Polycyclic compounds for organic electroluminescent devices

Abstract

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

Description

Detailed Description of the Invention

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

[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 improvements in electroluminescent devices.

[0003] WO2010 / 104047A1 and WO2019 / 132506A1 disclose polycyclic compounds that can be used in organic electroluminescent devices. They do not disclose the compounds of the present invention. Furthermore, in Nature Communications | 8:1948, Wang et al. investigate the antiaromatic properties of the compounds. However, Wang et al. do not disclose the use of these compounds in organic electroluminescent devices.

[0004] In general, there is still a need for improvements in these heterocyclic compounds, for example for use as emitters, in particular as fluorescent emitters, in particular with regard to lifetime and color purity, as well as with regard to device efficiency and operating voltage.

[0005] It is therefore an object of the present invention to provide a compound that is suitable for use in an organic electronic device, in particular an organic electroluminescent device, and that, when used in such a device, results in good device properties, and to provide a corresponding electronic device.

[0006] More particularly, the problem addressed by the present invention is to provide compounds that provide long life, good efficiency and low operating voltage.

[0007] Furthermore, the compounds should have good processability and they should exhibit particularly good solubility.

[0008] A further problem addressed by the present invention can be seen as providing compounds that are particularly suitable for use as emitters in phosphorescent and fluorescent electroluminescent devices. More particularly, the problem addressed by the present invention is to provide emitters that are suitable for red, green or blue electroluminescent devices.

[0009] Furthermore, the compounds, especially when used as emitters in organic electroluminescent devices, should result in devices with excellent color purity.

[0010] A further problem addressed by the present invention can be seen as providing compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, in particular as matrix materials. More particularly, the problem addressed by the present invention is to provide red, yellow and blue phosphorescent electroluminescent devices.

[0011] Furthermore, when this compound is used as a matrix material, a hole transport material or an electron transport material in an organic electroluminescent device, it will result in a device with excellent color purity.

[0012] A further challenge is to provide electronic components with excellent performance at very low cost and with consistent quality.

[0013] Furthermore, the electronic device must be capable of being used or adapted for many purposes. More particularly, the performance of the electronic device must be maintained over a wide temperature range.

[0014] Surprisingly, it has been found that certain compounds, described in detail below, solve this problem and are preferably very suitable for use in electroluminescent devices, resulting in organic electroluminescent devices that exhibit very good properties, particularly in terms of lifetime, color purity, efficiency and operating voltage. The present invention therefore provides these compounds and electronic devices, particularly organic electroluminescent devices, comprising these compounds.

[0015] The present invention provides compounds comprising at least one structure of formula (I), preferably compounds of formula (I). [ka] where the symbols and subscripts used are: Z is identical or different at each occurrence and is N or B; Q may be the same or different at each occurrence and may be C=O, C(=O)-C(=O), (R d )2C-C(R d )2, (R d )2C=C(R d ), or having 5 to 60 aromatic ring atoms and bonded to Y through two adjacent, mutually bonded carbon atoms 1 and Y 2 and in each case one or more R d an aromatic or heteroaromatic ring system optionally substituted by radicals; Y 1 , Y 2 are identical or different at each occurrence and are N(Ar), N(R), B(Ar), B(R), Al(Ar) or Al(R), preferably N(Ar), N(R), B(Ar) or B(R); Y 3 , Y 4are identical or different at each occurrence and are N(Ar), N(R), P(Ar), P(R), P(=O)Ar, P(=O)R, P(=S)Ar, P(=S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, C(R), Si(R), C=NR, C=NAr, C=C(R), O, S, Se, S=O, or SO, preferably N(Ar), N(R), B(Ar), B(R), P(=O)R, P(=O)Ar, C=O, C(R), Si(R), O, S, Se, S=O, or SO, more preferably C=O, N(Ar) or B(Ar); Ar is the same or different at each occurrence and is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, optionally substituted by one or more R radicals; wherein the Ar group, together with the Ar or R radicals or further groups, may form a ring system; X 1 are the same or different for each occurrence, and N, CR a , CAr, or C when a ring system is formed by bonding to an Ar or R radical or further group, preferably CR a or C, provided that X per ring 1 , X 2 Not more than two of the groups are N; X 2 are the same or different for each occurrence, and N, CR b or CAr, preferably CR b where X per ring 1 , X 2 Not more than two of the groups are N; X 3 are the same or different for each occurrence, and N, CR c , CAr, or C when a ring system is formed by bonding to an Ar or R radical or further group, preferably CR c or C; R, R a , R b , R c , R dare the same or different at each occurrence and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2, C(=O)OAr', C(=O)OR 1 , 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, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is in each case composed of one or more R 1 radical, where one or more non-adjacent CH groups are 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-, -Se-, -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 or a ring system having 5 to 60 aromatic ring atoms, optionally substituted by a radical, and one or more R 1 an aryloxy or heteroaryloxy group optionally substituted by a radical; and at the same time, two R, Ra , R b , R c , R d The radicals, together or with further groups, may form a ring system; Ar' may be the same or different in each occurrence and have 5 to 60 aromatic ring atoms and one or more R 1 at the same time, two Ar' radicals bonded to the same carbon, silicon, nitrogen, phosphorus or boron atom are bridged by a single bond or 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 may also be coupled together via a bridge selected from: R 1 are the same or different at each occurrence and are H, D, F, Cl, Br, I, CN, NO2, N(Ar'')2, N(R 2 )2, C(=O)OAr'', C(=O)OR 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 these is an R 2 radical, where one or more non-adjacent CH groups are 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 in which 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 may be 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 radical, and one or more R 2 an aryloxy or heteroaryloxy group, optionally substituted by a radical, or a aryloxy group having 5 to 60 aromatic ring atoms and one or more R 2 aralkyl or heteroaralkyl groups, or combinations of these systems, optionally substituted by radicals; at the same time, two or more, preferably adjacent, R 1 The radicals may together form a ring system; at the same time, one or more R 1 The radical may, together with further moieties of the compound, form a ring system; Ar″ may be the same or different in each occurrence and has 5 to 30 aromatic ring atoms and one or more R 2 at the same time, two Ar" radicals 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, SO2, N(R 2 ), P(R 2 ) and P(=O)R 2 may also be coupled together via a bridge selected from: R 2are identical or different at each occurrence and are selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more, preferably adjacent, substituents R 2 may together form a ring system.

[0016] In the sense of the present invention, an aryl group contains 6 to 60, preferably 6 to 40, carbon atoms; in the sense of the present invention, a heteroaryl group contains 2 to 60, preferably 2 to 40, carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and / or S. An aryl or heteroaryl group is understood here to mean a single aromatic ring, i.e., benzene, or a single heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatics connected to each other by a single bond (e.g., biphenyl) are not referred to as aryl or heteroaryl groups, but are aromatic ring systems.

[0017] In the sense of the present invention, an electron-deficient heteroaryl group is a heteroaryl group having at least one heteroaromatic 6-membered ring with at least one nitrogen atom.An additional aromatic or heteroaromatic 5- or 6-membered ring may be fused to this 6-membered ring.Examples of electron-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, or quinoxaline.

[0018] Within the meaning of the present invention, an aromatic ring system has 6 to 60 carbon atoms in the ring system. Within the meaning of the present invention, a heteroaromatic ring system contains 2 to 60 carbon atoms and at least one heteroatom in the ring system, provided that the total number of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. Within the meaning of the present invention, an aromatic or heteroaromatic ring system does not necessarily contain only aryl or heteroaryl groups, but should also be understood to mean a system in which two or more aryl or heteroaryl groups can 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, triarylamine, diaryl ether, and stilbene are also considered aromatic ring systems within the meaning 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-diarylfluorene or a group in which two or more aryl and / or heteroaryl groups are linked together by a single bond.

[0019] In the sense of the present invention, an aliphatic hydrocarbyl radical or an alkyl group or an alkenyl or alkynyl group having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, in which each hydrogen atom or CH2 group may be replaced by the above-mentioned 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, xyl, 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 or octynyl radical. 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 radical 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, alkyl, alkoxy or thioalkyl groups according to the invention may be linear, branched or cyclic, in which one or more adjacent CH groups may be replaced by the above groups; 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, particularly preferably CN.

[0020] 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 above-mentioned radicals and which may be bonded to the aromatic or heteroaromatic system in any desired position, are in particular benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, triphenylene, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, Dihydropyrene, tetrahydropyrene, 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-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalimidazole, 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, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,It is understood to mean radicals derived from 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 radicals derived from combinations of these systems.

[0021] In the sense of the present invention, the term that two or more radicals may together form a ring is understood to mean, inter alia, that two radicals are linked to one another by a chemical bond, with the formal removal of two hydrogen atoms, as illustrated by the following scheme: [ka]

[0022] Furthermore, however, the above terms are also understood to mean that when one of the two radicals is hydrogen, the second radical is bonded to the bonded position of the hydrogen atom to form a ring, as exemplified by the following scheme: [ka]

[0023] Preferably, in formula (I), X 1 , X 2 and X 3 Of the groups, up to four, preferably up to two, may be N; more preferably, X 1 , X 2 and X 3 All of the bases are CR a , C.R. b , C.R. c or C when the R or Ar groups form a ring system through the bond.

[0024] In a preferred embodiment, the compound of the present invention comprises at least one structure of formula (II); more preferably, the compound of the present invention may be selected from compounds of formula (II). [ka] where Y 1 , Y 2 , Y 3 , Y 4 , Z, Q, R a , R b and R c has the meaning given above, in particular in formula (I), and the index j is 0, 1 or 2, preferably 0 or 1, where the sum of the index j is preferably 0, 1 or 2.

[0025] In a preferred embodiment, in formula (I) and / or (II), the Q groups at each occurrence may be identical or different and may be C=O, C(=O)-C(=O), (R d )2C=C(R d ) or phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or triphenylene, each of which may be selected from Y 1 and Y 2 group via two adjacent, mutually bonded carbon atoms, and one or more R d It may be substituted by a radical.

[0026] In a further preferred embodiment, the compound of the present invention comprises a structure of formula (IIIa) to (IIIk), and more preferably, the compound of the present invention may be selected from the compounds of formula (IIIa) to (IIIk). [ka] [ka] [ka] Here, the symbol Y 1 , Y 2 , Y 3 , Y 4 , X 1 , X 2 , X 3 , R d and Z have the meanings given above, especially in formula (I), and X 4 are the same or different for each occurrence, and N, CR d or C when a ring system is formed by bonding to an Ar or R radical or further group, preferably CR d or C and Y 5 is C(R), NR, NAr′, BR, BAr′, O or S, preferably C(R), NAr′ or O, where R and Ar′ have the meanings given above, in particular in formula (I).

[0027] In this context, structures of formulae (IIIa) to (IIIj) are preferred, structures of formulae (IIIa) and (IIIb) are particularly preferred, and structures of formula (IIIa) are especially preferred.

[0028] Preferably, in formulas (IIIa) to (IIIk), X 1 , X 2 , X 3 , X 4 Up to four, preferably up to two of the groups may be N; more preferably, X 1 , X 2 , X 3 , X 4 All of the bases are CR a , C.R. b , C.R. c , C.R. d or C when the R or Ar groups form a ring system through the bond.

[0029] In a further preferred embodiment, the compound of the present invention may comprise a structure of any one of formulas (IVa) to (IVn), and more preferably, the compound of the present invention is selected from the compounds of formulas (IVa) to (IVn). [ka] [ka] [ka] Here, the symbol Y 1 , Y 2 , Y 3 , Y 4 , Z, R a , R b , R c and R d has the meaning given above, in particular in formula (I), the index j is 0, 1 or 2, preferably 0 or 1, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y 5 is C(R), NR, NAr′, BR, BAr′, O or S, preferably C(R), NAr′ or O, where R and Ar′ have the meanings given above, in particular in formula (I).

[0030] In this context, structures / compounds of formulae (IVa) to (IVm) are preferred, structures / compounds of formulae (IVa) and (IVb) are particularly preferred, and structures / compounds of formula (IVa) are especially preferred.

[0031] The sum of the subscripts j and m in the structures / compounds of formulae (IVa) to (IVn) is preferably 8 or less, particularly preferably 6 or less, and more preferably 4 or less.

[0032] Furthermore, in preferred forms of formulae (I), (II), (IIIa) to (IIIk), (IVa) to (IVn) and / or these formulae shown below, it is particularly preferred that Z is N and at least one, preferably two, Y 1 , Y 2This may be the case when the group is B(Ar), B(R), Al(Ar), or Al(R), preferably B(Ar) or B(R). 1 , Y 2 Forms in which the radicals are B(Ar), B(R), Al(Ar) or Al(R), preferably B(Ar) or B(R), will be advantageously used as emitters.

[0033] Furthermore, in preferred forms of formulae (I), (II), (IIIa) to (IIIk), (IVa) to (IVn) and / or these formulae shown below, it is particularly preferred that Z is N and at least one, preferably two, Y 1 , Y 2 This may be the case when the group is N(Ar) or N(R), preferably N(Ar).

[0034] Z is N and at least one, preferably two, Y 1 , Y 2 The form in which the group is N(Ar) or N(R), preferably N(Ar), may be advantageously used in particular as a hole-conducting material.

[0035] In a further aspect, in the formulae (I), (II), (IIIa) to (IIIk), (IVa) to (IVn) and / or preferred aspects of these formulae described hereinafter, it is particularly preferred that at least one, preferably two Y 1 , Y 2 The group is N(Ar) or N(R) and at least one, preferably two Y 3 , Y 4 This may be the case when the group is B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, more preferably C=O, B(R) or B(Ar). At least one, preferably two Y 1 , Y 2 The group is N(Ar) or N(R) and at least one, preferably two Y 3 , Y 4Forms in which the groups are B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, more preferably C=O, B(R) or B(Ar), will be advantageously used as light emitters.

[0036] In a further aspect, in the formulae (I), (II), (IIIa) to (IIIk), (IVa) to (IVn) and / or preferred aspects of these formulae described hereinafter, it is particularly preferred that at least one, preferably two Y 1 , Y 2 The group is N(Ar) or N(R) and at least one, preferably two, Y 3 , Y 4 This may be the case when the group is N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar).

[0037] At least one, preferably two Y 1 , Y 2 The group is N(Ar) or N(R) and at least one, preferably two Y 3 , Y 4 Forms in which the groups are N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar), will be advantageously used in particular as hole-conducting materials.

[0038] Furthermore, in preferred forms of formulae (I), (II), (IIIa) to (IIIk), (IVa) to (IVn) and / or these formulae shown below, it is particularly preferred that Z is B and at least one, preferably two, Y 1 , Y 2 This may be the case when the group is N(Ar) or N(R), preferably N(Ar). When Z is B, at least one, preferably two Y 1 , Y 2Forms in which the group is N(Ar) or N(R), preferably N(Ar), will be advantageously used as emitters.

[0039] Furthermore, in preferred forms of formulae (I), (II), (IIIa) to (IIIk), (IVa) to (IVn) and / or these formulae shown below, it is particularly preferred that Z is B and at least one, preferably two, Y 1 , Y 2 This may be the case when the group is B(Ar), B(R), Al(Ar), or Al(R), preferably B(Ar) or B(R).

[0040] Z is N and at least one, preferably two, Y 1 , Y 2 Forms in which the groups are B(Ar), B(R), Al(Ar), or Al(R), preferably B(Ar) or B(R), may be particularly advantageous for use as electron transport materials.

[0041] In a further aspect, in the formulae (I), (II), (IIIa) to (IIIk), (IVa) to (IVn) and / or preferred aspects of these formulae described hereinafter, it is particularly preferred that at least one, preferably two Y 1 , Y 2 The group is B(Ar), B(R), Al(Ar) or Al(R), preferably B(Ar) or B(R), more preferably B(Ar), and at least one, preferably two, Y 3 , Y 4 This may be the case where the group is N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar). At least one, preferably two Y 1 , Y 2 The group is B(Ar), B(R), Al(Ar) or Al(R), preferably B(Ar) or B(R), more preferably B(Ar), and at least one, preferably two, Y 3 , Y 4Forms in which the groups are N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar), will be advantageously used as emitters.

[0042] In a further aspect, in the formulae (I), (II), (IIIa) to (IIIk), (IVa) to (IVn) and / or preferred aspects of these formulae described hereinafter, it is particularly preferred that at least one, preferably two Y 1 , Y 2 The group is B(Ar), B(R), Al(Ar) or Al(R), preferably B(Ar) or B(R), more preferably B(Ar), and at least one, preferably two, Y 3 , Y 4 This may be the case when the group is B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, more preferably C=O, B(R) or B(Ar).

[0043] At least one, preferably two Y 1 , Y 2 The group is B(Ar), B(R), Al(Ar) or Al(R), preferably B(Ar) or B(R), more preferably B(Ar), and at least one, preferably two, Y 3 , Y 4 Forms in which the groups are B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, more preferably C=O, B(R) or B(Ar), may be particularly advantageous for use as electron transporting materials.

[0044] More preferably, the compound comprises at least one structure of formula (Va)-(Vk); more preferably, the compound is selected from compounds of formula (Va)-(Vk). [ka] [ka] Here, the symbol Y 3 , Y 4 , X 1 , X 2 , X 3 and Z have the meanings given above, in particular in formula (I), and the symbol X 4 and Y 5 has the meaning given above, especially in formulae (IIIa) to (IIIk), and further symbols are as follows: Z 1 , Z 2 is identical or different at each occurrence and is N, B or Al, preferably N or B; X is the same or different at each occurrence and is N, CR, or X 3 is C when a ring system is formed by bonding to a radical or further group, preferably CR or C, with the proviso that per ring not more than two X groups are N, in which R has the meaning given above, in particular in formula (I); Y 6 , Y 7 are identical or different at each occurrence and are a bond, N(Ar′), N(R), P(Ar′), P(R), P(═O)Ar′, P(═O)R, P(═S)Ar′, P(═S)R, B(Ar′), B(R), Al(Ar′), Al(R), Ga(Ar′), Ga(R), C═O, C(R), Si(R), C═NR, C═NAr′, C═C(R), O, S, Se, S═O, or SO, preferably a bond, N(Ar′), N(R), B(Ar′), B(R), P(═O)R, P(═O)Ar′, C═O, C(R), Si(R), O, S, Se, S═O, or SO, more preferably a bond, wherein R and Ar′ have the meanings given above, in particular in formula (I); p and q are the same or different at each occurrence and are 0 or 1, where 0 means that the corresponding group is absent.

[0045] In this context, structures / compounds of formulae (Va) to (Vj) are preferred, structures / compounds of formulae (Va) and (Vb) are particularly preferred, and structures / compounds of formula (Va) are especially preferred.

[0046] Furthermore, in formulas (Va) to (Vk), X, X 1 , X 2 , X 3 , X 4 Not more than four, preferably not more than two of the groups are N; more preferably, X, X 1 , X 2 , X 3 , X 4 All of the groups are CR, CR a , C.R. b , C.R. c , C.R. d or C when the bond forms a ring system.

[0047] More preferably, the compound comprises at least one structure of formula (VI-1) to (VI-39); more preferably, the compound is selected from the compounds of formula (VI-1) to (VI-39). [ka] [ka] [ka] [ka] [ka] [ka] [ka] where Y 3 , Y 4 , Z, R, R a , Rb , R c and R d has the meaning given above, especially in formula (I), and further symbols have the following meanings: Z 1 , Z 2 is identical or different at each occurrence and is N, B or Al, preferably N or B; l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2; m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2; j is 0, 1 or 2, preferably 0 or 1; k is 0 or 1; and Y 5 is C(R), NR, NAr′, BR, BAr′, O or S, preferably C(R), NAr′ or O, where R and Ar′ have the meanings given above, in particular in formula (I).

[0048] Here, preferred are structures or compounds of formulae (VI-1), (VI-2), (VI-5), (VI-6), (VI-9) and (VI-10), and particularly preferred are structures or compounds of formulae (VI-1), (VI-5) and (VI-9).

[0049] In the structures of formulae (VI-1) to (VI-39), the sum of the subscripts j, k, l and m may be preferably 8 or less, particularly preferably 6 or less, and more preferably 4 or less.

[0050] Furthermore, in the preferred forms of the formulae (IIIa) to (IIIk), (IVa) to (IVn), (Va) to (Vk), (VI-1) to (VI-39) and / or the following formulae, it is particularly preferred that two Y 5 This may be the case when the groups are identical.

[0051] Furthermore, in the preferred forms of the formulae (IIIa) to (IIIk), (IVa) to (IVn), (Va) to (Vk), (VI-1) to (VI-39) and / or the following formulae, it is particularly preferred that two Y 5 The groups may be different.

[0052] Furthermore, in preferred forms of formulae (I), (II), (IIIa) to (IIIk), (IVa) to (IVn), (Va) to (Vk), (VI-1) to (VI-39) and / or these formulae described hereinafter, it is particularly preferred that Z is N and at least one, preferably two, Y 3 , Y 4 This may be the case when the group is B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, more preferably C=O, B(R) or B(Ar). Z is N and at least one, preferably two, Y 3 , Y 4 Forms in which the groups are B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO2 will be advantageously used as emitters.

[0053] Furthermore, in preferred forms of formulae (I), (II), (IIIa) to (IIIk), (IVa) to (IVn), (Va) to (Vk), (VI-1) to (VI-39) and / or these formulae shown below, it is particularly preferred that Z is N and at least one, preferably two, Y 3 , Y 4 This may be the case when the group is N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar).

[0054] Z is N and at least one, preferably two, Y 3 , Y 4Forms in which the groups are N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar), will be advantageously used in particular as hole-conducting materials.

[0055] Furthermore, in preferred forms of formulae (Va) to (Vk), (VI-1) to (VI-39) and / or these formulae shown below, it is particularly preferred that Z is N and at least one, preferably two, Z 1 , Z 2 The group may be B or Al, preferably B. Z is N and at least one, preferably two Z 1 , Z 2 Forms in which the radical is B or Al, preferably B, will be advantageously used as emitters.

[0056] Furthermore, in preferred embodiments of formulae (Va) to (Vk), (VI-1) to (VI-39) and / or the following formulae, it is particularly preferred that Z is N and at least one, preferably two, Z 1 , Z 2 This may be the case when the group is N.

[0057] Z is N and at least one, preferably two, Z 1 , Z 2 Forms in which the group is N may be advantageously used, particularly as hole-conducting materials.

[0058] In a further aspect, in formulas (I), (II), (IIIa) to (IIIk), (IVa) to (IVn), (Va) to (Vk), (VI-1) to (VI-39) and / or preferred aspects of these formulas shown below, it is particularly preferred that Z is B and at least one, preferably two, Y 3 , Y 4 This may be the case when the group is N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar). Z is B and at least one, preferably two, Y 3 , Y4 Forms in which the groups are N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar), will be advantageously used as emitters.

[0059] In a further aspect, in the preferred aspects of formulae (Va) to (Vk), (VI-1) to (VI-39) and / or the following formulae, particularly Z is B and at least one, preferably two, Z 1 , Z 2 It may be the case that the group is N. Z is B and at least one, preferably two Z 1 , Z 2 Forms in which the group is N will be advantageously used, particularly as emitters.

[0060] Furthermore, in preferred embodiments of formulae (I), (II), (IIIa) to (IIIk), (IVa) to (IVn), (Va) to (Vk), (VI-1) to (VI-39) and / or the formulae thereafter, it is particularly preferred that Z is B and at least one, preferably two, Y 3 , Y 4 This may be the case when the group is B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably C=O, B(Ar), B(R), P(=O)Ar, P(=O)R, S=O or SO, more preferably C=O, B(R) or B(Ar). At least one, preferably two Y 3 , Y 4 Forms in which the groups are B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably C=O, B(Ar), B(R), P(=O)Ar, P(=O)R, S=O or SO, more preferably C=O, B(R) or B(Ar) will be advantageously used as electron transporting materials.

[0061] Furthermore, in preferred forms of formulae (Va) to (Vk), (VI-1) to (VI-39) and / or these formulae shown below, it is particularly preferred that Z is B and at least one, preferably two, Z 1 , Z 2 This may be the case when the group is B or Al, preferably B.

[0062] Z is B and at least one, preferably two, Z 1 , Z 2 Forms in which the group is B or Al, preferably B, may be advantageously used particularly as electron transport materials.

[0063] In a further aspect, in the formulae (Va) to (Vk), (VI-1) to (VI-39) and / or preferred aspects of these formulae described hereinafter, in particular at least one, preferably two Z 1 , Z 2 group is N and at least one, preferably two, Y 3 , Y 4 This may be the case when the group is B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, more preferably C=O, B(R) or B(Ar). At least one, preferably two Z 1 , Z 2 group is N and at least one, preferably two, Y 3 , Y 4 Forms in which the groups are B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, more preferably C=O, B(R) or B(Ar), will be advantageously used as light emitters.

[0064] In a further aspect, in the formulae (Va) to (Vk), (VI-1) to (VI-39) and / or preferred aspects of these formulae described hereinafter, in particular at least one, preferably two Z 1 , Z 2 group is N and at least one, preferably two, Y 3 , Y 4 This may be the case when the group is N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar).

[0065] At least one, preferably two Z 1 , Z 2 group is N and at least one, preferably two, Y 3 , Y 4 Forms in which the groups are N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar), will be advantageously used in particular as hole-conducting materials.

[0066] Furthermore, in the preferred forms of formulae (Va) to (Vk), (VI-1) to (VI-39) and / or the formulae described hereinafter, it is particularly preferred that at least one, preferably two Z 1 , Z 2 The group is B or Al, preferably B, and at least one, preferably two, Y 3 , Y 4 This may be the case when the group is N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar).

[0067] At least one, preferably two Z 1 , Z 2 The group is B or Al, preferably B, and at least one, preferably two, Y 3 , Y 4Forms in which the groups are N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar), will be advantageously used in particular as emitters.

[0068] Furthermore, in the preferred forms of formulae (Va) to (Vk), (VI-1) to (VI-39) and / or the formulae described hereinafter, it is particularly preferred that at least one, preferably two Z 1 , Z 2 is B or Al, preferably B, and at least one, preferably two, Y 3 , Y 4 This may be the case when the group is B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, more preferably C=O, B(R) or B(Ar).

[0069] At least one, preferably two Z 1 , Z 2 The group is B or Al, preferably B, and at least one, preferably two, Y 3 , Y 4 Forms in which the groups are B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, more preferably C=O, B(R) or B(Ar), may be advantageously used in particular as electron transporting materials.

[0070] More preferably, the compound comprises at least one of the structures of formulae (VII-1) to (VII-18); more preferably, the compound is selected from the compounds of formulae (VII-1) to (VII-18): [ka] [ka] [ka] where Z, R, R a , R b , R c and R d has the meaning given above, especially in formula (I), and further symbols have the following meanings: Z 1 , Z 2 , Z 3 , Z 4 is identical or different at each occurrence and is N, B or Al, preferably N or B; l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2; m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2; j is 0, 1 or 2, preferably 0 or 1; k is 0 or 1.

[0071] In the structures of formulae (VII-1) to (VII-18), the sum of the subscripts j, k, l and m may be preferably 8 or less, particularly preferably 6 or less, and more preferably 4 or less.

[0072] Furthermore, in the preferred forms of formulae (VII-1) to (VII-18) and / or the following formulae, it is particularly preferred that at least one, preferably two Z 1 and Z 2 group is N and at least one, preferably two, Z 3 and Z 4 This may be the case when the group is B or Al, preferably B. At least one, preferably two Z 1 and Z 2 group is N and at least one, preferably two, Z 3 and Z 4 Forms in which the radical is B or Al, preferably B, will be advantageously used as emitters.

[0073] Furthermore, in the preferred forms of formulae (VII-1) to (VII-18) and / or the following formulae, it is particularly preferred that at least one, preferably two Z 1 and Z 2 group is N and at least one, preferably two, Z 3 and Z 4 In some cases, the group is N. 1 , Z 2 , Z 3 , Z 4 Forms in which most, preferably all, of the groups are N will be advantageously used, particularly as hole-conducting materials.

[0074] In a further aspect, in the formulae (VII-1) to (VII-18) and / or in the preferred aspects of these formulae below, in particular at least one, preferably two Z 1 and Z 2 The group is B or Al, preferably B, and there is at least one, preferably two, Z 3 and Z 4 In some cases, the group is N. At least one, preferably two Z 1 and Z 2 The group is B or Al, preferably B, and there is at least one, preferably two, Z 3 and Z 4 The form in which the group is N will be advantageously used as an emitter.

[0075] In a further aspect, in the formulae (VII-1) to (VII-18) and / or in the preferred aspects of these formulae below, in particular at least one, preferably two Z 1 and Z 2 The group is B or Al, preferably B or Al, preferably B, and at least one, preferably two, Z 3 and Z 4 This may be the case when the group is B or Al, preferably B.

[0076] Z 1 , Z 2 , Z 3, Z 4 Forms in which many, preferably all, of the groups are B or Al, preferably B, may be advantageously used particularly as electron transporting materials.

[0077] Depending on the structure, Z, Z 1 , Z 2 , Z 3 , Z 4 Many, preferably all, of the groups are N, and Y 1 , Y 2 , Y 3 , Y 4 Forms in which a majority, preferably a majority, of the groups are N(Ar), N(R), P(Ar), P(R), O, S or Se will be particularly advantageously used as hole-conducting materials.

[0078] Z is B, and depending on the structure, Z 1 , Z 2 , Z 3 , Z 4 Many, preferably all, of the groups are B or Al, preferably B, and Y 1 , Y 2 , Y 3 , Y 4 In particular, a form in which many, preferably all, of the above are B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, more preferably C=O, B(R) or B(Ar) may be advantageously used as a hole-conducting material.

[0079] In a preferred embodiment of the present invention, at least two R, R a , R b , R c , R d The radical is two R, R a , R b , R c , R d It may also be the case that the radical, together with the further group to which it is attached, forms a fused ring, where two R, R a , R b , Rc , R d The radicals form at least one structure of formula (RA-1) to (RA-12): [ka] where R 1 has the meaning described above, and the dotted line indicates the connection site through which the two R and R a , R b , R c , R d The radicals attached and further symbols have the following meanings: Y 8 are the same or different for each occurrence, and C(R 1 )2, (R 1 )2C-C(R 1 )2, (R 1 )C=C(R 1 ), NR 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; R e are identical or different at each occurrence and are selected from the group consisting of F, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, 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 the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is, in each case, selected from the group consisting of one or more R 2 radical, where one or more adjacent CH groups are 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 1), -O-, -S-, SO or SO2), 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 radical, and one or more R 2 an aryloxy or heteroaryloxy group optionally substituted by a radical; e Radical or one R e The radical is R 1 Together with the radical or further groups, it may form a ring system; where R 1 and R 2 has the meaning given above, especially in formula (I), 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, more preferably 0, 1 or 2.

[0080] In a preferred embodiment of the present invention, at least two R, R a , R b , R c , R d The radical is two R, R a , R b , R c , R d The radical, together with the further group to which it is attached, forms a fused ring, where two R, R a , R b , R c , R d The radical preferably forms at least one of the structures of formulae (RA-1a) to (RA-4f): [ka] Here, the dotted bond indicates the connection site through which the two R and Ra , R b , R c , R d radicals are bonded, the subscript m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the symbol R 1 , R 2 , R e and the subscripts s and t have the meanings given above, in particular in formula (I) and / or formulae (RA-1) to (RA-12).

[0081] Furthermore, at least two R, R form a structure of formula (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) and form a fused ring. a , R b , R c , R d The radicals are adjacent X, X 1 , X 2 , X 3 , X 4 R, R from the group a , R b , R c , R d This may be the case where R denotes a radical or R denotes a radical linking adjacent carbon atoms, where these carbon atoms are preferably linked to each other via a bond.

[0082] In a more preferred embodiment, at least two R, R a , R b , R c , R d The radical is two R, R a , R b , R c , R d The radical, together with the further group to which it is attached, forms a fused ring, where two R, R a , R b , R c , R d The radicals form a structure of formula (RB): [ka] where R 1has the meaning given above, in particular in formula (I), and the dotted bond indicates a bonding site through which two R, R a , R b , R c , R d radicals are bonded, the subscript m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y 9 is C(R 1 )2, NR 1 , NAr, B.R. 1 , BAr, O or S, preferably C(R 1 )2, NAr' or O.

[0083] wherein at least two R, R form a structure of formula (RB) and form a fused ring. a , R b , R c , R d The radicals are adjacent X, X 1 , X 2 , X 3 , X 4 R, R from the group a , R b , R c , R d This may be the case where R denotes a radical or denotes R radicals attached to adjacent carbon atoms, where these carbon atoms are preferably connected to each other via a bond.

[0084] More preferably, the compound comprises at least one of the structures of formulae (VIII-1) to (VIII-21); more preferably, the compound is selected from the compounds of formulae (VIII-1) to (VIII-21), wherein the compound has at least one fused ring: [ka] [ka] [ka] Here, the symbol Y 3 , Y 4, Z, R, R a , R b , R c and R d has the meaning given above, in particular in formula (I), the symbol o indicates the attachment site, and further symbols have the following meanings: Z 1 , Z 2 is identical or different at each occurrence and is N, B or Al, preferably N or B; l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2; m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2; n is 0, 1, 2 or 3, preferably 0, 1 or 2; j is 0, 1 or 2, preferably 0 or 1; k is 0 or 1.

[0085] Preferably, the fused ring has at least two R, ... a , R b , R c , R d Radical and two R, R a , R b , R c , R d The radical is formed by further groups to which it is attached, where at least two R, R a , R b , R c , R d The radicals form structures of formulae (RA-1) to (RA-12), (RA-1a) to (RA-4f) and / or (RB), preferably structures of formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

[0086] Preferably, the compound may have at least two fused rings, where at least one fused ring is formed from a structure of formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f), and a further ring is formed from a structure of formulae (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), where the compound comprises at least one of the structures of formulae (IX-1) to (IX-21), and preferably the compound is selected from the compounds of formulae (IX-1) to (IX-21). [ka] [ka] [ka] Here, the symbol Y 3 , Y 4 , Z, R, R a , R b , R c and R d has the meaning given above, in particular in formula (I), the symbol o indicates the attachment site, and further symbols have the following meanings: Z 1 , Z 2 is identical or different at each occurrence and is N, B or Al, preferably N or B; l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2; m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2; n is 0, 1, 2 or 3, preferably 0, 1 or 2; j is 0, 1 or 2, preferably 0 or 1; and k is 0 or 1.

[0087] In particular, in formulae (VIII-1) to (VIII-21) and / or (IX-1) to (IX-21), the sum of the subscripts k, j, l, m and n is 0, 1, 2 or 3, preferably 0, 1 or 2.

[0088] Here, the formulas (IX-1) to (IX-21) may have at least two fused rings, and the fused rings may be the same, and two R, R a , R b , R c , R d The moiety formed by the radical can be represented by at least one of the structures of formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

[0089] Furthermore, the formulae (IX-1) to (IX-21) may have at least two fused rings, where the fused rings are different and two R, R a , R b , R c , R d The moiety formed by the radical can in each case be represented by at least one of the structures of formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

[0090] Furthermore, the formulae (IX-1) to (IX-21) may have at least two fused rings, where the fused rings are different and two R, R a , R b , R c , R d The moiety formed by the radicals is represented by at least one of the structures of formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f), and one of the two fused rings is represented by one of the structures of formula (RB). a , R b , R c , R d It has a moiety formed by a radical.

[0091] Furthermore, the substituents R, R according to the above formula a , R b , R c , R d and R e , R 1 and R 2 where R, Ra , R b , R c , R d , R e , R 1 and R 2 together with the ring atoms of the ring system to which R, R are attached do not form a fused aromatic or heteroaromatic ring system. a , R b , R c , R d , R e and R 1 Possible substituents R which may be attached to the radical 1 and R 2 This includes the formation of fused aromatic or heteroaromatic ring systems with

[0092] Especially R, R a , R b , R c , R d , R e , R 1 and / or R 2 When two radicals, which may be selected from, together form a ring system, this ring system may be monocyclic or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. In this case, the radicals that together form the ring system may be adjacent, that is, they may be bonded to the same carbon atom or to carbon atoms that are 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 e , R 1 and / or R 2 The ring systems provided in may be connected to each other by a single bond, which may result in ring closure. In this case, the respective corresponding bonding sites are preferably R, R a , R b , R c , R d , R e , R 1 and / or R 2 Available at.

[0093] In a preferred embodiment, the compounds of the present invention can be represented by at least one of the structures of formulas (I), (II), (IIIa)-(IIIk), (IVa)-(IVn), (Va)-(Vk), (VI-1)-(VI-39), (VII-1)-(VII-18), (VIII-1)-(VIII-21), and / or (IX-1)-(IX-21). Preferably, the compounds of the present invention comprising the structure of formula (I), (II), (IIIa) to (IIIk), (IVa) to (IVn), (Va) to (Vk), (VI-1) to (VI-39), (VII-1) to (VII-18), (VIII-1) to (VIII-21) and / or (IX-1) to (IX-21) have a molecular weight of 5000 g / mol or less, preferably 4000 g / mol or less, particularly preferably 3000 g / mol or less, especially preferably 2000 g / mol or less, and most preferably 1200 g / mol or less.

[0094] A further feature of the preferred compounds of the present invention is that they are sublimable. These compounds generally have a molar mass of less than about 1200 g / mol.

[0095] Preferred aromatic or heteroaromatic ring systems R, R a , R b , R c , R dAr' and / 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 naphtha benzofuran, benzothiophene, carbazole optionally bonded through the 1, 2, 3, 4 or 9 position, dibenzofuran optionally bonded through the 1, 2, 3 or 4 position, dibenzothiophene optionally bonded through the 1, 2, 3 or 4 position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene (each of which may be selected from the group consisting of one or more R 1 or optionally substituted by an R radical).

[0096] Preferably, at least one substituent R, R a , R b , R c , R d are identical or different at each occurrence and are selected from the group consisting of H, D, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, or an aromatic or heteroaromatic ring system selected from the groups of the following formulae Ar-1 to Ar-75, in which the substituents R, R a , R b , R c , R d preferably forms a ring according to the structure of formula (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), or is a , R b , R c , R dis the same or different at each occurrence and is selected from the group consisting of H, D, or an aromatic heteroaromatic ring system selected from the groups of formulae Ar-1 to Ar-75 below, and / or the Ar′ group is the same or different at each occurrence and is selected from the groups of formulae Ar-1 to Ar-75 below. [ka] [ka] [ka] [ka] where R 1 is as described above, the dotted lines indicate the connection sites, and further: Ar 1 are the same or different at each occurrence and have 6 to 18 aromatic ring atoms, and in each case, one or more R 1 a divalent aromatic or heteroaromatic ring system optionally substituted by radicals; A may be the same or different at each occurrence, and C(R 1 )2, NR 1 , O or S; p is 0 or 1, where p=0 is Ar 1 means that the group is absent and the corresponding aromatic or heteroaromatic group is directly attached to the corresponding radical; q is 0 or 1, where q=0 means that there is no A group attached at this position, and R 1 It means that the radical is instead bonded to the corresponding carbon atom.

[0097] The above groups for Ar may have two or more A groups, and these possible options include all combinations of the definitions of A. A preferred embodiment in this case is when one A group is NR 1 and the other A group is C(R 1 )2 or both A groups are NR 1or both A groups are O.

[0098] A is NR 1 When the substituent R attached to the nitrogen atom is 1 preferably has 5 to 24 aromatic ring atoms and one or more R 2 In a particularly preferred embodiment, the R 1 The substituents, which may be the same or different at each occurrence, are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, in particular 6 to 18 aromatic ring atoms, which have no fused aryl groups and which have no fused heteroaryl groups, in which two or more aromatic or heteroaromatic 6-membered ring groups are bonded to each other, and in each case, one or more R 2 Preferably, the alkyl group is a phenyl, biphenyl, terphenyl, or quaterphenyl having the bonding patterns shown in Ar-1 to Ar-11 above, and these structures are represented by R 1 In addition, R of 1 or more 2 The triazines, pyrimidines and quinazolines shown above in Ar-47 to Ar-50, Ar-57 and Ar-58 are more preferred, and these structures are represented by R 1 In addition, R of 1 or more 2 It may be substituted by a radical.

[0099] Preferred substituents R, R a , R b , R c , R d and R e The following describes this.

[0100] In a preferred embodiment of the present invention, R, R a , R b , R c , R d are the same or different for each occurrence and are 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 or 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, in each case one or more R 1 The aromatic or heteroaromatic group is optionally substituted by a radical.

[0101] In a further preferred embodiment of the present invention, R, R a , R b , R c , R d are the same or different at each occurrence 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 case, one or more R 1 or 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, in each case one or more R 1 is selected from the group consisting of aromatic or heteroaromatic ring systems optionally substituted by radicals.

[0102] Furthermore, 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, have 6 to 30 aromatic ring atoms, and one or more R 1 In a further preferred embodiment of the invention, the substituents R, R are selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals, and N(Ar') groups. a , R b , R c , R d form a ring having the structure of formula (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), or R, R a , Rb , R c , R d are the same or different in each occurrence and are H, D, have 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 an aromatic, heteroaromatic ring system, or an N(Ar') group, optionally substituted by a radical. a , R b , R c , R d are the same or different at 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, more preferably 6 to 13 aromatic ring atoms (each of which may be selected from the group consisting of one or more R 1 and optionally substituted by a radical.

[0103] In a preferred embodiment of the present invention, R e are identical or different at each occurrence 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 case, one or more R 1 and 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case one or more R 2 is selected from the group consisting of aromatic or heteroaromatic ring systems optionally substituted by radicals.

[0104] In a further preferred embodiment of the invention, R e are identical or different at each occurrence and are 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 case, one or more R 1 and substituted by at least one R 2 More preferably, R is selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals. eare identical or different at 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 case, one or more R 2 or 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 2 The ring system is selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals.

[0105] In a preferred embodiment of the present invention, R e are the same or different in each occurrence and are either 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 case, one or more R 2 or 6 to 24 aromatic ring atoms, in each case one or more R 2 and at the same time, two R are selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by a radical; e The radicals may together form a ring system. More preferably, R e are identical or different at each occurrence and are straight-chain 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, in each case, one or more R 2 or 6 to 12 aromatic ring atoms, in particular 6 aromatic ring atoms, in each case one or more preferably non-aromatic, R 2 and at the same time, two R e The radicals may together form a ring system. Most preferably, R eare the same or different at each occurrence and are selected from the group consisting of straight chain alkyl groups having 1, 2, 3 or 4 carbon atoms or branched alkyl groups having 3 to 6 carbon atoms. Most preferably, R e is a methyl group or a phenyl group, where two phenyl groups may together form a ring system, and is preferably a methyl group rather than a phenyl group.

[0106] Preferred aromatic or heteroaromatic ring system substituents R, R a , R b , R c , R d , R e or Ar 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-bonded naphthalene R, R or R is independently substituted or unsubstituted, and ... 1 or R 2The structures Ar-1 to Ar-75 shown above are particularly preferred, and preferably the structures of formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), and (Ar-75), and particularly preferably the structures of formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16). Regarding the structures Ar-1 to Ar-75, these are selected from the group consisting of the substituent R 1 It should be mentioned that in the case of the ring system Ar, these substituents R 1 should be replaced by R, e In the case of these substituents R 1 is R 2 should be replaced by

[0107] Further suitable R and R a , R b , R c , R d The group has the formula -Ar 4 -N(Ar 2 )(Ar 3 ) group, where Ar 2 , Ar 3 and Ar 4 are identical or different at each occurrence and have 5 to 24 aromatic ring atoms, and in each case, one or more R 1 Ar is an aromatic or heteroaromatic ring system optionally substituted by a radical. 2 , Ar 3 and Ar 4 The total number of aromatic ring atoms in the aryl group is 60 or less, preferably 40 or less.

[0108] In this case, 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, the nitrogen atom is ortho to the bond, and Ar 4 and Ar 2 are bonded to each other, and Ar 2 and Ar 3 In a further aspect of the invention, Ar 2 , Ar 3 and Ar 4 None of the groups are bonded to each other.

[0109] 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 radical. 4 is ortho-, meta-, or para-phenylene or ortho-, meta-, or para-biphenyl (each of which may be one or more R 1 The alkyl group is preferably selected from the group consisting of alkyl, alkyl substituted with alkyl groups, and alkyl substituted with alkyl radicals, but preferably unsubstituted. Most preferably, the alkyl group is selected from the group consisting of alkyl, alkyl substituted with alkyl groups, and alkyl substituted with alkyl radicals, and alkyl substituted with alkyl groups. 4 is an unsubstituted phenylene group.

[0110] Preferably, Ar 2 and Ar 3 are the same or different at each occurrence and have 6 to 24 aromatic ring atoms, and in each case, one or more R 1 Aromatic or heteroaromatic ring systems, optionally substituted by radicals. Particularly preferred Ar 2 and Ar 3The groups may be the same or different at each occurrence and may be 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 and most preferably selected from the group consisting of Ar 2 and Ar 3 are identical or different on each occurrence 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.

[0111] In a further preferred embodiment of the invention, R 1 are the same or different at each occurrence 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 case, one or more R 2 or 6 to 24 aromatic ring atoms, in each case one or more R 2In a particularly preferred embodiment of the invention, R is selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals. 1 are identical or different at each occurrence 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 an alkyl group is one or more R 5 radicals, but is preferably unsubstituted), or 6 to 13 aromatic ring atoms, in each case one or more R 2 The radical is selected from the group consisting of an aromatic or heteroaromatic ring system which may be substituted, but is preferably unsubstituted.

[0112] In a further preferred embodiment of the invention, R 2 is the same or different at 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 with an alkyl group having 1 to 4 carbon atoms, but is preferably unsubstituted).

[0113] At the same time, in compounds of the invention processed by vacuum deposition, the alkyl groups preferably have 5 or fewer carbon atoms, more preferably 4 or fewer carbon atoms, and most preferably 1 or fewer carbon atoms. For compounds processed from solution, preferred compounds are those substituted with alkyl groups, especially branched alkyl groups, having up to 10 carbon atoms, or with oligoarylene groups, such as ortho-, meta-, or para-terphenyl or branched terphenyl or quaterphenyl groups.

[0114] Furthermore, it may be a compound comprising exactly two or exactly three structures of formula (I), (II), (IIIa) to (IIIk), (IVa) to (IVn), (Va) to (Vk), (VI-1) to (VI-39), (VII-1) to (VII-18), (VIII-1) to (VIII-21) and / or (IX-1) to (IX-21), wherein preferably Y1 , Y 2 , Y 3 , Y 4 One of the aromatic heteroaromatic ring systems to which at least one of the groups is attached is shared by the two structures.

[0115] In a preferred embodiment, the compound is selected from compounds of formula (D-1) and (D-2): [ka] Here, Q a The group is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case may be substituted by one or more R radicals; L 1 The group denotes a linking 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 radicals, and the further symbols and indices used have the meanings given above, especially in formula (I).

[0116] In a further preferred embodiment of the present invention, L 1 is a bond or an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms, which may be one or more R 1 It may be substituted by a radical, but is preferably unsubstituted, where R 1 may have the meanings given above, especially in formula (I). More preferably, L 1 is an aromatic ring system having 6 to 10 aromatic ring atoms, or an aromatic ring system having 6 to 13 heteroaromatic ring atoms (each of which may be one or more R 2 It may be substituted by a radical, but is preferably unsubstituted, where R 2 may have the meaning given above, especially in formula (I).

[0117] More preferably, the symbol L shown in the formula (D2) 1is identical or different at each occurrence and is a bond or an aryl or heteroaryl radical having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, in which the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is bonded directly, i.e. via an atom of the aromatic or heteroaromatic group, to the respective atom of the further group.

[0118] Furthermore, L shown in formula (D2) 1 The group may be in the case of an aromatic ring system having up to two fused aromatic and / or heteroaromatic six-membered rings, preferably without fused aromatic or heteroaromatic ring systems. Thus, naphthyl structures are preferred over anthracene structures. Furthermore, fluorenyl, spirobifluorenyl, dibenzofuranyl, and / or dibenzothienyl structures are preferred over naphthyl structures.

[0119] Particularly preferred are non-fused structures, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0120] Suitable aromatic or heteroaromatic ring systems L 1 Examples of are selected from the group consisting of ortho-, meta- or para-phenylene, ortho-, meta- or para-biphenylene, terphenylene, especially branched terphenylene, quaternary phenylene, especially branched quaternary phenylene, fluorenylene, spirobifluorenylene, dibenzofuranylene, dibenzothienylene, and carbazolylene, each of which may be selected from the group consisting of one or more R 1 The radicals may be substituted, but are preferably unsubstituted.

[0121] The above preferred embodiments may optionally be combined with one another, subject to the limitations of claim 1. In a particularly preferred embodiment of the invention, the above preferred embodiments occur simultaneously.

[0122] Examples of preferred compounds according to the above aspects are those shown in the table below.

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

[0123] Preferred forms of the compounds of the present invention are specifically illustrated in the Examples, and these compounds can be used alone or in combination with further compounds for all purposes of the present invention.

[0124] The preferred embodiments described above can be combined with one another if desired, provided that the conditions set out in claim 1 are met. In a particularly preferred embodiment of the invention, the preferred embodiments described above are applied simultaneously.

[0125] The compounds of the invention can in principle be prepared in a variety of ways, but the methods described below have been found to be particularly suitable.

[0126] Therefore, the present invention provides a method for synthesizing a base skeleton having a Z group or a precursor of a Z group, and then synthesizing a base skeleton having a Z group or a precursor of a Z group by adding Y 1 , Y 2 , Y 3 , Y 4 is introduced by a nucleophilic aromatic substitution reaction or a coupling reaction.

[0127] Suitable compounds comprising a basic skeleton bearing a Z group are often commercially available, the starting compounds detailed in the examples being obtainable by known methods, as referenced therein.

[0128] These compounds can be reacted with further compounds in known coupling reactions, the conditions required for this purpose are well known to those skilled in the art, and the detailed explanations in the examples will assist those skilled in the art in carrying out these reactions.

[0129] Particularly suitable and preferred coupling reactions resulting in CC and / or CN bond formation are those according to Buchwald, Suzuki, Yamamoto, Stille, Heck, Negishi, Sonogashira and Hiyama. These reactions are well known and the examples provide further guidance to those skilled in the art.

[0130] The basics of the preparation methods detailed above are in principle known from the literature for similar compounds and can be readily adapted by those skilled in the art to prepare the compounds of the present invention. Further information can be found in the Examples.

[0131] These methods, optionally followed by purification, such as recrystallization or sublimation, provide the compounds of the present invention in high purity, preferably greater than 99% ( 1 H-NMR and / or HPLC).

[0132] The compounds of the present invention can also be mixed with polymers. Likewise, these compounds can be covalently incorporated into polymers. This is particularly possible for compounds substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic ester, or with reactive polymerizable groups such as olefins or oxetanes. They can be used as monomers to prepare corresponding oligomers, dendrimers or polymers. Oligomerization or polymerization is preferably carried out via halogen or boronic acid functional groups, or via polymerizable groups. Such groups can further crosslink the polymer. The compounds and polymers of the present invention can be used in the form of crosslinked or non-crosslinked layers.

[0133] The present invention further provides polymers, oligomers, or dendrimers comprising one or more of the structures of formula (I) and preferred forms of this formula or compounds of the present invention detailed above, wherein there are one or more bonds to the compounds of the present invention or the structures of formula (I) and preferred forms of this formula in the polymer, oligomer, or dendrimer. The linkages of the structures of (I) and preferred forms of this formula or compounds thus form side chains of the polymer or oligomer or are linked within the main chain. The polymers, oligomers, or dendrimers may be conjugated, partially conjugated, or non-conjugated. The oligomers or polymers may be linear, branched, or dendritic. The same preferred forms apply to the repeating units of the compounds of the present invention in oligomers, dendrimers, and polymers as described above.

[0134] To prepare oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with further monomers. The units of formula (I) or the preferred forms described above and below are preferably present in an amount 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 include fluorene (e.g., according to EP842208 or WO2000 / 022026), spirobifluorene (e.g., according to EP707020, EP894107 or WO2006 / 061181), paraphenylene (e.g., according to WO92 / 18552), carbazole (e.g., according to WO2004 / 070772 or WO2004 / 113468), thiophene ( For example, according to EP 1028136), dihydrophenanthrene (for example, WO 2005 / 014689), cis- and trans-indenofluorene (for example, according to WO 2004 / 041901 or WO 2004 / 113412), ketone (for example, according to WO 2005 / 040302), phenanthrene (for example, according to WO 2005 / 104264 or WO 2007 / 017066), or a plurality of these units. The polymers, oligomers and dendrimers may also comprise further units, for example hole-transporting units, in particular those based on triarylamines, and / or electron-transporting units.

[0135] Furthermore, the compounds of the present invention are particularly interesting because they are characterized by a high glass transition temperature. In this regard, preferred are compounds of the present invention comprising the structure of formula (I) or the preferred forms described above and below, which have a glass transition temperature (measured according to DIN 51005 (2005-08 edition)) 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.

[0136] To process the compounds of the present invention in a liquid phase, for example by spin coating or printing, a formulation of the compounds of the present invention is required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it is 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 a mixture of these solvents.

[0137] Therefore, the present invention also relates to a formulation or composition comprising at least one compound of the present invention and at least one additional compound.The additional compound is, for example, a solvent, in particular one of the solvents mentioned above, or a mixture of these solvents.If the additional compound comprises a solvent, this mixture is referred to as a formulation.Alternatively, the additional compound may be at least one additional organic or inorganic compound, such as an emitter and / or a matrix material, which is also used in electronic devices, and where these compounds are different from the compound of the present invention.Suitable emitters and matrix materials are described below in the context of organic electroluminescent devices.This additional compound may also be a polymer.

[0138] Therefore, the present invention 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, and is introduced between the anode and the cathode.Preferably, the organic functional material is selected from the group consisting of fluorescent emitters, phosphorescent emitters, TADF (thermally activated delayed fluorescence) emitters, host materials, electron transport materials, electron injection materials, hole conduction materials, hole injection materials, electron blocking materials, hole blocking materials, wide gap materials and n-dopants.

[0139] The present invention further provides the use of the compounds of the present invention in electronic devices, in particular organic electroluminescent devices, preferably as emitters, more preferably as green, red or blue emitters. In this case, the compounds of the present invention preferably exhibit fluorescent properties, thus providing selective fluorescent emitters. Furthermore, the compounds of the present invention may be used as host materials, electron transport materials and / or hole transport materials. 1 , Z 2 , Z 3 , Z 4 Compounds of the present invention in which most, preferably all, of the groups are N can be advantageously used as hole-conducting materials. 1 , Z 2, Z 3 , Z 4 It is also possible to advantageously use the compounds of the invention as electron transport materials, in which many, preferably all, of the groups are B. Furthermore, the compounds of the invention may be part of a PCC (pixel color converter) for light conversion, for example to convert UV / deep blue to blue, green, yellow or red, or blue to green, yellow or red.

[0140] The present invention further provides an electronic device comprising at least one compound of the present invention. In the sense of the present invention, an electronic device 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 of inorganic materials.

[0141] 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 plasma light-emitting devices (D.M. 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 photodetectors, organic photoreceptors, organic field-quenched devices (O-FQDs), organic electronic 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), and in particular phosphorescent OLEDs.

[0142] An organic electroluminescent device comprises a cathode, an anode, and at least one emitting layer. In addition to these layers, it may also comprise additional layers, such as, in each case, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers. For example, an interlayer with exciton blocking functionality may also be introduced between two emitting layers. Similarly, an interlayer with exciton blocking functionality may also be introduced between two emitting layers. However, it should be noted that each of these layers does not necessarily have to be present. In this case, the organic electroluminescent device may comprise an emitting layer or multiple emitting layers. When multiple emitting layers are present, they preferably have multiple emission maxima in the range of 380 nm to 750 nm, resulting in white light emission as a whole, i.e., various emitting compounds capable of emitting fluorescence or phosphorescence are used in the emitting layers. Particularly preferred is a system with three light-emitting layers, the three layers exhibiting blue, green, and orange or red emission. The organic electroluminescent device according to the invention may be a tandem OLED, in particular for white emission.

[0143] The compounds of the present invention may be used in different layers depending on the exact structure. Preferably, the compounds of formula (I) or the preferred forms described above are used in an organic electroluminescent device as emitters, preferably as red, green or blue emitters, in the light-emitting layer.

[0144] When the compounds of the present invention are used as emitters in a light-emitting layer, known suitable matrix materials are preferably used.

[0145] Preferred mixtures of the compounds of the present invention and matrix material comprise 99% to 1% by volume, preferably 98% to 10% by volume, more preferably 97% to 60% by volume, and in particular 95% to 80% by volume of matrix material, based on the total 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, and in particular 5% to 20% by volume of phosphor, based on the total mixture of phosphor and matrix material.

[0146] Suitable matrix materials which may be used in combination with the compounds of the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. triarylamines according to WO2004 / 013080, WO2004 / 093207, WO2006 / 005627 or WO2010 / 006680, carbazole derivatives such as CBP(N,N-biscarbazolylbiphenyl) or carbazole derivatives as disclosed in WO2005 / 039246, US2005 / 0069729, JP2004 / 288381, EP1205527, WO2008 / 086851 or WO2013 / 041176, indolocarbazole derivatives, for example according to WO2007 / 063754 or W2008 / 056746, indenocarbazole derivatives, for example according to WO2010 / 136109, W2011 / 0004 55, WO2013 / 041176 or WO2013 / 056776, azacarbazole derivatives, e.g., according to EP1617710, EP1617711, EP1731584, JP2005 / 347160, bipolar matrix materials, e.g., according to WO2007 / 137725, silanes, e.g., according to WO2005 / 111172, azaboroles or boronic acid esters, e.g., according to WO2006 / 117052, triazine derivatives, e.g., according to WO2007 / 063754, WO2008 / 056746, WO2010 / 015306, WO2011 / 057706, WO2011 / 060859 or WO2011 / 060877, zinc complexes, for example according to EP 652273 or WO2009 / 062578, diazasilol or tetraazasilol derivatives, for example according to WO2010 / 054729, diazaphosphole derivatives, for example according to WO2010 / 054730, bridged carbazole derivatives, for example Triphenylene derivatives, for example according to WO2011 / 042107, WO2011 / 060867, WO2011 / 088877 and WO2012 / 143080, dibenzofuran derivatives, for example according to WO2012 / 048781, dibenzofuran derivatives, for example according to WO2015 / 169412, WO2016 / 015810, WO2016 / 023608, WO2017 / 148564 or WO2017 / 148565, and bizcarbazoles, for example according to JP3139321B2.

[0147] Furthermore, the co-host used may be a compound that does not participate to a significant extent, if at all, in charge transport, as disclosed in, for example, WO2010 / 108579. Particularly suitable for combination with the compound of the present invention as a co-matrix material are compounds that have a large band gap and do not participate to a significant extent, if at all, in charge transport in the emissive layer. Such materials are preferably pure hydrocarbons. Examples of such materials can be found, for example, in WO2009 / 124627 or WO2010 / 006680.

[0148] In a preferred embodiment, the compound of the present invention used as an emitter is preferably used in combination with one or more phosphorescent materials (triplet emitters) and / or TADF (thermally activated delayed fluorescence) host materials. Preferably, a hyperfluorescent and / or hyperphosphorescent system is formed here. Such a hyperfluorescent and / or hyperphosphorescent system forms a preferred embodiment of the composition of the present invention.

[0149] WO2015 / 091716A1 and WO2016 / 193243A1 disclose OLEDs that contain both phosphorescent compounds and fluorescent emitters in the light-emitting layer, and energy is transferred from the phosphorescent compound to the fluorescent emitter (hyperphosphorescence).In this sense, the phosphorescent compound therefore acts as a host material.As those skilled in the art know, in order to allow the energy from the host material to be transferred to the emitter with maximum efficiency, the host material has higher singlet and triplet energies than the emitter.The systems disclosed in the prior art have just such an energy relationship.

[0150] In the sense of the present invention, phosphorescence is understood to mean luminescence from excited states, in particular excited triplet states, having a higher spin multiplicity, i.e. a spin state > 1. In the sense of the present application, all luminescent complexes containing transition metals or lanthanides, in particular all iridium, platinum and copper complexes, are to be considered as phosphorescent compounds.

[0151] Suitable phosphorescent compounds (= triplet emitters) are in particular compounds which emit light when appropriately excited, preferably in the visible range, and which further comprise at least one atom, in particular a metal with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. Preferred phosphorescent 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.

[0152] Examples of the above-mentioned luminescent materials are disclosed in applications WO00 / 70655, WO2001 / 41512, WO2002 / 02714, WO2002 / 15645, EP1191613, EP1191612, EP1191614, WO05 / 033244, WO05 / 019373, US2005 / 0258742, WO2009 / 146770, WO2010 / 015307, WO2010 / 031485, WO2010 / 054731, WO2010 / 054728, WO2010 / 086089, WO2010 / 099852, WO2010 / 102709, WO20 11 / 032626, WO2011 / 066898, WO2011 / 157339, WO2012 / 007086, WO2014 / 008982, WO2014 / 023377, WO2 014 / 094961, WO2014 / 094960, WO2015 / 036074, WO2015 / 104045, WO2015 / 117718, WO2016 / 015815, W O2016 / 124304, WO2017 / 032439, WO2018 / 011186, WO2018 / 001990, WO2018 / 019687, WO2018 / 019688, These can be found in WO2018 / 041769, WO2018 / 054798, WO2018 / 069196, WO2018 / 069197, WO2018 / 069273, WO2018 / 178001, WO2018 / 177981, WO2019 / 020538, WO2019 / 115423, WO2019 / 158453 and WO2019 / 179909. In general, all phosphorescent complexes that are used in the prior art in the field of phosphorescent electroluminescent devices and that are known to those skilled in the art in the field of organic electroluminescent devices are suitable, and those skilled in the art can use further phosphorescent complexes without any inventive effort.

[0153] The compounds of the present invention may preferably be used in combination with the TADF host materials and / or TADF emitters described above.

[0154] The process for thermally activated delayed fluorescence (TADF) is disclosed, for example, in BHUoyama et al., Nature 2012, Vol. 492, 234. To enable this process, for example, -1 A relatively low singlet-triplet separation ΔE(S1-T1) of less than 0.05 is required for the emitter. To broaden the T1 → S1 transition, which is in principle spin-forbidden, the matrix can be provided with additional compounds with spin-orbit coupling, as well as the emitter, whereby the intersystem separation is achieved by spatial proximity or possible interactions between molecules, or the spin-orbit coupling occurs via metal atoms present in the emitter.

[0155] In a further embodiment of the present invention, the organic electroluminescent device of the present invention does not comprise a hole injection layer and / or a hole transport layer and / or a hole blocking layer and / or an electron transport layer, which means that the light-emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. Furthermore, a metal complex identical to or similar to the metal complex in the light-emitting layer can also be used as a hole transport or hole injection material directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0156] Preferably, it is also an organic electroluminescent device comprising a compound of formula (I) or the preferred forms described above as a hole-conducting material in the hole-conducting layer, where Z is N and at least one, preferably two, Y 1 , Y 2 In particular, compounds in which Z is N and at least one, preferably two, Y 3 , Y 4The group is N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar). Further preferred forms of the compound of the present invention suitable as a hole-conducting material are as described above, and reference is made to these.

[0157] Preferably, the organic electroluminescent device also comprises a compound of formula (I) or the preferred form described above as an electron transport material in the electron conducting layer, where Z is preferably B and at least one, preferably two, Y 1 , Y 2 The groups are B(Ar), B(R), Al(Ar), or Al(R), preferably B(Ar) or B(R). Furthermore, it is preferred that Z is B and at least one, preferably two, Y 3 , Y 4 The group is B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(=O)Ar, P(=O)R, C=O, S=O or SO, preferably C=O, B(Ar), B(R), P(=O)Ar, P(=O)R, S=O or SO, more preferably C=O, B(R) or B(Ar). Further preferred forms of the compound of the present invention suitable as an electron transport material are as described above, and reference is made to these.

[0158] In the additional layer of the organic electroluminescent device of the present invention, any material that is commonly used according to the prior art can be used.Therefore, those skilled in the art can use any material known for organic electroluminescent device in combination with the compound of the present invention according to formula (I) or above-mentioned preferred form without inventive ingenuity.

[0159] More preferably, it is an organic electroluminescent device in which one or more layers are coated by a sublimation process. In this case, the material is -5 less than mbar, preferably 10 -6It is applied by vapor deposition in a vacuum sublimation system at an initial pressure of less than 10 mbar. The initial pressure may be lower, for example, -7 It may be less than mbar.

[0160] Also preferred are organic electroluminescent devices characterized in that one or more layers are coated using the OVPD (organic vapor phase deposition) method or by means of carrier gas sublimation. In this case, the material is 10 -5 It is applied at pressures of mbar to 1 bar. A special method of this method is the OVJP (organic vapor jet printing) method, in which the material is applied directly through a nozzle and thus structured.

[0161] 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, such as screen printing, flexographic printing, offset printing or nozzle printing, particularly preferably by LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble compounds are required, which can be obtained, for example, by suitable substitution.

[0162] The formulations applying the compounds of formula (I) or the preferred forms thereof as described above are novel. Thus, the present invention further provides formulations comprising at least one solvent and a compound of formula (I) or the preferred forms thereof as described above.

[0163] Furthermore, hybrid methods are also possible, for example, where one or more layers are applied from solution and one or more further layers are applied by vapor deposition.

[0164] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices comprising the compounds of the present invention without the need for inventive skill.

[0165] The compound of the present invention and the organic electroluminescent device of the present invention have the special feature that the lifetime is improved compared to the prior art.At the same time, the further electronic properties of the electroluminescent device, such as efficiency or operating voltage, remain at least as good.In a further variant, the compound of the present invention and the organic electroluminescent device of the present invention are characterized by improved efficiency and / or operating voltage and longer lifetime compared to the prior art.

[0166] The electronic devices, in particular organic electroluminescent devices, of the present invention are notable for one or more of the following surprising advantages over the prior art: 1. Electronic devices, in particular organic electroluminescent devices, comprising compounds of formula (I) or the preferred forms as emitters described above and below have an emission in the blue, green and yellow regions of the color spectrum. 2. Electronic devices, especially organic electroluminescent devices, comprising compounds of formula (I) or the preferred forms described above and below, especially as emitters, electron conducting materials and / or electron transporting materials, have very good lifetimes. In this context, these compounds in particular provide low roll-off, i.e., a small drop in the power efficiency of the device at high luminance. 3. The electronic device, particularly the organic electroluminescent device, comprising the compound of formula (I) or the preferred forms described above and below has excellent efficiency as a light emitter, a hole conducting material and / or an electron transporting material. In this context, the compound of formula (I) or the preferred forms described above and below, when used in the electronic device, provides a low operating voltage. 4. The compounds of the present invention of formula (I) or the preferred forms described above and below exhibit very high stability and longevity. 5. The compounds of formula (I) or the preferred forms described above and below can be used to avoid the formation of light loss channels in electronic devices, particularly organic electroluminescent devices, resulting in devices characterized by high PL efficiency and high EL efficiency of the emitter and excellent energy transfer to the dopant of the material. 6. Compounds of formula (I) or the preferred forms described above and below have excellent glass film formation. 7. Compounds of formula (I) or the preferred forms described above and below form very good films from solution and exhibit excellent solubility.

[0167] The above advantages are not accompanied by excessively high degradation of further electronic properties.

[0168] It should be noted that variations of the embodiments described in the present invention are included within the scope of the present invention. Each feature disclosed in the present invention can be replaced with an alternative feature that fulfills the same purpose or an equivalent or similar purpose, unless this is explicitly excluded. Therefore, each feature disclosed in the present invention should be considered as an example of a general series, or an equivalent or similar feature, unless otherwise specified.

[0169] All features of the present invention can be combined with one another in any way, unless the particular features and / or steps are mutually exclusive. This is particularly true of the preferred features of the present invention. Similarly, features of non-essential combinations can be used separately (and not in combination).

[0170] It should be noted that many features, particularly those of the preferred forms of the invention, should be considered inventive in their own right and not merely as part of the forms of the invention, and that independent protection can be sought for these features in addition to, or as an alternative to, the invention as presently claimed.

[0171] The technical teachings disclosed with the present invention may be abstracted and combined with other embodiments.

[0172] The present invention is further illustrated in the following examples, which are not intended to limit the scope of the present invention. Using the details described, one skilled in the art will be able to prepare further compounds according to the present invention and use them in electronic devices without resorting to inventive steps, thereby practicing the present invention throughout the scope of the claims.

[0173] Working Example: The following syntheses are carried out in dry solvents under a protective gas atmosphere unless otherwise specified. Metal complexes are further handled in the dark or under yellow light. Solvents and reagents can be purchased, for example, from Sigma-Aldrich or ABCR. Each number in square brackets or the number indicated for each compound refers to the CAS number of the literature-known compound. When a compound has multiple enantiomeric, diastereomeric, or tautomeric forms, one form is represented in a representative manner.

[0174] Synthesis of synthon S: Example S1: [ka] The workup procedure is carried out under protective gas and with the exclusion of light. To a well-stirred solution of 36.6 g (100 mmol) of N,N-bis-(1-methyl-2-indolyl)-4-methylaniline [415975-13-2] in 300 ml of dichloromethane cooled to 0 °C, 35.6 g (200 mmol) of N-bromosuccinimide is added over 60 minutes, and the mixture is stirred at 0 °C for 5 hours. The precipitated succinimide is removed by filtration, and the organic phase is washed three times with 200 g of ice water and once with saturated sodium chloride solution and dried over magnesium sulfate.

[0175] The drying agent is removed by filtration, the filtrate is concentrated to dryness, and the residue is extracted by stirring with 150 ml of methanol. Yield: 35.2 g (67 mmol) 67%; purity about 95% 1 By H NMR.

[0176] The following compounds may be prepared similarly: [ka]

[0177] Example S100: Step 1: Lithiation of S1 [ka] A baked-out, argon-inerted four-neck flask equipped with a magnetic stir bar, dropping funnel, water separator, reflux condenser, and argon blanket is charged with 26.2 g (50 mmol) of S1 in 1300 ml of tert-butylbenzene. The reaction mixture is cooled to -40°C, and 110.5 ml (210 mmol) of tert-butyllithium, 1.9 M in n-pentane, is added dropwise. The mixture is stirred at -40°C for an additional 30 minutes, allowed to return to room temperature, and heated to 70°C, during which time n-pentane is distilled off on the water separator over approximately 1 hour.

[0178] Step 2: Transmetalation and cyclization [ka] The reaction mixture is cooled to -40°C. 10.4 ml (110 mmol) of boron tribromide is added dropwise over approximately 10 minutes. After the addition is complete, the reaction mixture is stirred at room temperature for 1 hour. The reaction mixture is cooled to 0°C, and 19.2 ml (110 mmol) of diisopropylethylamine is added dropwise over approximately 30 minutes. The reaction mixture is stirred at 160°C for 16 hours. After cooling, the diisopropylethylammonium hydrobromide is filtered using a double-ended frit, and the filtrate is cooled to -78°C.

[0179] Step 3: Arylation [ka] A double-baked, argon-inerted Schrenko flask equipped with a magnetic stir bar was charged with 27.8 g (150 mmol) of 2-bromo-1,3-dimethylbenzene [576-22-7] in 1000 mL of diethyl ether and cooled to -78 °C. Then, 60.0 mL (150 mmol) of n-butyllithium, 2.5 M in n-hexane, was added dropwise; the mixture was stirred for an additional 30 minutes. The reaction mixture was warmed to room temperature, and the solvent was completely removed under reduced pressure. The lithium organyl was suspended in 300 mL of toluene and transferred to the cold reaction mixture from Step 2. The mixture was stirred for an additional hour, and the reaction mixture was allowed to warm to room temperature overnight. 15 mL of acetone was carefully added to the reaction mixture, and it was concentrated to dryness. The oily residue is absorbed in ECM on ISOLUTE™ and hot filtered through a silica gel bed with n-pentane-DCM mixture (10:1). The filtrate is concentrated to dryness.

[0180] Step 4: Demethylation of S100 [ka] The procedure is similar to that described by T. Rosenau et al., Org. Lett., 2006, 6(4), 541. The product from step 3 is divided into four portions, converted, and the reaction zone is left for 10 minutes. The collected eluate is finally extracted from ethanol by stirring. Yield over four stages: 5.1 g (9 mmol), 18%; Purity: about 95%. 1 By H NMR.

[0181] The following compounds may be prepared similarly: [ka] [ka] [ka] [ka]

[0182] Example D100: [ka] To a solution of 5.65 g (10.0 mmol) of S100 in 200 ml of THF, 4.8 g (20.0 mmol) of sodium hydride is added in portions with good stirring and ice cooling, and the mixture is stirred for 1 hour. 10.0 ml (10.0 mmol) of a phosgene solution (1 M in toluene) is added dropwise, the mixture is stirred for 1 hour, and the solvent is removed under reduced pressure. The residue is sublimed under high vacuum (approximately 10 -4 mbar, T 250-300°C), the product sublimes to leave the salt. The sublimate is fractionally sublimed again. Yield: 1.66 g (2.8 mmol) 28%; purity ca. 99.9% 1 By H NMR.

[0183] The following compounds may be prepared similarly: [ka]

[0184] Example D200: [ka] A mixture of 5.65 g (10.0 mmol) of D100, 2.83 g (12.0 mmol) of 1,2-dibromobenzene [583-53-9], 2.88 g (30.0 mmol) of sodium tert-butoxide, 48.6 mg (0.24 mmol) of tri-tert-tributylphosphine, 44.9 mg (0.20 mmol) of palladium(II) acetate, and 70 ml of o-xylene was stirred under reflux for 16 hours. The mixture was cooled to 50 °C, 100 ml of water and 200 ml of ethyl acetate were added, the organic phase was separated, washed three times with 100 ml of water and twice with 100 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant was filtered off in the form of an ethyl acetate slurry using a Celite bed, the filtrate was concentrated to dryness, and the residue was hot extracted with ethanol. Further purification is achieved by flash chromatography (A. Semrau's Trent automated column system, ethyl acetate / n-heptane gradient), repeated hot extraction-recrystallization (dichloromethane / acetonitrile (1:2 vv)) and final fractional sublimation or high vacuum thermal treatment. Yield: 2.83 g (4.4 mmol) 44%; purity approximately 99.9%. 1 By H NMR.

[0185] The following compounds may be prepared similarly: [ka] [ka] [ka] [ka] [ka] [ka]

[0186] Example dopant D203P [ka] Prepared by flash vacuum pyrolysis from D203, carrier gas: argon, reduced pressure approximately 10 -2 t or r, pyrolysis zone temperature 550°C, catalyst: 5% PdO on alumina. Chromatographic separation: DCM / n-heptane, silica gel. Yield: 22%.

[0187] In a similar manner, D204P can be prepared from D204; yield: 16%. [ka]

[0188] OLED component manufacturing 1) Vacuum processed parts: The OLEDs according to the invention and the prior art OLEDs are produced by the general method described in WO2004 / 058911, adapted to the circumstances described therein (layer thickness range, materials used).

[0189] In the following examples, various OLED results are shown. Glass plates coated with 50 nm of structured ITO (indium tin oxide) (cleaned in a Miele laboratory glass washer, with Merck Extran detergent) are pretreated with UV ozone for 25 minutes (UVP PR-100 UV ozone generator) and then coated within 30 minutes with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH (Germany), spin-coated from an aqueous solution, for process improvement purposes, and baked at 180 °C for 10 minutes. These coated glass plates form the substrates on which the OLEDs are applied.

[0190] The OLEDs basically have the following layer structure: substrate; hole-injection layer 1 (HIL1) composed of Ref-HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm thick; hole-transport layer 1 (HTL2) composed of 160 nm HTM1 for the UV&blue OLED, 50 nm thick for the green and yellow OLEDs, and 110 nm thick for the red OLED; hole-transport layer 2 (HTL2) composed of 10 nm HTM1 for the blue OLED, 20 nm HTL2 for the green&yellow OLED, and 10 nm HTL2 for the red OLED; emissive layer (EML): 25 nm thick for the blue OLED, 40 nm thick for the green&yellow OLED, and 35 nm thick for the red OLED; hole-blocking layer (HBL) 10 nm; electron-transport layer (ETL) 30 nm HTL; electron-injection layer (EIL) composed of 1 nm ETM2; and finally, a cathode formed by a 100 nm thick aluminum layer.

[0191] First, we will describe vacuum-processed OLEDs. For this purpose, all materials are applied by thermal evaporation in a vacuum chamber. In this case, the emissive layer always consists of at least one matrix material (host material) and a light-emitting dopant (emitter), which is mixed into the matrix material in a specific volume ratio by co-evaporation. A specification such as SMB1:D1 (95:5%) means that the material SMB1 is present in the layer in a volume ratio of 95% and D1 in a volume ratio of 5%. Similarly, the electron-transporting layer may also consist of a mixture of two materials. The exact structure of the OLED can be seen in Table 1. The materials used in the manufacture of the OLED are listed in Table 4.

[0192] OLEDs are characterized by standard methods. 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 as a function of luminous flux density, calculated from the current-voltage-luminance characteristic (IUL characteristic), assuming Lambertian emission characteristics. The electroluminescence spectrum is calculated for a luminous flux density of 1000 cd / m 2 is determined by.

[0193] Use of the compounds of the present invention as materials in OLEDs One use of the compounds of the present invention is as a dopant and transport or blocking material (HBL) in the light-emitting layer of an OLED. Compound D-Ref.1 from Table 4 is used as a prior art comparison. The OLED results are summarized in Table 2. [Table 1] [Table 2]

[0194] 2) Solution-processed parts: The fabrication of solution-based OLEDs is basically disclosed in the literature (e.g., WO2004 / 037887 and WO2010 / 097155). In the following examples, two fabrication methods (application from gas phase and solution processing) are combined, where the previous layers, including the light-emitting layer, are fabricated from solution, and the subsequent layers (hole-blocking layer / electron-transporting layer) are applied by evaporation under reduced pressure. For this purpose, the above general methods are combined as follows and adapted to the situation described here (layer thickness variations, materials):

[0195] The structure used is: -substrate, -ITO (50 nm), -PEDOT (20 nm), - hole transport layer (HIL2) (20 nm), -Emitting layer (host H 192%, dopant 8%) (60 nm), -Electron transport layer (ETM150%+ETM250%) (20nm), - Cathode (Al).

[0196] The substrates used were glass substrates coated with a 50 nm thick structured ITO (indium tin oxide). For better results, these were coated with a buffer (PEDOT) Clevios P VP AI 4083 (Heraeus Clevios GmbH, Leverkusen); the PEDOT was on the surface. Spin coating was performed from water under air. The layer was subsequently baked at 180 °C for 10 minutes. A hole-transporting and light-emitting layer was then applied to the glass substrate and coated. The hole-transporting layer was a polymer with the structure shown in Table 4. It was constructed according to WO 2010 / 097155. The polymer was dissolved in toluene; the solution typically had a solids content of about 5 g / L. A layer thickness of typically 20 nm was achieved by spin coating. The layer was applied under an inert gas atmosphere, in this case argon, and baked at 180 °C for 60 minutes.

[0197] The light-emitting layer (EML) always consists of at least one matrix material (host material) and a light-emitting dopant (emitter). When given in the form H1(92%):D1(8%), this means that the material H1 is present in the light-emitting layer at a weight ratio of 92% and the dopant D1 at a weight ratio of 8%. The light-emitting layer mixture is dissolved in toluene or chlorobenzene. The typical solid content of such a solution is about 18 g / L, when a layer thickness of 60 nm, typical of the device, is achieved by spin coating. The layer is spin-coated in an inert gas atmosphere, in this case argon, and baked at 140-160 °C for 10 min. The materials used are listed in Table 4.

[0198] The materials for the electron transport layer and cathode are applied by thermal evaporation in a vacuum chamber. For example, the electron transport layer may consist of more than one material, and the materials are added to each other by co-evaporation in a specific volume ratio. When given in the form ETM1:ETM2 (50%:50%), it means that the ETM1 and ETM2 materials are present in a volume ratio of 50% each. The materials used are shown in Table 4. [Table 3] [Table 4-1] [Table 4-2]

[0199] The compounds of the present invention exhibit higher EQE values (external quantum efficiency) at lower operating voltages compared to the reference, which leads to a significant improvement in the power efficiency of the device and thereby to lower power consumption.

Claims

1. A compound having a structure selected from the group consisting of formulas (VI-9) to (VI-12), (VI-21) to (VI-24), (VI-27), (VI-30) and (VI-36). 【Chemical 1】 【change】 (wherein the symbols and subscripts used have the following meanings: Z is N; Y 3 and Y 4 are the same or different and are N(Ar), N(R), P(Ar), P(R), P(═O)Ar, P(═O)R, P(═S)Ar, P(═S)R, B(Ar), B(R), C═O, C(R) 2 , Si(R) 2 , C═NR, C═NAr, C═C(R) 2 , S, S═O, or SO 2 ; R b is a linear alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms; R, R a and R d are the same or different, H, D, OH, F, Cl, Br, I, CN, NO 2 , N(Ar') 2 , N(R 1 ) 2 , C(=O)OAr', C(=O)OR 1 , 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 the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R 1 groups, and where one or more non-adjacent CH 2 groups are 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—, —Se—, —S—, SO or SO 2 ), or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, in each case optionally substituted by one or more R 1 groups, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more R 1 groups; at the same time, two R, R a , R d groups may together or with further groups form a ring; R 1 's are the same or different and are H, D, F, Cl, Br, I, CN, NO 2 , N(Ar″) 2 , N(R 2 ) 2 , C(═O)OAr″, C(═O)OR 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, 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 substituted by one or more R 2 groups, where one or more non-adjacent CH 2 groups are optionally 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 SO 2 , and where one or more hydrogen atoms are optionally 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 of which is optionally substituted by one or more R 2 groups, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and optionally substituted by one or more R 2 groups. at the same time, two or more R 1 groups may together form a ring; at the same time, one or more R 1 groups may together with further moieties of the compound form a ring; R 2 are the same or different and are selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl 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, and may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms; and two or more substituents R 2 may together form a ring; Ar are the same or different and are aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, optionally substituted with one or more R groups; Ar' is the same or different and is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, optionally substituted by one or more R 1 groups; at the same time, two Ar' groups bonded to the same carbon, silicon, nitrogen, phosphorus or boron atom can be bonded together via a bridge of a single bond or a bridge selected from B(R 1 ), C(R 1 ) 2 , Si(R 1 ) 2 , C═O, C═NR 1 , C═C(R 1 ) 2 , O, S, S═O, SO 2 , N(R 1 ), P(R 1 ) and P(═O)R 1 ; Ar" is the same or different and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, optionally substituted by one or more R2 groups; at the same time, two Ar" groups bonded to the same carbon, silicon, nitrogen, phosphorus or boron atom can be bonded together via a bridge of a single bond or a bridge selected from B(R2), C(R2)2, Si(R2)2, C=O, C=NR2, C=C(R2)2, O, S, S=O, SO2, N(R2), P(R2) and P(=O)R2; Z １ , Z ２ is N; l is 0, 1, 2, 3, 4 or 5; m is 0, 1, 2, 3 or 4; j is 0, 1 or 2; k is 0 or 1; and Y ５ is C(R) ２ , NR, NAr′, BR, BAr′, O or S, where R and Ar′ have the above meanings; Herein, an aromatic ring system is defined as an aryl group, a group in which two or more aryl groups are directly bonded to each other, a fluorene group, or a 9,9'-spirobifluorene group; Herein, a heteroaromatic ring system is defined as a heteroaryl group or a group in which a heteroaryl group is directly bonded to one or more further aryl or heteroaryl groups.

2. The compound of claim 1, having a structure selected from the group consisting of formulas (VII-13) to (VII-18): 【Chemistry 2】 (where Z, R, R ａ , R ｂ , R ｄ , Z 1 and Z 2 have the meanings given in claim 1 and further symbols have the following meanings: Z ３ , Z ４ are the same or different and are N or B; l is 0, 1, 2, 3, 4 or 5; m is 0, 1, 2, 3 or 4; j is 0, 1 or 2; k is 0 or 1.

3. At least two R,R ａ , R ｄ The group is two R, R ａ , R ｄ The group forms a fused ring together with the group to which it is attached, where two R, R ａ , R ｄ 3. The compound according to claim 1 or 2, wherein the group forms at least one structure of formula (RA-1) to (RA-12). 【Chemistry 3】 (where R １ has the meaning described above, and the dotted bond indicates a connection site through which two R, R ａ , R ｄ The groups to which they are attached and further symbols have the following meanings: Y ８ are the same or different, 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 ｅ are 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 the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is, in each case, selected from one or more R ２ groups, wherein one or more non-adjacent CH ２ The group is RC=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 SO 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 or a ring system having 5 to 60 aromatic ring atoms, optionally substituted by a group, and one or more R ２ an aryloxy or heteroaryloxy group optionally substituted by a group; ｅ group or one R ｅ The group is R １ may form a ring with a group or with a further group, where R １ and R ２ has the meaning 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

4. A compound selected from the group consisting of: 【Chemistry 4】 【change】 【change】 【change】 【change】

5. A formulation comprising at least one compound according to any one of claims 1 to 4.

6. 5. A composition comprising at least one compound according to any one of claims 1 to 4 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.

7. A base skeleton having a Z group or a precursor of a Z group is synthesized, and Y ３ , Y ４ A process for the preparation of compounds according to any one of claims 1 to 3, characterized in that at least one of the groups is introduced by an aromatic nucleophilic substitution or coupling reaction.

8. Use of the compound according to any one of claims 1 to 4 in an electronic device.

9. An electronic device comprising at least one compound according to any one of claims 1 to 4.

Images