Aromatic Compounds for Organic Electroluminescent Devices

Abstract

The present invention relates to compounds suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, comprising said compounds.

Description

Detailed Description of the Invention

[0001] The present invention relates to aromatic compounds for use in electronic devices, particularly organic electroluminescent devices, and to electronic devices, particularly organic electroluminescent devices, comprising these polycyclic 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, the antiaromatic properties of the compounds are discussed in Wang et al., Nature Communications, 2017, 8, 1948. However, Wang et al. does not disclose the use of these compounds in organic electroluminescent devices.

[0004] In general, there is still a need for improvements in these polycyclic 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. Furthermore, the compounds should have good processability and they should exhibit particularly good solubility.

[0007] 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.

[0008] Furthermore, the compounds, especially when used as emitters in organic electroluminescent devices, should result in devices with excellent color purity.

[0009] A further challenge is to provide electronic components with excellent performance at very low cost and with consistent quality.

[0010] 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.

[0011] It has surprisingly been found that certain compounds, described in detail below, solve this problem, are suitable for use in electroluminescent devices, and provide improvements in organic electroluminescent devices, particularly with respect to lifetime, color purity, efficiency, and operating voltage. The present invention therefore provides these compounds, and electronic devices, particularly organic electroluminescent devices, comprising these compounds.

[0012] The present invention provides compounds comprising at least one structure of formula (Ia) and / or (Ib), preferably compounds of formula (Ia) and / or (Ib). [ka] where the symbols and subscripts used are: Z 1 , Z 2is identical or different at each occurrence and is N, P, B, Al, P(=O), P(=S) or Ga, preferably N, B or Al, more preferably N or B; Y 1 , Y 2 , Y 3 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), O, S, S=O or SO, more preferably a bond, C(R), O, S, C=O, N(Ar) or B(Ar); p 2 , p 3 are the same or different and are 0 or 1; X is N, CR, or Y 1 , Y 2 or Y 3 is C when the group is attached thereto, provided that no more than two X groups in one ring are N; R may be the same or different at each occurrence and is H, D, OH, F, Cl, Br, I, CN, NO, N(Ar), N(R 1 )2, C(=O)N(Ar)2, C(=O)N(R 1 )2, C(Ar)3, C(R 1 )3, Si(Ar)3, Si(R 1 )3, B(Ar)2, B(R 1 )2, C(=O)Ar, C(=O)R 1 , P(=O)(Ar)2, P(=O)(R 1 )2, P(Ar)2, P(R 1 )2, S(=O)Ar, S(=O)R 1 , S(=O)2Ar, S(=O)2R 1 , OSO2Ar, OSO2R 1, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is in each case a group selected from the group consisting 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-, -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 radicals may together form a ring system; Ar may be the same or different at each occurrence and have 5 to 60 aromatic ring atoms; 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: R1 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)Ar', C(=O)R 2 , P(=O)(Ar')2, P(Ar')2, B(Ar')2, B(R 2 )2, C(Ar')3, C(R 2 )3, Si(Ar')3, Si(R 2 ) 3, a linear alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms (each of which may be one or more R 2 radical, wherein 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 an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (each of which may be replaced by one or more R 2 or 5 to 60 aromatic ring atoms, and one or more R 2 an aryloxy or heteroaryloxy group, optionally substituted by a radical, or a aryloxy group having 5 to 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 form a ring system with further moieties of said compound; Ar' may be the same or different in each occurrence and have 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 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 2 are 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.

[0013] An aryl group, within the meaning of the present invention, contains 6 to 40 carbon atoms; a heteroaryl group, within the meaning of the present invention, contains 2 to 40 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. 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. Aromatic systems connected to each other by a single bond (e.g. biphenyl), in contrast, are not referred to as aryl or heteroaryl groups, but are aromatic ring systems.

[0014] 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.

[0015] 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.

[0016] In the sense of the present invention, an aliphatic hydrocarbyl radical or an alkyl group or an alkenyl or alkynyl group having 1 to 20 carbon atoms, each hydrogen atom or CH2 group being optionally 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, cyclopentyl, cyclopentyl, cyclopentyl, cyclohex ... Hexyl, 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.

[0017] 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.

[0018] 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]

[0019] 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]

[0020] In a preferred form, the compounds of the present invention may comprise the structure of formula (IIa), (IIb), (IIc) and / or (IId); more preferably, the compounds of the present invention are selected from compounds of formula (IIa), (IIb), (IIc) and / or (IId). [ka] where p 2 , p 3 , Y 1 , Y 2 , Y 3 , X, Z1 , Z 2 and R has the meaning given above, in particular in formula (Ia) and / or (Ib), the index n is 0, 1, 2 or 3, preferably 0, 1 or 2, the index j is 0, 1 or 2, preferably 0 or 1, and the index k is 0 or 1, preferably 0, wherein the sum of the indices k, j and n is preferably 0, 1, 2, 3, 4, 5 or 6.

[0021] Preferably, in formulae (Ia), (Ib), (IIa), (IIb), (IIc) and (IId), not more than four, preferably not more than two, X groups are N, and more preferably, all X groups are CR.

[0022] In a further preferred form, the compound of the present invention comprises a structure of formula (IIIa), (IIIb), (IIIc) and / or (IIId), where the compound of the present invention may more preferably be selected from compounds of formula (IIIa), (IIIb), (IIIc) and / or (IIId). [ka] where Y 1 , Y 2 , Y 3 , X, Z 1 , Z 2 and R has the meaning given above, in particular in formula (Ia) and / or (Ib), the index l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2, the index l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the index n is 0, 1, 2 or 3, preferably 0, 1 or 2, where the sum of the indexes l, m and n is preferably 2, 3, 4, 5, 6, 7 or 8, preferably structures of formula (IIIa) and (IIIb), particularly preferably structures of formula (IIIa).

[0023] The sum of the indices m, n and l in the structures / compounds of formula (IIIa), (IIIb), (IIIc) and (IIId) is preferably 10 or less, particularly preferably 8 or less, more preferably 6 or less.

[0024] Furthermore, in the formulas including (Ia), (Ib), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc), (IIId) and / or preferred forms of these formulas described below, Z 1 If N, then Y 1 is not N(Ar), N(R), or Z 1 If N, then Z 2 It may be the case that is not N.

[0025] Furthermore, in the formulas including (Ia), (Ib), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc), (IIId) and / or preferred forms of these formulas described below, Z 1 is N and Y 1 is N(Ar), then Y 1 The Ar group of the N(Ar) radical represented by 1 Compounds in which any two of the four X groups, together with the four R radicals derived from the X groups of the ring system to which the radicals are attached, form adjacent aromatic ring systems are excluded.

[0026] In a further aspect, the formulae including (Ia), (Ib), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc), (IIId) and / or preferred aspects of these formulae below, Z 1 is selected from N and P, and Y 1 the group is P(=O)Ar, P(=O)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(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 B(R) or B(Ar); or Z1 is selected from N and P, and Z 2 the group is B, Al, P(=O), P(=S) or Ga, preferably B, Al or P(=O), more preferably B, or Z 2 is selected from N and P, and Y 2 , Y 3 This may be the case where at least one of the groups is P(=O)Ar, P(=O)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, S=O or SO2, preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO2, more preferably B(R) or B(Ar).

[0027] In a further aspect, the formulae including (Ia), (Ib), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc), (IIId) and / or preferred aspects of these formulae below, Z 1 is selected from B, Al, P(=O), P(=S) and Ga, and Y 1 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), or Z 1 is selected from B, Al, P(=O), P(=S) and Ga, and Z 2 , Y 3 The group is N or P, preferably N or P, more preferably N; Z 2 is selected from B, Al, P(=O), P(=S) and Ga, and Y 2 , Y 3 This may be the case where at least one of the groups 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).

[0028] More preferably, Z 1and / or Z 2 is B. Furthermore, Z 1 and / or Z 2 is more preferably N. In a particularly preferred embodiment, Z 1 and Z 2 one of the groups is B and Z 1 and Z 2 One of the groups is N.

[0029] In a preferred embodiment of the invention, at least two R radicals, together with the further group to which they are attached, form a fused ring, which may be the case, where the two R radicals form at least one of the structures of formulae (RA-1) to (RA-12). [ka] where R 1 has the meaning given above, the dotted line indicates the attachment site to the atom of the group to which the two R radicals are attached, and further symbols have the following meanings: Y 4 may be 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 a are the same or different at each occurrence and are selected from the group consisting of F, a straight-chain 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 2radical, where one or more non-adjacent CH groups are 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; a It is also possible for the radicals to form together a ring system; 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.

[0030] Furthermore, there may be cases where at least two R radicals forming a fused ring in the structure of formulae (RA-1) to (RA-12) are R radicals from adjacent X groups.

[0031] In a preferred embodiment of the invention, at least two R radicals, together with the further group to which they are attached, form a fused ring, wherein the two R radicals preferably form at least one of the structures of formulae (RA-1a) to (RA-4f). [ka] Here, the symbol R a and R 1 and the subscripts s and t have the meanings given above, especially in formulae (RA-1) to (RA-12), and the subscript m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0032] In a further preferred form, at least two R radicals, together with the additional group to which they are attached, form a fused ring, wherein the two R radicals form a structure of formula (RB). [ka] where R 1 has the meaning given above, in particular in formula (Ia) and / or (Ib), the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y 5 is C(R 1 )2, NR 1 , NAr, O or S, preferably C(R 1 )2, NAr or O.

[0033] Here, it may be the case that at least two R radicals forming a fused ring forming a structure of formula (RB) are R radicals from adjacent X groups.

[0034] More preferably, the compound comprises at least one of the structures of formula (IVa) to (IVr); more preferably, the compound is selected from compounds of formula (IVa) to (IVr), wherein the compound has at least one fused ring. [ka] [ka] where Y 1 , Y 2 , Y 3 , X, Z 1 , Z 2and R have the meanings described above, in particular in formula (Ia) and / or (Ib), the symbol o indicates the attachment site of the fused ring, the subscript l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2, the subscript m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the subscript n is 0, 1, 2 or 3, preferably 0, 1 or 2, the subscript j is 0, 1 or 2, preferably 0 or 1, and the subscript k is 0 or 1, preferably 0, where the sum of the subscripts k, j, l, m and n is preferably 0, 1, 2, 3, 4, 5 or 6. Preference is given to structures / compounds of formulae (IVa) to (IVk), particularly preferred are structures / compounds of formulae (IVa) to (IVd).

[0035] In particular, in formulae (IVa) to (IVr), the fused ring is formed together with the ring atom marked with the symbol o by at least one of the structures of formulae (RA-1) to (RA-12), formulae (RA-1a) to (RA-4f), and / or formula (RB), and particularly preferred are the structures of formulae (RA-1) to (RA-12), and formulae (RA-1a) to (RA-4f).

[0036] In a preferred form, the compounds comprise a structure having the following characteristics, along with the skeletal ring formation shown in the table below, and are selected according to the following criteria: [ka] [ka] [ka] [ka] [ka]

[0037] 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 (Va) to (Vs), and preferably the compound is selected from compounds of formulae (Va) to (Vz). [ka] [ka] [ka] where Y 1 , Y 2 , Y 3 , X, Z 1 , Z 2 and R have the meanings given above, in particular in formula (Ia) and / or (Ib), the symbol o denotes at least one attachment site of the structures of formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) or of formula (RB), the subscript l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2, the subscript m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the subscript n is 0, 1, 2 or 3, preferably 0, 1 or 2, the subscript j is 0, 1 or 2, preferably 0 or 1, and the subscript k is 0 or 1, preferably 0, where the sum of the subscripts k, j, l, m and n is preferably 0, 1, 2, 3 or 4, more preferably 2, 3 or 4. Preference is given to structures / compounds of formulae (Va) to (Vq). Preferably, the sum of the indices k, j, l, m and n is 0, 1, 2 or 3, preferably 1 or 2.

[0038] Here, it may be the case that formulae (Va) to (Vs) have at least two fused rings, where the fused rings are identical and the moiety formed by the two R radicals can be represented by at least one of the structures of formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

[0039] Furthermore, it may be the case that formulae (Va) to (Vs) have at least two fused rings, where the fused rings are different and the moiety formed by the two R radicals 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).

[0040] Furthermore, there may be cases where formulas (Va) to (Vs) have at least two fused rings, where the fused rings are different and the moiety formed by the two R 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 has a moiety formed by two R radicals represented by one of the structures of formula (RB).

[0041] The substituents R and R in the above formula a , R 1 and R 2 However, R and R a , R 1 and R 2 together with the ring atoms of the ring system to which they are attached do not form a fused aromatic or heteroaromatic ring system. a and R 1 Possible substituents R which may be attached to the radical 1 and R 2 together to form a fused aromatic or heteroaromatic ring system.

[0042] Especially R, R a , R 1 and / or R 2When 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 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 1 and / or R 2 Available at.

[0043] In a preferred embodiment, the compounds of the present invention can be represented by at least one of the structures of formula (Ia), (Ib), (IIa)-(IId), (IIIa)-(IIId), (IVa)-(IVr), and / or (Va)-(Vs). Preferably, the compounds of the present invention comprising the structure of formula (Ia), (Ib), (IIa)-(IId), (IIIa)-(IIId), (IVa)-(IVr), and / or (Va)-(Vs) 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.

[0044] 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.

[0045] Preferred aromatic or heteroaromatic ring systems R, R aand / 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, indole, benzofuran, benzothiophene, carbazole which may be bonded via the 1-, 2-, 3- or 4-position, dibenzofuran which may be bonded via the 1-, 2-, 3- or 4-position, dibenzothiophene which may be bonded via 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 bonded via one or more R 1 and optionally substituted by a radical.

[0046] Preferably, at least one substituent R at each occurrence is the same or different and is selected from the group consisting of H, D, or an aromatic or heteroaromatic ring system selected from the groups of formulae Ar-1 to Ar-75 below, wherein the substituent R preferably forms a ring according to the structure of formulae (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), or the substituent R at each occurrence is the same or different and is selected from an aromatic or heteroaromatic ring system selected from the groups of formulae Ar-1 to Ar-75 below, and / or the Ar group at each occurrence is the same or different 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 bonded to HetAr; 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.

[0047] 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 1 or both A groups are O.

[0048] 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 1The 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, 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.

[0049] Preferred substituents R and R a The following describes this.

[0050] In a preferred embodiment of the invention, R is the same or different at each occurrence and is selected from the group consisting of H, D, F, CN, NO, 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.

[0051] In a further preferred embodiment of the invention, R is, at each occurrence, identical or different and is selected from 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, wherein 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.

[0052] Additionally, at least one substituent R may be the same or different at each occurrence and may be H, D, or a group having 6 to 30 aromatic ring atoms, and may be one or more R 1 In a further preferred embodiment of the invention, the R substituents form a ring according to the structure of formula (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), or R, which may be identical or different at each occurrence, is selected from the group consisting of H, D, 6 to 30 aromatic ring atoms, and one or more R 1 and N(Ar) groups. More preferably, R is the same or different at each occurrence and is selected from the group consisting of H or 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, and in each case, one or more R 1 is selected from the group consisting of aromatic or heteroaromatic ring systems optionally substituted by radicals.

[0053] In a preferred embodiment of the present invention, R a 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 1and 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case one or more R 1 is selected from the group consisting of aromatic or heteroaromatic ring systems optionally substituted by radicals.

[0054] In a further preferred embodiment of the invention, R a 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 1 More preferably, R is selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals. a are 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 1 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 1 The ring system is selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals.

[0055] In a preferred embodiment of the present invention, R a 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 1 or 6 to 24 aromatic ring atoms, in each case one or more R 1 and at the same time, two R are selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by a radical;a The radicals may together form a ring system. More preferably, R a 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 1 or 6 to 12 aromatic ring atoms, in particular 6 aromatic ring atoms, in each case one or more preferably non-aromatic, R 1 and at the same time, two R a The radicals may together form a ring system. Most preferably, R a are 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 a 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.

[0056] Preferred aromatic or heteroaromatic ring systems R, R aor Ar is phenyl, biphenyl, particularly ortho-, meta- or para-biphenyl, terphenyl, particularly ortho-, meta- or para-terphenyl or branched terphenyl, quaterphenyl, particularly 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, particularly 1- or 2-bonded naphthalene, indole, benzofuran, benzothiophene, carbazole which may be bonded via the 1-, 2-, 3- or 4-position, dibenzofuran which may be bonded via the 1-, 2-, 3- or 4-position, dibenzothiophene which may be bonded via 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 bonded via one or more R 1 The structures Ar-1 to Ar-75 shown above are particularly preferred, and 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) are preferred, and structures of formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16) are particularly preferred.

[0057] Further preferred R groups are of the formula -Ar 4 -N(Ar 2 )(Ar 3 ) group, where Ar 2 , Ar 3 and Ar 4 are the same 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 Ar4 The total number of aromatic ring atoms in the aryl group is 60 or less, preferably 40 or less.

[0058] In this case, Ar 4 and Ar 2 may be bonded to each other, and / or Ar 2 and Ar 3 is a single bond, C(R 1 )2, NR 1 , O and S. Preferably, Ar 4 and Ar 2 to each other, or Ar 2 and Ar 3 The bonds of Ar to each other are in each case ortho to the position of the bond to the nitrogen atom, for example, preferably forming a carbazole. 2 , Ar 3 and Ar 4 None of the groups are bonded to each other.

[0059] 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.

[0060] 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 1Aromatic or heteroaromatic ring systems, optionally substituted by radicals. Particularly preferred Ar 2 and Ar 3 The 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.

[0061] In a further preferred embodiment of the invention, R 1 are the same or different at each occurrence and are selected from H, D, F, CN, a linear alkyl group which may have 1 to 10 carbon atoms or a branched or cyclic alkyl group which may have 3 to 10 carbon atoms, where the alkyl group may in each case be selected from one or more R 2or 6 to 24 aromatic ring atoms, in each case one or more R 2 In 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 5 The radical is selected from the group consisting of an aromatic or heteroaromatic ring system which may be substituted, but is preferably unsubstituted.

[0062] 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).

[0063] 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.

[0064] Furthermore, it may be a compound containing exactly two or exactly three structures of formula (Ia), (Ib), (IIa) to (IId), (IIIa) to (IIId), (IVa) to (IVr) and / or (Va) to (Vs), wherein preferably Y 1 , Y 2 , Y 3 one of the groups, or Y 1 , Y 2 , Y 3 One of the aromatic or heteroaromatic ring systems to which at least one of the groups is attached is shared by both structures.

[0065] In a preferred embodiment, the compound comprises at least one of the structures of formulae (D-1) to (D-5), where the compound more preferably conforms to formulae (D-1) to (D-5). [ka] [ka] where Y 2a is C or Si, and L 1 The group represents a linking group, preferably a bond or a group having 5 to 40, preferably 5 to 30, aromatic ring atoms, and one or more R 1 an aromatic or heteroaromatic ring system, optionally substituted by radicals, and the further symbols and indices used have the meanings given above, in particular in formula (Ia) and / or (Ib).

[0066] 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, in particular in formula (Ia) and / or (Ib). More preferably, L 1is 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 meanings given above, especially in formula (Ia) and / or (Ib).

[0067] More preferably, the symbol L shown in the formula including (D2) and (D3) 1 is 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.

[0068] Furthermore, L shown in formulas (D2) and (D3) 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.

[0069] Particularly preferred are non-fused structures, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0070] Suitable aromatic or heteroaromatic ring systems L 1Examples 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 It may be substituted by a radical, but is preferably unsubstituted.

[0071] 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.

[0072] Examples of preferred compounds according to the above aspects are the compounds shown in the table below. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0073] 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.

[0074] 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.

[0075] 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.

[0076] Therefore, the present invention provides Z 1 A base skeleton having a group or Z 1 Further provided are methods for preparing compounds of the present invention, wherein a precursor of the group is synthesized and then the ring closure reaction is carried out by a nucleophilic aromatic substitution reaction or a coupling reaction.

[0077] The present invention also provides Z 1 A base skeleton having a group or Z 1 The precursor of the Z group was synthesized. 2 , Y 1 , Y 2 , Y 3 Further provided are methods for preparing compounds of the invention, wherein at least one of the groups is introduced by a nucleophilic aromatic substitution or coupling reaction.

[0078] Z 1 Suitable compounds comprising a basic skeleton bearing groups are often commercially available, the starting compounds detailed in the examples being obtainable by known methods, as referenced therein.

[0079] These compounds contain at least one Z 2 , Y 1 , Y 2 , Y 3 in known coupling reactions, the conditions required for this purpose are well known to those skilled in the art, and the detailed descriptions in the examples will assist those skilled in the art in carrying out these reactions.

[0080] 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.

[0081] 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.

[0082] 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).

[0083] 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.

[0084] The present invention further provides polymers, oligomers or dendrimers comprising one or more structures of formula (Ia) and / or (Ib) and preferred forms of this formula or compounds of the invention as detailed above, wherein there are one or more bonds to the polymer, oligomer or dendrimer to the compounds of the invention or to the structures of formula (Ia) and / or (Ib) and preferred forms of this formula.

[0085] Depending on the structure of (Ia) and / or (Ib) and the preferred forms or linkages of the compounds of this formula, they may therefore form side chains of a polymer or oligomer or be linked within the main chain. The polymer, oligomer or dendrimer may be conjugated, partially conjugated or non-conjugated. The oligomer or polymer may be linear, branched or dendritic. The same preferred forms as described above apply to the repeating units of the compounds of the present invention in oligomers, dendrimers and polymers.

[0086] To prepare oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with further monomers. The units of formula (Ia) and / or (Ib), or units of 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 EP 842208 or WO 2000 / 022026), spirobifluorene (e.g., according to EP 707020, EP 894107 or WO 2006 / 061181), paraphenylene (e.g., according to WO 92 / 18552), carbazole (e.g., according to WO 2004 / 070772 or WO 2004 / 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.

[0087] Furthermore, the compounds of the present invention are particularly interesting because they are characterized by a high glass transition temperature. In this connection, preferred are compounds of the present invention comprising the structure of formula (Ia) and / or (Ib) 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] The electronic device is preferably selected from the group consisting of, more preferably selected from the group consisting of organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), preferably organic light-emitting diodes (OLEDs), small molecule-based organic light-emitting diodes (sOLED), polymer-based organic light-emitting diodes (PLED), light-emitting electrochemical cells (LEC), organic laser diodes (O-laser), organic plasma light-emitting devices (DM Koller et al., Nature Photonics 2008, 1-4), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic photodetectors, organic photoreceptors, organic field-quenched devices (O-FQDs), organic electronic sensors, preferably organic electroluminescent devices (OLEDs, sOLEDs, PLEDs, LECs, etc.), 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.

[0094] 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.

[0095] The compounds of the present invention may be used in different layers depending on the exact structure. Preferably, the compounds of formula (Ia) and / or (Ib) or the preferred forms described above are used in organic electroluminescent devices as emitters, preferably as red, green or blue emitters, in the light-emitting layer.

[0096] When the compounds of the present invention are used as emitters in a light-emitting layer, known suitable matrix materials are preferably used.

[0097] 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.

[0098] 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. according to WO2004 / 013080, WO2004 / 093207, WO2006 / 005627 or WO2010 / 006680, triarylamines, carbazole derivatives, e.g. CBP (N,N-biscarbazolylbiphenyl) or compounds according to WO2005 / 039246, US2005 / 0069729, JP2004 / 288381, EP1205527, WO2008 / 086851 or WO2013 / 041176, indolocarbazole derivatives, for example according to WO2007 / 063754 or WO2008 / 056746, indenocarbazole derivatives, for example according to WO2010 / 136109, WO2011 / 000455, WO2013 / 041176 or WO2013 / 056776, azacarbazole derivatives, for example according to EP1617710, EP1617711, EP1731584, JP2005 / 347160, bipolar matrix materials, for example according to WO20 07 / 137725, silanes, for example according to WO 2005 / 111172, azaboroles or boronic esters, for example according to WO 2006 / 117052, triazine derivatives, for example according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, zinc complexes, for example according to EP 652273 or WO 2009 / 062578, diazasilol or tetraazasilol derivatives, for example according to WO 2010 / 05 4729, diazaphosphole derivatives, for example according to WO 2010 / 054730, bridged carbazole derivatives, for example according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080, triphenylene derivatives, for example according to WO 2012 / 048781, dibenzofuran derivatives, for example according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565, and also bizcarbazoles,For example, see JP3139321B2. Further preferred matrix or host materials are anthracenes. Particularly preferred anthracenes are disclosed in WO2014 / 106523A1, very particularly preferably of formula (II). Further particularly preferred anthracenes are disclosed in WO2007 / 065547A1, very particularly preferably of formula (2) and (3), in particular of formulas (A1) to (A64). Further particularly preferred anthracenes are disclosed in WO2007 / 065548A1, very particularly preferably of formula (1), in particular of formulas H1 to H20.

[0099] 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.

[0100] In a preferred embodiment, the compounds of the present invention used as emitters are preferably used in combination with one or more phosphorescent materials (triplet emitters) and / or compounds that are TADF (thermally activated delayed fluorescence) host materials, preferably forming hyperfluorescent and / or hyperphosphorescent systems.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] Examples of the above mentioned luminescent materials are described in the applications WO00 / 70655, WO2001 / 41512, WO2002 / 02714, WO2002 / 15645, EP1191613, EP1191612, EP1191614, WO05 / 033244, WO05 / 019373, US2005 / 0258742, WO2009 / 146770, WO2010 / 015307, WO 2010 / 031485, WO2010 / 054731, WO2010 / 054728, WO2010 / 086089, WO2010 / 099852, WO2010 / 102709 , WO2011 / 032626, WO2011 / 066898, WO2011 / 157339, WO2012 / 007086, WO2014 / 008982, WO2014 / 023 377, WO2014 / 094961, WO2014 / 094960, WO2015 / 036074, WO2015 / 104045, WO2015 / 117718, WO2016 / 015815, WO2016 / 124304, WO2017 / 032439, WO2018 / 011186, WO2018019687, WO2018019688, WO2018 041769, WO2018054798, WO2018069196, WO2018069197, WO2018069273, WO2018134392, WO2018178001, WO2018177981, WO2019020538, WO2019115423, WO2019158453 and WO2019179909. 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 having to resort to inventive ingenuity.

[0105] The compounds of the present invention may preferably be used in combination with the TADF host materials and / or TADF emitters described above.

[0106] 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.

[0107] 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.

[0108] 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 that is known for organic electroluminescent device in combination with the compound of the present invention according to formula (Ia) and / or (Ib) or above-mentioned preferred form without inventive ingenuity.

[0109] 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.

[0110] 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 version of this method is the OVJP (organic vapor jet printing) method, in which the material is applied directly through a nozzle and thus structured.

[0111] 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.

[0112] The formulations applying the compounds of formula (Ia) and / or (Ib) or the preferred forms thereof as described above are novel. Thus, the present invention further provides a formulation comprising at least one solvent and a compound of formula (Ia) and / or (Ib) or the preferred forms thereof as described above.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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 the compounds of formula (Ia) and / or (Ib) or the preferred forms described above and below as emitters have very low emission bands with low FWHM (Full Width Half Maximum) values ​​and produce particularly pure color emission, recognizable by low CIEy values. 2. Electronic devices, particularly organic electroluminescent devices, comprising (Ia) and / or (Ib) or the preferred forms described above and below as emitters have excellent efficiency. In this sense, the compounds of the present invention having the structures of (Ia) and / or (Ib) or the preferred forms described above and below, when used in electronic devices, provide low operating voltages. 3. The compounds of formula (Ia) and / or (Ib) or the preferred forms described above and below can be used to avoid the formation of light loss channels in electronic devices, especially organic electroluminescent devices, which are consequently characterized by high PL efficiency and high EL efficiency of the emitter and excellent energy transfer to the dopant of the material. 4. Compounds of formula (Ia) and / or (Ib) or the preferred forms described above and below have excellent glass film formation. 5. Compounds of formula (Ia) and / or (Ib) or the preferred forms described above and below form very good films from solution and exhibit excellent solubility.

[0117] The above advantages are not accompanied by excessively high degradation of further electronic properties.

[0118] 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.

[0119] 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).

[0120] 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.

[0121] The technical teachings disclosed with the present invention may be abstracted and combined with other embodiments.

[0122] The present invention is further illustrated by the following examples, which are not intended to limit the invention. Using the details described, one skilled in the art will be able to prepare further compounds according to the invention and use them in electronic devices without resorting to inventive efforts, and thereby practice the invention throughout the scope of the claims.

[0123] 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.

[0124] Synthesis of synthon S: Example S1: [ka] To a well-stirred mixture of 33.3 g (100 mmol) of 1-bromo-2-iodonaphthalene [90948-03-1], 4.6 g (50 mmol) of aniline [62-53-3], and 24.2 g (250 mmol) of sodium tert-butoxide in 600 mL of toluene, 405 mg (2 mmol) of tri-tert-butylphosphine [131274-22-2], and 404 mg (1.8 mmol) of palladium(II) acetate were added, and the mixture was stirred at 70 °C for 16 h. After cooling, the reaction mixture was washed three times with 500 mL of water and once with 500 mL of saturated sodium chloride solution. The organic phase was dried over magnesium sulfate, the magnesium sulfate was filtered off through a silica gel bed in the form of a toluene slurry, and the filtrate was concentrated to dryness under reduced pressure. The residue was subjected to flash chromatography, silica gel, n-heptane / ethyl acetate, Trent automated column system according to A. Semrau. Yield: 14.4 g (28.5 mmol) 57%; purity about 95%. 1 By H NMR.

[0125] The following compounds may be prepared similarly: [ka] [ka] [ka] [ka]

[0126] Synthesis of Compounds of the Invention Example D1: [ka] A well-stirred mixture of 29.5 g (100 mmol) of dibenzo[c,h]acridine-7(14H)-one [50405-28-2], 30.0 g (110 mmol) of 2-iodo-1,3-dichlorobenzene [19230-28-5], 41.5 g (300 mmol) of potassium carbonate (anhydrous), 42.6 g (300 mmol) of sodium sulfate (anhydrous), 21.0 g (330 mmol) of copper powder, 100 g of glass beads (3 mm diameter), and 300 ml of nitrobenzene was boiled under reflux for 24 hours. After cooling, a mixture of 1000 ml of methanol and 500 ml of water was added, and the mixture was stirred for an additional hour. The solid was suction filtered, washed five times with 100 ml of methanol each, and dried under reduced pressure. The residue is taken up in 500 ml of o-dichlorobenzene, boiled under reflux for 30 minutes, and then, while hot, suction filtered through a Celite bed in the form of an o-dichlorobenzene slurry. The filtrate is concentrated under reduced pressure at 80 °C to a volume of approximately 50 ml, and while hot, 100 ml of ethanol is added to crystallize the product. After cooling, the crystals are suction filtered, washed three times with 50 ml of ethanol each time, and dried under reduced pressure. Purification is carried out by repeated hot extraction crystallization with dichloromethane (DCM) (alternative solvents: toluene, benzonitrile, chlorobenzene, dimethylacetamide, etc.), and finally by fractional sublimation or thermal treatment under high vacuum. Yield: 13.3 g (36 mmol), 36%; purity: >99.5% 1 By H NMR / HPLC.

[0127] The following compounds may be prepared similarly: [ka] [ka] [ka]

[0128] Example D50: The following sequence of steps 1-3 is carried out as a one-pot reaction. [ka]

[0129] 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 28.0 g (50 mmol) of S1 in 1500 ml of tert-butylbenzene. The reaction mixture is cooled to -45°C, and 110.5 ml (210 mmol) of tert-butyllithium, 1.9 M in n-pentane, is added dropwise over 30 minutes. The mixture is stirred at -40°C for an additional 30 minutes, allowed to return to room temperature, and heated to 70°C, while the n-pentane is distilled off on the water separator over approximately 1 hour.

[0130] Step 2: Transmetallation and cyclization [ka] The reaction mixture is cooled to -40°C. 5.2 ml (55 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 and then cooled to -40°C.

[0131] Step 3: Arylation [ka] A twice-baked, argon-inerted Schrenko flask equipped with a magnetic stir bar was charged with 8.8 g (60 mmol) of 1,3-dichlorobenzene [541-73-1] in 300 mL of THF and cooled to -78 °C. Next, 24.0 mL (60 mmol) of n-butyllithium, 2.5 M in n-hexane, was added dropwise over approximately 20 minutes; the mixture was then stirred for an additional 1.5 hours. The reaction mixture was allowed to warm 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. 50 mL of methanol was carefully added to the reaction mixture, and the solvent was completely removed under reduced pressure.

[0132] Step 4: Cyclization The solid from step 3 is taken up in 300 ml of dimethylacetamide (DMAC), 27.6 g (200 mmol) of potassium carbonate, 50 g of glass beads (3 mm diameter), and 1.72 g (3 mmol) of (NHC)Pd(Allyl)Cl [478980-03-9] are added, and the well-stirred reaction mixture is heated at 130 °C for 18 h. The hot reaction mixture is filtered through a Celite bed to form a hot DMAC slurry. The filtrate is heavily concentrated under reduced pressure, 300 ml of hot ethanol is added, and the mixture is stirred for an additional hour. While the mixture is still hot, the product is suction filtered, washed three times with 50 ml of ethanol each, and dried under reduced pressure. Purification is achieved by repeated hot extraction and crystallization with dichloromethane (DCM) (alternative solvents: toluene, benzonitrile, chlorobenzene, dimethylacetamide, etc.), and finally by fractional sublimation or thermal treatment under high vacuum. Yield: 9.4 g (22 mmol), 44%; Purity: >99.5% 1 By H NMR / HPLC.

[0133] The following compounds may be prepared similarly: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0134] 1) Vacuum processed elements: 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).

[0135] 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. The OLED basically has the following layer structure: substrate, hole injection layer 1 (HL1) consisting of Ref-HTM1 doped with 5% NDP-9 (available from Novaled), hole transport layer 1 (HTL1) consisting of 20 nm / 160 nm HTL1, optional hole transport layer 2 (HTL2), 10 nm / emissive layer (EML), 20 nm / hole blocking layer (HBL), 10 nm / electron transport layer (ETL), electron injection layer (EIL) consisting of 20 nm / 1 nm ETM2, and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer.

[0136] 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 the material 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 3.

[0137] 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 These are used to calculate the CIE 1931y color coordinates.

[0138] Use of the compounds of the present invention as materials in OLEDs One use of the compounds of the present invention is as a hole transport material and dopant in the light-emitting layer of an OLED. Compound D-Ref.1 from Table 3 is used as a prior art comparison. The OLED results are summarized in Table 2. [Table 1] [Table 2] [Table 3]

[0139] The compounds of the present invention exhibit a narrower electroluminescence spectrum, as determined by a smaller EL-FWHM value (EL electroluminescence - Full Width Half Maximum - width of the EL emission spectrum at half the peak height (nm)), and a bluer emission, as determined by a shorter emission wavelength ELmax., compared with the reference, which results in a significant improvement in color purity (smaller CIEy value). Furthermore, compared with the reference, the EQE value (external quantum efficiency) is significantly higher and the operating voltage is significantly lower, which results in a significant improvement in the power efficiency of the device and lower power consumption.

Claims

1. A compound of formula (IIIa) and / or (IIId). 【Chemistry 1】 (where the symbols and subscripts used are as follows: In formula (IIIa), Z 1 is N and Y 1 is C(R) 2 , O, C═O or B(Ar); In formula (IIId), Z 1 is N and Z 2 is B, or Z 1 is B and Z 2 is N; j is 0, 1 or 2; l is 0, 1, 2, 3, 4 or 5; n is 0, 1, 2 or 3; R is the same or different at each occurrence and has 5 to 60 aromatic ring atoms, and in each case is one or more R １ an aromatic ring system, optionally substituted by a radical; and at the same time, two R radicals together form a ring system via a bridge by a single bond; Ar has 5 to 60 aromatic ring atoms and one or more R １ a heteroaromatic ring system, optionally substituted by radicals; R １ are the same or different for each occurrence, H, D, F, Cl, Br, I, CN, NO ２ , N(Ar′) ２ , N(R ２ ) ２ , C(=O)Ar', C(=O)R ２ , P(=O)(Ar') ２ , P(Ar′) ２ , B(Ar′) ２ , B(R ２ ) ２ , C(Ar′) ３ , C(R ２ ) ３ , Si(Ar′) ３ , Si(R ２ ) ３ a straight-chain 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 may be one or more R ２ radical, wherein one or more non-adjacent CH ２ The group is -R ２ C=CR ２ -, -C≡C-, Si(R ２ ) ２ , C=O, C=S, C=Se, C=NR ２ , -C(=O)O-, -C(=O)NR ２ -, N.R. ２ , P(=O)(R ２ ), —O—, —S—, SO or SO ２ and where one or more hydrogen atoms are 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 may be replaced by one or more R ２ or 5 to 60 aromatic ring atoms, 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 an aralkyl or heteroaralkyl group, or a combination of these systems, optionally substituted by a radical; Ar′ is the same or different at 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 B(R ２ ), C(R ２ ) ２ , Si(R ２ ) ２ , C=O, C=NR ２ , C=C(R ２ ) ２ ,O,S,S=O,SO ２ , N(R ２ ), P(R ２ ) and P(=O)R ２ may also be coupled together via a bridge selected from: R ２ are the same 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.

2. The compound of claim 1, wherein two R radicals are bonded together to form a fluorene.

3. The R 1 radical is an aromatic ring system having 5 to 60 aromatic ring atoms, each of which is represented by one or more R ２ 3. The compound according to claim 1 or 2, wherein:

4. A compound selected from the group consisting of the following: 【Chemistry 2-1】 【Chemistry 2-2】 【Chemistry 2-3】 【Chemistry 2-4】

5. 5. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 4, wherein apart from hydrogen atoms or substituents there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

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

7. A composition comprising at least one compound according to any one of claims 1 to 4, or an oligomer, polymer or dendrimer according to claim 5, and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF, host materials, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials and hole blocking materials.

8. Z １ A base skeleton having a group or Z １ A process for the preparation of compounds according to any one of claims 1 to 3, characterized in that a precursor of the group is synthesised and the ring-closing reaction is carried out by an aromatic nucleophilic reaction or a coupling reaction.

9. Use of a compound according to any one of claims 1 to 4, or an oligomer, polymer or dendrimer according to claim 5, in an electronic device.

10. An electronic device comprising a compound according to any one of claims 1 to 4, or an oligomer, polymer or dendrimer according to claim 5.

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