the groups are N; X ａ are the same or different in each case, N or CR ａ and X ｂ are the same or different in each case, N or CR ｂ and X, X in one ring ｂ no more than two of the groups are N; X ｃ are the same or different in each case, N or CR ｃ and R is the same or different in each occurrence and is H, D, OH, F, Cl, Br, I, CN, NO ２ , N(Ar) ２ , N(R ｄ ) ２ , C(=O)N(Ar) ２ , C(=O)N(R ｄ ) ２ , C(Ar) ３ , C(R ｄ ) ３ , Si(Ar) ３ , Si(R ｄ ) ３ , B(Ar) ２ , B(R ｄ ) ２ , C(=O)Ar, C(=O)R ｄ , P(=O)(Ar) ２ , P(=O)(R ｄ ) ２ , P(Ar) ２ , P(R ｄ ) ２ , S(=O)Ar, S(=O)R ｄ , S(=O) ２ Ar, S(=O) ２ R ｄ , OSO ２ Ar, OSO ２ R ｄ , a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein said alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is in each case linked to one or more R ｄ may be substituted by one or more non-adjacent CH ２ The group is R ｄ C=CR ｄ , C≡C, Si(R ｄ ) ２ , C=O, C=S, C=Se, C=NR ｄ , -C(=O)O-, -C(=O)NR ｄ -, NR ｄ , P(=O)(R ｄ ), —O—, —S—, SO, or SO ２ or 5 to 60 aromatic ring atoms, in each case one or more R ｄ an aromatic or heteroaromatic ring system optionally substituted by a group, or a ring system having 5 to 60 aromatic ring atoms and one or more R ｄ an aryloxy group or heteroaryloxy group optionally substituted by a group, or an aryloxy group or heteroaryloxy group having 5 to 60 aromatic ring atoms and one or more R ｄ an arylthio group or heteroarylthio group optionally substituted by a group, or an arylthio group having 5 to 60 aromatic ring atoms and one or more R ｄ a diarylamino group, an arylheteroarylamino group, a diheteroarylamino group, or an alkyl group having 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl group, and one or more R ｄ an aralkyl or heteroarylalkyl group optionally substituted by a group, and at the same time one R group may be taken together with a further group to form a ring system; Ar in each occurrence is the same or different and has 5 to 60 aromatic ring atoms, Above R ｄ and two Ar groups bonded to the same carbon, silicon, nitrogen, phosphorus, or boron atom are bridged by a single bond or separated by a B(R ｄ ), C(R ｄ ) ２ , Si(R ｄ ) ２ , C═O, C═NR ｄ , C=C(R ｄ ) ２ ,O,S,S=O,SO ２ , N(R ｄ ), P(R ｄ ), and P(═O)R ｄ and the bond may be via a bridge selected from R ａ , R ｂ , R ｃ , R ｄ are the same or different in each case and are H, D, OH, F, Cl, Br, I, CN, NO ２ , N(Ar′) ２ , N(R １ ) ２ , C(=O)N(Ar') ２ , C(=O)N(R １ ) ２ , C(Ar′) ３ , C(R １ ) ３ , Si(Ar′) ３ , Si(R １ ) ３ , B(Ar′) ２ , B(R １ ) ２ , C(=O)Ar', C(=O)R １ , P(=O)(Ar') ２ , P(=O)(R １ ) ２ , P(Ar′) ２ , P(R １ ) ２ , S(=O)Ar', S(=O)R １ , S(=O) ２ Ar', S(=O) ２ R １ , OSO ２ Ar', OSO ２ R １ , a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein said alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is in each case linked to one or more R １ may be substituted by one or more non-adjacent CH ２ The group is R １ C=CR １ , C≡C, Si(R １ ) ２ , C=O, C=S, C=Se, C=NR １ , -C(=O)O-, -C(=O)NR １ -, NR １ , P(=O)(R １ ), —O—, —S—, SO, or SO ２ or 5 to 60 aromatic ring atoms, in each case one or more R １ an aromatic or heteroaromatic ring system optionally substituted by a group, or a ring system having 5 to 60 aromatic ring atoms and one or more R １ an aryloxy group or a heteroaryloxy group optionally substituted by a group, and at the same time, two R ａ , R ｂ , R ｃ , R ｄ the groups together or with further groups may form a ring system; Ar′ in each occurrence is the same or different and has 5 to 60 aromatic ring atoms and is selected from one or more R １ and at the same time, two Ar′ groups bonded to the same carbon, silicon, nitrogen, phosphorus, or boron atom are bridged by a single bond or by 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,SO ２ , N(R １ ), P(R １ ), and P(═O)R １ and the bond may be via a bridge selected from R １ are in each case the same or different and are H, D, F, Cl, Br, I, CN, NO ２ , N(Ar″) ２ , N(R ２ ) ２ , C(=O)Ar'', C(=O)R ２ , P(=O)(Ar'') ２ , P(Ar″) ２ , B(Ar″) ２ , B(R ２ ) ２ , C(Ar″) ３ , C(R ２ ) ３ , Si(Ar″) ３ , Si(R ２ ) ３ a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be selected from the group consisting of one or more R ２ may be substituted by one or more non-adjacent CH ２ The group is -R ２ C=CR ２ -, -C≡C-, Si(R ２ ) ２ , C=O, C=S, C=Se, C=NR ２ , -C(=O)O-, -C(=O)NR ２ -, NR ２ , P(=O)(R ２ ), —O—, —S—, SO, or SO ２ and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ or 5 to 60 aromatic ring atoms, in each case one or more R ２ an aromatic or heteroaromatic ring system optionally substituted by a group, or a ring system having 5 to 60 aromatic ring atoms and one or more R ２ an aryloxy group or heteroaryloxy group optionally substituted by a group, or an aryloxy group or heteroaryloxy group having 5 to 60 aromatic ring atoms and one or more R ２ aralkyl or heteroaralkyl groups optionally substituted by groups, or combinations of these systems, and at the same time, two or more R １ The groups may together form a ring system, and at the same time, one or more R １ The group may form a ring system together with further moieties of the compound; Ar″ is the same or different in each occurrence and has 5 to 30 aromatic ring atoms and one or more R ２ and wherein two Ar″ groups bonded to the same carbon, silicon, nitrogen, phosphorus, or boron atom are bridged by a single bond or by a 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 the bond may be via a bridge selected from R ２ are in each occurrence the same or different and are selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon group 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, which may in turn be replaced by one or more alkyl groups each having 1 to 4 carbon atoms, and at the same time two or more substituents R ２ may be taken together to form a ring system.

2. It comprises at least one structure of formula (I-1) to (I-4), 【Transformation 5】 【change】 In the formula, symbol C ｂ , C ｃ , Y., W. １ , W ２ , Z, X, X ａ , X ｂ , and X ｃ has the definition as defined in claim 1 The compound of claim 1.

3. It is characterized by comprising at least one partial structure of formula (B1-1) to (B1-30), 【Transformation 6】 【change】 【change】 In the formula, the symbol C ｃ , W １ , Y.R.R. ｂ , R ｃ , and R ｄ has the definition given in claim 1, the dotted bond represents the site of fusion of said substructure to A, and further symbols and indices used are as follows: X １ are the same or different in each case, and N or CR ｄ wherein the X in one ring １ no more than two of the groups are N; Y １ are the same or different in each case, and C(R ｄ ) ２ , (R ｄ ) ２ C-C (R ｄ ) ２ , (R ｄ ) C=C(R ｄ ), N.R. ｄ ,NAr',O,S,SO,SO ２ , Se, P(O)R ｄ , B.R. ｄ , or Si(R ｄ ) ２ and k is 0 or 1; n is 0, 1, 2, or 3; m is 0, 1, 2, 3, or 4; l is 0, 1, 2, 3, 4, or 5; The compound of claim 1.

4. When the compound contains the partial structure (B2), the partial structure (B2) is selected from the structures of formulas (B2-1) to (B2-30), 【Transformation 7】 【change】 【change】 In the formula, the symbol C ｂ , W １ , W ２ , Z, R, R ｂ , R ｃ , and R ｄ has the definition given in claim 1, and the dotted bond represents the site of condensation of said moiety to A; X 1 is the same or different in each occurrence and is N or CR d , provided that no more than two of said X 1 groups in any one ring are N; Y 1 is the same or different in each occurrence and is C(R d ) 2 , (R d ) 2 C—C(R d ) 2 , (R d )C═C(R d ), NR d , NAr′, O, S, SO, SO 2 , Se, P(O)R d , BR d , or Si(R d ) 2 ; k is 0 or 1; n is 0, 1, 2, or 3; m is 0, 1, 2, 3, or 4; l is 0, 1, 2, 3, 4, or 5; The compound of claim 1.

5. It comprises at least one structure of the formulas (II-1) to (II-21), 【Transformation 8】 【change】 【change】 In the formula, the symbol C ｂ , C ｃ , Y., W. １ , W ２ , Z, R, R ａ , R ｂ , R ｃ , and R ｄ is defined in claim 1 and further indices used are: Y 1 is the same or different in each occurrence and is C(R d ) 2 , (R d ) 2 C—C(R d ) 2 , (R d )C═C(R d ), NR d , NAr′, O, S, SO, SO 2 , Se, P(O)R d , BR d , or Si(R d ) 2 ; m is 0, 1, 2, 3, or 4; l is 0, 1, 2, 3, 4, or 5; The compound of claim 1.

6. The fused ring C ｃ is selected from the structures of formulas (CCY-1) to (CCY-10), 【Chemistry 9】 wherein R has the definition given in claim 1, the dotted bond represents the point of attachment of the fused ring to a further group, and further Z １ , Z ４ are the same or different in each case, and C(R ３ ) ２ , O, S, or Si(R ３ ) ２ and Z ２ But C(R) ２ , O, S, NR, or C(=O), and two adjacent Z ２ the group is -CR=CR- or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms and optionally substituted with one or more R groups; G is an alkylene group having 1, 2, or 3 carbon atoms and optionally substituted with one or more R groups, -CR=CR-, or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms and optionally substituted with one or more R groups; R ３ are in each case the same or different and are H, D, F, Cl, Br, I, CN, NO ２ , N(Ar′) ２ , N(R ｄ ) ２ , C(=O)Ar', C(=O)R ｄ , P(=O)(Ar') ２ , P(Ar′) ２ , B(Ar′) ２ , B(R ｄ ) ２ , C(Ar′) ３ , C(R ｄ ) ３ , Si(Ar′) ３ , Si(R ｄ ) ３ a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be selected from the group consisting of one or more R ｄ may be substituted by one or more non-adjacent CH ２ The group is R ｄ C=CR ｄ -, -C≡C-, Si(R ｄ ) ２ , C=O, C=S, C=Se, C=NR ｄ , -C(=O)O-, -C(=O)NR ｄ -, NR ｄ , P(=O)(R ｄ ), —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 60 aromatic ring atoms, each of which may be replaced by one or more R ｄ an aromatic or heteroaromatic ring system optionally substituted by a group, or a ring system having 5 to 60 aromatic ring atoms and one or more R ｄ an aryloxy group or heteroaryloxy group optionally substituted by a group, or an aryloxy group or heteroaryloxy group having 5 to 60 aromatic ring atoms and one or more R ｄ an aralkyl group or a heteroaralkyl group optionally substituted by a group, or a combination of these systems, and at the same time, two R ３ The groups may together form an aliphatic or aromatic ring system, thus forming a spiro system, and further, R ３ But, R, R ａ , R ｃ , or R ３ Ar′ and R may form an aliphatic ring system together with the group. ｄ has the definition given in claim 1, provided that the two heteroatoms in these groups are not directly bonded to each other and the two C═O groups are not directly bonded to each other; The compound of claim 1.

7. The fused ring C ｃ is selected from the structures of formulas (CRA-1) to (CRA-13), 【Chemistry 10】 wherein R has the definition given in claim 1, the dotted bond represents the point of attachment of the fused ring to a further group, and the further symbols are defined as follows: Y ２ are the same or different in each case, and C(R) ２ , (R) ２ CC (R) ２ , (R)C═C(R), NR, NAr′, O, or S; R ｆ are in each occurrence the same or different and are selected from F, a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein said alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is in each occurrence selected from one or more R ｄ may be substituted by one or more non-adjacent CH ２ The group is R ｄ C=CR ｄ , C≡C, Si(R ｄ ) ２ , C=O, C=S, C=Se, C=NR ｄ , -C(=O)O-, -C(=O)NR ｄ -, NR ｄ , P(=O)(R ｄ ), —O—, —S—, SO, or SO ２ or 5 to 60 aromatic rings, and one or more R ｄ an aromatic or heteroaromatic ring system optionally substituted by a group, or a ring system having 5 to 60 aromatic ring atoms and one or more R ｄ an aryloxy group or a heteroaryloxy group optionally substituted by a group, and at the same time, two R ｆ The groups together or one R ｆ The groups together with the R group or with further groups can also form a ring system, R ｄ has the definition given in claim 1, r is 0, 1, 2, 3, or 4; s is 0, 1, 2, 3, 4, 5, or 6; t is 0, 1, 2, 3, 4, 5, 6, 7, or 8; v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; The compound of claim 1.

8. The fused ring C ｃ is selected from the structures of formulae (CRA-1a) to (CRA-4f), 【Chemistry 11】 wherein the dotted bond represents the point of attachment of the fused ring to a further group, the index m is 0, 1, 2, 3 or 4, and the symbols R, Rd have the definitions given in claim 1; R f is the same or different in each occurrence and is F, a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein said alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group in each occurrence may be substituted by one or more R d groups, and one or more non-adjacent CH 2 groups are selected from R d C═CR d , C≡C, Si(R d ) 2 , C═O, C═S, C═Se, C═NR d , —C(═O)O—, —C(═O)NR d —, NR d , P(═O)(R d ), —O—, —S—, SO, or SO 2 or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and optionally substituted by one or more R d groups, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and optionally substituted by one or more R d groups, wherein two R f groups together or one R f group together with an R group or together with a further group can also form a ring system, R d having the definition given in claim 1, s is 0, 1, 2, 3, 4, 5, or 6; t is 0, 1, 2, 3, 4, 5, 6, 7, or 8; v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; The compound of claim 1.

9. The fused ring C ｂ is selected from the structures of formulas (BCY-1) to (BCY-10), 【Chemistry 12】 wherein R has the definition given in claim 1, the dotted bond represents the point of attachment of the fused ring to a further group, and further Z 1 is the same or different in each occurrence and is C(R 3 ) 2 , O, S, or Si(R 3 ) 2 ; Z 2 is C(R) 2 , O, S, NR, or C(═O), and two adjacent Z 2 groups are —CR═CR— or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms and optionally substituted by one or more R groups; Z ３ are the same or different in each case, and C(R ３ ) ２ , O, S, or Si(R ３ ) ２ and G is an alkylene group having 1, 2, or 3 carbon atoms and optionally substituted with one or more R groups, -CR=CR-, or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms and optionally substituted with one or more R groups; R 3 is the same or different in each occurrence and is H, D, F, Cl, Br, I, CN, NO 2 , N(Ar′) 2 , N(R d ) 2 , C(═O)Ar′, C(═O)R d , P(═O)(Ar′) 2 , P(Ar′) 2 , B(Ar′) 2 , B(R d ) 2 , C(Ar′) 3 , C(R d ) 3 , Si(Ar′) 3 , Si(R d ) 3 , a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which is optionally substituted by one or more R d groups and which has one or more non-adjacent CH 2 The group is selected from the group consisting of R d C═CR d —, —C≡C—, Si(R d ) 2 , C═O, C═S, C═Se, C═NR d , —C(═O)O—, —C(═O)NR d —, NR d , P(═O)(R d ), —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 60 aromatic ring atoms, each optionally substituted by one or more R d groups, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and optionally substituted by one or more R d groups, or a heteroaryloxy group having 5 to 60 aromatic ring atoms and one or more R d an aralkyl or heteroaralkyl group optionally substituted by a group, or a combination of these systems, wherein two R 3 groups attached to the same carbon atom may together form an aliphatic or aromatic ring system and thus a spiro system, and further wherein R 3 together with an R, R a , R c or R 3 group may form an aliphatic ring system, and Ar′ and R d have the definitions given in claim 1, provided that the two heteroatoms in these groups are not directly bonded to each other and the two C═O groups are not directly bonded to each other; The compound of claim 1.

10. The fused ring C ｂ is selected from the structures of formulas (BRA-1) to (BRA-12), 【Chemistry 13】 wherein R has the definition given in claim 1 and the dotted bond represents the point of attachment of the fused ring to a further group; Y 2 is the same or different in each occurrence and is C(R) 2 , (R) 2 CC(R) 2 , (R)C═C(R), NR, NAr′, O, or S; R f is the same or different in each occurrence and is F, a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein said alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group in each occurrence may be substituted by one or more R d groups, and one or more non-adjacent CH 2 groups are selected from R d C═CR d , C≡C, Si(R d ) 2 , C═O, C═S, C═Se, C═NR d , —C(═O)O—, —C(═O)NR d —, NR d , P(═O)(R d ), —O—, —S—, SO, or SO 2 or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and optionally substituted by one or more R d groups, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and optionally substituted by one or more R d groups, wherein two R f groups together or one R f group together with an R group or together with a further group can also form a ring system, R d having the definition given in claim 1, r is 0, 1, 2, 3, or 4; s is 0, 1, 2, 3, 4, 5, or 6; t is 0, 1, 2, 3, 4, 5, 6, 7, or 8; v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; The compound of claim 1.

11. At least two R,R ａ , R ｂ , R ｃ , R ｄ The two R, R groups ａ , R ｂ , R ｃ , R ｄ The R, R groups form a fused ring together with the further groups to which they are bonded, and the two R, R groups ａ , R ｂ , R ｃ , R ｄ The group forms at least one structure of formula (Cy-1) to (Cy-10), 【Chemistry 14】 In the formula, R １ has the definition given in claim 1, and the dotted bond connects the two R, R ａ , R ｂ , R ｃ , R ｄ represents the point of attachment to the atom of the group to which the group is attached, and further Z ５ , Z ７ are the same or different in each case, and C(R ４ ) ２ ,O,S,NR ４ or C(=O), Z ６ But C(R １ ) ２ ,O,S,NR １ or C(=O), and two adjacent groups Z ２ But, -CR １ =CR １ - or 5 to 14 aromatic ring atoms and one or more R １ represents an ortho-linked arylene group or heteroarylene group optionally substituted by a group; G １ has 1, 2, or 3 carbon atoms and one or more R １ an alkylene group optionally substituted by a group, —CR １ =CR １ - or 5 to 14 aromatic ring atoms and one or more R １ an ortho-linked arylene or heteroarylene group optionally substituted by a group; R ４ are in each case the same or different and are H, D, F, Cl, Br, I, CN, NO ２ , N(Ar″) ２ , N(R ２ ) ２ , C(=O)Ar'', C(=O)R ２ , P(=O)(Ar'') ２ , P(Ar″) ２ , B(Ar″) ２ , B(R ２ ) ２ , C(Ar″) ３ , C(R ２ ) ３ , Si(Ar″) ３ , Si(R ２ ) ３ a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be selected from the group consisting of one or more R ２ may be substituted by one or more non-adjacent CH ２ The group is -R ２ C=CR ２ -, -C≡C-, Si(R ２ ) ２ , C=O, C=S, C=Se, C=NR ２ , -C(=O)O-, -C(=O)NR ２ -, NR ２ , P(=O)(R ２ ), —O—, —S—, SO, or SO ２ and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ or 5 to 60 aromatic ring atoms, each of which may be replaced by one or more R ２ an aromatic or heteroaromatic ring system optionally substituted by a group, having 5 to 60 aromatic ring atoms and one or more R ２ an aryloxy group or a heteroaryloxy group optionally substituted by a group, having 5 to 60 aromatic ring atoms and one or more R ２ an aralkyl group or a heteroaralkyl group optionally substituted by a group, or a combination of these systems, and at the same time, two R ４ The groups may together form an aliphatic or aromatic ring system, thus forming a spiro system, and further, R ４ But, R, R ａ , R ｂ , R ｃ , R ｄ , or R １ The symbol R １ and Ar″ has the definition given in claim 1, provided that the two heteroatoms in these groups are not directly bonded to each other and the two C═O groups are not directly bonded to each other; The compound of claim 1.

12. The at least two R, R ａ , R ｂ , R ｃ , R ｄ The two R, R groups ａ , R ｂ , R ｃ , R ｄ The R, R groups together with the further groups to which they are attached form a fused ring, and the two R, R ａ , R ｂ , R ｃ , R ｄ The group forms at least one structure of formulas (RA-1) to (RA-13), 【Chemistry 15】 In the formula, R １ has the definition given above, and the dotted bond connects the two R, R ａ , R ｂ , R ｃ , R ｄ represents the point of attachment to the atom of the group to which the group is attached, and further symbols have the following definitions: Y ４ are the same or different in each case, and C(R １ ) ２ , (R １ ) ２ C-C (R １ ) ２ , (R １ ) C=C(R １ ), N.R. １ , NAr′, O, or S; R ｇ are in each occurrence the same or different and are selected from F, a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein said alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is in each occurrence selected from one or more R ２ may be substituted by one or more adjacent CH ２ The group is R ２ C=CR ２ , C≡C, Si(R ２ ) ２ , C=O, C=S, C=Se, C=NR ２ , -C(=O)O-, -C(=O)NR ２ -, NR ２ , P(=O)(R ２ ), —O—, —S—, SO, or SO ２ or 5 to 60 aromatic ring atoms, in each case one or more R ２ an aromatic or heteroaromatic ring system, or a ring system having 5 to 60 aromatic ring atoms, optionally substituted by a group, and one or more R ２ an aryloxy group or a heteroaryloxy group optionally substituted by a group, and at the same time, two R ｇ The groups together or one R ｇ The group is R １ R may also be taken together with other groups or with further groups to form a ring system; ２ has the definition given in claim 1, r is 0, 1, 2, 3, or 4; s is 0, 1, 2, 3, 4, 5, or 6; t is 0, 1, 2, 3, 4, 5, 6, 7, or 8; v is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; The compound of claim 1.

13. At least two R,R ａ , R ｂ , R ｃ , R ｄ The two R, R groups ａ , R ｂ , R ｃ , R ｄ R, R are bonded to a further group together to form a fused ring, ａ , R ｂ , R ｃ , R ｄ wherein the group forms a structure of formula (RB), 【Chemistry 16】 In the formula, R １ has the definition given in claim 1, and the dotted bond connects the two R, R ａ , R ｂ , R ｃ , R ｄ represents a bonding site bonded via a group, the index m being 0, 1, 2, 3, or 4; ５ But C(R １ ) ２ , N.R. １ , NAr', BR １ , BAr′, O, or S; The compound of claim 1.

14. The R ｂ and / or R ｄ The group is C(Ar') ３ , C(R １ ) ３ , Si(Ar′) ３ , Si(R １ ) ３ , B(R １ ) ２ or one or more groups selected from １ represents a fluorene group optionally substituted by a group, or R ｂ Or R ｄ 2. The compound of claim 1, wherein said compound is formed together with a group.

15. 15. An oligomer, polymer, or dendrimer comprising one or more compounds according to any one of claims 1 to 14, 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.

16. A combination comprising at least one compound according to any one of claims 1 to 14 and at least one further compound.

17. A formulation comprising at least one oligomer, polymer, or dendrimer according to claim 15 and at least one further compound.

18. 15. A composition comprising at least one compound according to any one of claims 1 to 14 and at least one further compound selected from the group consisting of a fluorescent emitter, a phosphorescent emitter, an emitter exhibiting TADF, 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.

19. A composition comprising at least one oligomer, polymer, or dendrimer according to claim 15, and at least one further compound selected from the group consisting of a fluorescent emitter, a phosphorescent emitter, an emitter exhibiting TADF, 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.

20. 19. The composition according to claim 18, characterized in that at least one further compound is a TADF host material and / or at least one further compound is a phosphorescent emitter (triplet emitter).

21. The composition described in claim 19, characterized in that at least one further compound is a TADF host material and / or at least one further compound is a phosphorescent emitter (triplet emitter).

22. A method for preparing the compound according to any one of claims 1 to 14, characterized by synthesizing a basic skeleton having an aromatic amino group and introducing at least one aromatic or heteroaromatic group.

23. Use of a compound according to any one of claims 1 to 14 in an electronic device.

24. Use of an oligomer, polymer, or dendrimer according to claim 15 in an electronic device.

25. An electronic device comprising at least one compound according to any one of claims 1 to 14.

26. An electronic device comprising at least one oligomer, polymer, or dendrimer according to claim 15.

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