Heterocyclic compounds comprising dibenzofuran and / or dibenzothiophene structures

Abstract

To provide compounds useful as matrix materials which are suitable for red-, yellow- and green-phosphorescing, and blue-phosphorescing organic electroluminescent devices, and which lead to long lifetime, good efficiency and low operating voltage.SOLUTION: The present invention provides a compound represented by the formula (Ia) (where Y represents O or S; L1 and L2 each represent a bond or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms, which are optionally substituted by one or more R1 radicals; R1 represents H, D, F, Cl or the like; Q1 and Q2 each represent a group including a structure such as pyrimidine, triazine, quinazoline, or benzimidazole).SELECTED DRAWING: None

Description

Detailed Description of the Invention

[0001] The present invention describes dibenzofuran and / or dibenzothiophene derivatives substituted with electron transporting groups, in particular for use in electronic devices. The present invention further relates to processes for the preparation of the compounds of the invention and to electronic devices comprising these compounds.

[0002] The structures of organic electroluminescent devices (OLEDs), in which organic semiconductors are used as functional materials, are described, for example, in US4539507, US5151629, EP0676461 and WO98 / 27136. The emitting materials used are often phosphorescent organometallic complexes. For quantum mechanical reasons, the use of organometallic compounds as phosphorescent emitters allows for up to four times the energy and power efficiency. There is still a need for improvements in OLEDs in general, and in phosphorescent OLEDs in particular, for example with regard to efficiency, operating voltage and lifetime.

[0003] The properties of phosphorescent OLEDs are not only determined by the triplet emitter emitter used. More specifically, other materials used, such as matrix materials, are of particular importance. Improvements to these materials can lead to clear improvements in OLED properties.

[0004] According to the prior art, among other materials, carbazole derivatives (for example according to WO2014 / 015931), indolocarbazole derivatives (for example according to WO2007 / 063754 or WO2008 / 056746) or indenocarbazole derivatives (for example according to WO2010 / 136109 or WO2011 / 000455), especially those substituted with electron-deficient heteroaromatics (for example triazines), are used as matrix materials for phosphorescent emitters. Furthermore, for example, bisdibenzofuran derivatives (for example according to EP2301926) are used as matrix materials for phosphorescent emitters. WO2013 / 077352 discloses triazine derivatives in which the triazine group is linked to the dibenzofuran group via a divalent arylene group. These compounds are described as hole-blocking materials. The use of these compounds as hosts for phosphorescent emitters is not disclosed. Furthermore, EP2752902 discloses heterocyclic compounds having dibenzofuran and dibenzothiophene structures.However, dibenzofuran and dibenzothiophene structures have only one binding site to other heterocycles, that is, they are only monosubstituted.Similar compounds are further known from KR20130115160.

[0005] In the case of these materials, which are generally used as matrix materials, there is still a need for improvements in the devices, especially with regard to their lifetime, but also with regard to their efficiency and operating voltage.

[0006] The object of the present invention is to provide a compound suitable for use in phosphorescent or fluorescent OLEDs, particularly as a matrix material.More specifically, the object of the present invention is to provide a matrix material suitable for red, yellow and green phosphorescent OLEDs, and possibly blue phosphorescent OLEDs, which provides long life, good efficiency and low operating voltage.In particular, the properties of the matrix material have a substantial effect on the life and efficiency of organic electroluminescent devices.

[0007] Furthermore, the compounds must be processable in a very simple manner and must in particular exhibit good solubility and film-forming properties, for example they must exhibit oxidative stability on heating and improved glass transition temperatures.

[0008] A further object is to provide electronic components with excellent performance at very low cost and with consistent quality.

[0009] Additionally, electronic devices must be capable of being used or adapted for many purposes, and more particularly, the performance of the electronic devices must be maintained over a wide temperature range.

[0010] Surprisingly, it has been found that devices comprising a compound comprising the compound of formula (I) below provide improvements over the prior art, particularly when used as a matrix material for phosphorescent dopants.

[0011] Thus, the present invention provides a compound comprising the structure of formula (I): [ka] where the symbols used are as follows: Y is O or S; X is the same or different for each occurrence and is N or CR 1 , preferably CR 1 with the proviso that not more than two of the X groups in one ring are N and C is L 2 is the binding site for the group; Q 1 , Q 2 is, independently in each occurrence, an electron transport group; L 1 , L 2 has a bond or 5 to 30 aromatic ring atoms and is at least one R 1 an aromatic or heteroaromatic ring system, optionally substituted by radicals; R 1 are the same or different for each occurrence, H, D, F, Cl, Br, I, B (OR2 )2, CHO, C(=O)R 2 , C.R. 2 =C(R 2 )2, CN, C(=O)OR 2 , C(=O)N(R 2 )2, Si(R 2 )3, N(R 2 )2, NO2, P(=O)(R 2 )2, OSO2R 2 , OR 2 , S(=O)R 2 , S(=O)2R 2 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be selected from the group consisting of one or more 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=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 40 aromatic ring atoms and in each case having one or more R 2 an aromatic or heteroaromatic ring system, or a ring system having 5 to 40 aromatic ring atoms, optionally substituted by a radical, and one or more R 2 an aryloxy or heteroaryloxy group, or a combination of these systems, optionally substituted by a radical; at the same time, two or more adjacent R 1 The substituents may together form a mono- or polycyclic, aliphatic or aromatic ring system; R 2 are the same or different for each occurrence, H, D, F, Cl, Br, I, B (OR 3 )2, CHO, C(=O)R3 , C.R. 3 =C(R 3 )2, CN, C(=O)OR 3 , C(=O)N(R 3 )2, Si(R 3 )3, N(R 3 )2, NO2, P(=O)(R 3 )2, OSO2R 3 , OR 3 , S(=O)R 3 , S(=O)2R 3 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be selected from the group consisting of one or more R 3 radical, where one or more non-adjacent CH groups are replaced by -R 3 C=CR 3 -, -C≡C-, Si(R 3 )2, C=O, C=S, C=NR 3 , -C(=O)O-, -C(=O)NR 3 -, NR 3 , P(=O)(R 3 ), -O-, -S-, SO or SO2, and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2), or having 5 to 40 aromatic ring atoms and in each case having one or more R 3 an aromatic or heteroaromatic ring system, or a ring system having 5 to 40 aromatic ring atoms, optionally substituted by a radical, and one or more R 3 an aryloxy or heteroaryloxy group, or a combination of these systems, optionally substituted by a radical; at the same time, two or more adjacent R 2 The substituents may together form a mono- or polycyclic, aliphatic or aromatic ring system; R 3are identical or different at each occurrence and are H, D, F, or an aliphatic, aromatic and / or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, in which a hydrogen atom may be replaced by F; at the same time, two or more adjacent R 3 The substituents may together form a mono- or polycyclic, aliphatic or aromatic ring system.

[0012] In the context of the present invention, adjacent carbon atoms are carbon atoms that are directly bonded to each other. Furthermore, in the definition of radicals, "adjacent radicals" means that these radicals are bonded to the same carbon atom or adjacent carbon atoms. These definitions apply in particular to the terms "adjacent groups" and "adjacent substituents".

[0013] The expression that two or more radicals may form a ring with each other is understood in the context of the present invention to mean, in particular, that the two radicals are linked to each other by a chemical bond under the formal removal of two hydrogen atoms. This is illustrated by the following scheme: [ka]

[0014] Furthermore, however, the above expression is also understood to mean that if one of the two radicals is hydrogen, the second radical is bonded to the bonded position of the hydrogen atom to form a ring, which is illustrated by the following scheme: [ka]

[0015] In the context of the present invention, a fused aryl group is a group in which two or more aromatic groups are fused to each other through one common side, i.e., fused rings, for example, two carbon atoms belong to at least two aromatic or heteroaromatic rings, such as in naphthalene.In contrast, for example, fluorene is not a fused aryl group in the context of the present invention, since the two aromatic groups in fluorene do not have a common side.

[0016] In the context of the present invention, an aryl group contains 6 to 40 carbon atoms; in the context of the present invention, a heteroaryl group contains 2 to 40 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl or heteroaryl group is understood here to mean a single aromatic ring, i.e. benzene, or a single heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or fused, aryl or heteroaryl groups, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

[0017] In the context of the present invention, an aromatic ring system has 6 to 40 carbon atoms in the ring system. In the context of the present invention, a heteroaromatic ring system contains 1 to 40 carbon atoms and at least one heteroatom in the ring system, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and / or S. In the context of the present invention, an aromatic or heteroaromatic ring system should be understood to mean a system that does not necessarily contain only aryl or heteroaryl groups, but in which two or more aryl or heteroaryl groups can also be interrupted by non-aromatic units (preferably less than 10% of atoms other than H), such as carbon, nitrogen or oxygen atoms or carbonyl groups. For example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, stilbenes, etc., are also considered as aromatic ring systems in the context of the present invention, as are systems in which two or more aryl groups are interrupted, for example, by linear or cyclic, alkyl groups or by silyl groups. Additionally, systems in which two or more aryl or heteroaryl groups are directly bonded to each other, such as biphenyl, terphenyl, quaterphenyl, or bipyridine, are also considered aromatic or heteroaromatic ring systems.

[0018] In the context of this invention a cyclic alkyl, alkoxy or thioalkoxy group is taken to mean a monocyclic, bicyclic or polycyclic group.

[0019] In the context of the present invention, C1-C alkoxy groups, in which individual hydrogen atoms or CH2 groups may be substituted by the above-mentioned groups, are also included. 20The alkyl group in the formula (I) is, for example, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hepta- 1-yl, 1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl, 1,1-dimethyl-n-hexadece-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-oct-1-yl, 1,1-diethyl-n-dec-1-yl, 1, It is understood to mean 1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl, 1,1-diethyl-n-hexadece-1-yl, 1,1-diethyl-n-octadec-1-yl, 1-(n-propyl)cyclohex-1-yl, 1-(n-butyl)cyclohex-1-yl, 1-(n-hexyl)cyclohex-1-yl, 1-(n-octyl)cyclohex-1-yl and 1-(n-decyl)cyclohex-1-yl radicals. Alkenyl groups are understood to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl.An alkynyl group is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. C1-C. 40 An alkoxy group is taken to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy.

[0020] Aromatic or heteroaromatic ring systems, which have 5 to 40 aromatic ring atoms, which in each case may be substituted by the abovementioned radicals and which may be bonded to the aromatic or heteroaromatic system in any desired position, are understood to mean, for example, radicals derived from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzofluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenylene, fluorene, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, Carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, Isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazapyrylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, and benzothiadiazole.

[0021] In a preferred configuration, the compound of the present invention may form a structure of formula (II). [ka] During the ceremony, Symbols X, Y, L 1 , L 2 , Q 1 and Q 2 has the meaning given above, especially in formula (I).

[0022] Further, in formula (I) or (II), not more than two of the X groups are N, preferably not more than one of the X groups is N, and preferably all X are CR 1 where X denotes the CR 1 Preference is given to compounds characterized in that of the groups, preferably at most 4, more preferably at most 3 and particularly preferably at most 2 are not CH groups.

[0023] Furthermore, in formula (I) and / or (II), R of the X group 1 This may be the case where the radical does not form a fused ring system with the ring atoms of the benzofuran and / or benzothiophene structure. 1 Any R that may be attached to a radical 2 , R 3 In formula (I) and / or (II), R of the X group includes the formation of a fused ring system with the substituent. 1It is preferred that the radicals do not form ring systems with the ring atoms of the benzofuran and / or benzothiophene structures. 1 Any R that may be attached to a radical 2 , R 3 The formation of a ring system with the substituents is included.

[0024] Preferably, the compound of the present invention may comprise the structure of formula (Ia): [ka] In the formula, the symbols Y and R 1 , L 1 , L 2 , Q 1 and Q 2 has the meaning given above, in particular in formula (I) and / or (II), and q is 0, 1 or 2, preferably 0 or 1.

[0025] In a further configuration, the compound of the present invention may comprise the structure of formula (IIa): [ka] In the formula, the symbols Y and R 1 , L 1 , L 2 , Q 1 and Q 2 has the meaning given above, in particular in formula (I) and / or (II), and q is 0, 1 or 2, preferably 0 or 1.

[0026] Furthermore, in formula (Ia) and / or (IIa), R 1 This may be the case where the substituents do not form a fused ring system with the ring atoms of the benzofuran and / or benzothiophene structure. 1 Any R that may be attached to a radical 2 , R 3 In formula (Ia) and / or (IIa), R of the benzofuran and / or benzothiophene structure includes the formation of a fused ring system with the substituent.1 It is preferred that the substituents do not form ring systems with the ring atoms of the benzofuran and / or benzothiophene structures. 1 Any R that may be attached to a radical 2 , R 3 The formation of a ring system with the substituents is included.

[0027] In a preferred embodiment, the compound comprising the structure of formula (I), (II) and / or (IIa) can be represented by the structure of formula (I), (II) and / or (IIa), and is particularly preferably a compound of formula (I), (Ia), (II) and / or (IIa). Preferably, the compound comprising the structure of formula (I), (Ia), (II) and / or (IIa) has a molecular weight of less than 5000 g / mol, preferably less than 4000 g / mol, particularly preferably less than 3000 g / mol, especially preferably less than 2000 g / mol, and most preferably less than 1200 g / mol.

[0028] A further feature of the preferred compounds of the invention is that they are sublimable. These compounds generally have a molar mass of less than about 1200 g / mol.

[0029] Q 1 and Q 2 The group is an electron transport group. These groups are well known in the art and facilitate a compound's ability to transport and / or conduct electrons.

[0030] Furthermore, the compounds of formula (I) may comprise, in formula (I), (II), (Ia) and / or (IIa), Q 1 and / or Q 2 A surprising advantage is shown when the group comprises at least one structure selected from the group pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and / or benzimidazole.

[0031] More preferably, preferably Q 1 and / or Q2 At least one, and preferably both, of the groups is a heteroaromatic ring system having 5 to 24 ring atoms, where the ring atoms include at least one nitrogen atom and the ring system is formed from one or more R 1 Radical (R 1 has the meaning given above, in particular in formula (I),

[0032] In a further embodiment, Q is particularly as described in formula (I), (II), (Ia) and / or (IIa). 1 and / or Q 2 At least one, and preferably both, of the groups is a heteroaromatic ring system (wherein the ring atoms include 1 to 4 nitrogen atoms and the ring system contains one or more R 1 Radical (R 1 may also be the case where is optionally substituted by) having the meanings given above, in particular in formula (I).

[0033] Furthermore, Q as described in particular in formula (I), (II), (Ia) and / or (IIa) 1 and / or Q 2 At least one, and preferably both, of the groups have 6 to 10 ring atoms and one or more R 1 Radical (R 1 has the meaning given above, in particular in formula (I), being a heteroaromatic ring system, optionally substituted by.

[0034] Preference is given to Q as described in particular in formula (I), (II), (Ia) and / or (IIa) 1 and / or Q 2 Groups may be selected from structures of formula (Q-1), (Q-2) and / or (Q-3). [ka] In the formula, the symbols X and R 1 has the meaning given above, especially in formula (I), the dotted line indicates the point of attachment, and Ar 1has 6 to 40 carbon atoms and, in each case, one or more R 2 Aromatic or heteroaromatic ring systems, optionally substituted by radicals, having 5 to 60 aromatic ring atoms and one or more R 2 an aryloxy group, optionally substituted by a radical, or an aryloxy group having 5 to 60 aromatic ring atoms, and in each case one or more R 2 an aralkyl group (wherein two or more adjacent R 1 and / or R 2 The substituents may optionally be monocyclic or polycyclic, aliphatic ring systems (which may include one or more R 3 may be substituted by radicals, where R 2 and R 3 has the meaning given above, especially in formula (I),

[0035] In a further embodiment, Q is especially as shown in formula (I), (II), (Ia) and / or (IIa). 1 and / or Q 2 The group is selected from structures of formula (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12) and / or (Q-13). [ka] [ka] In the formula, the symbol Ar 1 and R 1 has the meaning described above, especially in formula (I) and (Q-1), the dotted line indicates the point of connection and l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2, m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and n is 0, 1, 2 or 3, preferably 0 or 1.

[0036] Furthermore, Q as shown in particular in formula (I), (II), (Ia) and / or (IIa) 1and / or Q 2 The group may be in the case selected from the structures of formula (Q-14), (Q-15), (Q-16) and / or (Q-17). [ka] In the formula, the symbol Ar 1 and R 1 has the meaning described above, especially in formulas (I) and (Q-1), the dotted line indicates the point of connection, and m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and n is 0, 1, 2 or 3, preferably 0 or 1.

[0037] Preferably, the symbol Ar 1 is an aryl or heteroaryl radical in which the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is bonded directly (i.e. via an aromatic or heteroaromatic group) to the respective atom of a further group (e.g. a carbon or nitrogen atom of the groups (Q-1) to (Q-17) shown above).

[0038] In a further preferred embodiment of the present invention, Ar 1 are identical or different at each occurrence and are an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably an aromatic ring system having 6 to 12 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 aromatic ring atoms, and in each case 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, in particular in formula (I). 1The radicals of the group are selected from the group consisting of phenyl, ortho-, meta-, or para-biphenyl, terphenyl, particularly branched terphenyl, quaterphenyl, particularly branched quaterphenyl, 1-, 2-, 3-, or 4-fluorenyl, 1-, 2-, 3-, or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3-, or 4-dibenzofuranyl, 1-, 2-, 3-, or 4-dibenzothienyl, and 1-, 2-, 3-, or 4-carbazoyl, each of which may be one or more of R 2 The radicals may be substituted, but are preferably unsubstituted.

[0039] Advantageously, Ar of formula (Q-1) to (Q-17) 1 has 6 to 12 aromatic ring atoms and one or more R 2 is an aromatic ring system, optionally substituted, but preferably unsubstituted, by a radical, where R 2 may have the meaning given above, especially in formula (I).

[0040] Preferably, R in formulas (Q-1) to (Q-17) 2 The radical is R 2 The aryl or heteroaryl group Ar to which the radical is attached 1 does not form a main fused ring with the ring atoms of R 2 Any R that may be attached to a radical 3 This includes forming a fused ring system together with the substituents.

[0041] Furthermore, the compounds of formula (I), (II), (Ia) and / or (IIa) may further comprise Q 1 and / or Q 2 Surprising advantages are shown where the groups are selected from the structures of formula (Q-18), (Q-19), (Q-20), (Q-21), (Q-22), (Q-23), (Q-24), (Q-25), (Q-26), (Q-27) and / or (Q-28). [ka] In the formula, the symbol R 1has the meaning given above, especially in formula (I), and the dotted line indicates the point of connection.

[0042] In a preferred embodiment, in the above formulae, in particular in formulae (I), (Ia), (II) and / or (IIa), Q 1 Group and Q 2 The group is selected from the groups of formulae (Q-1) to (Q-13).

[0043] In a further embodiment, in the above formulae, particularly in formulae (I), (Ia), (II) and / or (IIa), Q 1 Group and Q 2 The group is selected from the groups of the formulae (Q-14) to (Q-17).

[0044] Furthermore, in the above formulae, particularly in formulae (I), (Ia), (II) and / or (IIa), Q 1 Group and Q 2 In some cases, the group may be selected from the groups of formulae (Q-18) to (Q-28).

[0045] Furthermore, in the above formulae, particularly in formulae (I), (Ia), (II) and / or (IIa), Q 1 , Q 2 One of the groups may be selected from the groups of formulae (Q-1) to (Q-13), and Q 1 , Q 2 One of the groups may be selected from the groups of formulae (Q-14) to (Q-17).

[0046] Furthermore, in the above formulae, particularly in formulae (I), (Ia), (II) and / or (IIa), Q 1 , Q 2 one of the groups is selected from the groups of formulae (Q-1) to (Q-13), and Q 1 , Q 2 It may also be the case that one of the groups is selected from the groups of formulae (Q-18) to (Q-28).

[0047] Furthermore, in the above formulae, particularly in formulae (I), (Ia), (II) and / or (IIa), Q 1 , Q2 one of the groups is selected from the groups of formulae (Q-14) to (Q-17), and Q 1 , Q 2 It may also be the case that one of the groups is selected from the groups of formulae (Q-18) to (Q-28).

[0048] In a further configuration, the electron transport group Q 1 and Q 2 are identical in the above formulae, in particular in formulae (I), (Ia), (II) and / or (IIa).

[0049] In addition, the electron transport group Q 1 and Q 2 may be the case where are not identical in the above formulae, in particular in formulae (I), (Ia), (II) and / or (IIa).

[0050] X is CR 1 or the aromatic and / or heteroaromatic groups are R 1 When substituted by a substituent, these R 1 The substituents are preferably H, D, F, CN, N(Ar 1 )2, C(=O)Ar 1 , P(=O)(Ar 1 )2, a straight chain alkyl or alkoxy group having 1 to 10 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, each of which may be selected from the group consisting of one or more R 2 radicals, in which one or more non-adjacent CH groups may be replaced by O and one or more hydrogen atoms may be replaced by D or F), having 5 to 24 aromatic ring atoms, in each case one or more R 2 an aromatic or heteroaromatic ring system or a ring system having 5 to 25 aromatic ring atoms, which may be substituted by a radical, but is preferably unsubstituted, and which has one or more R 2At the same time, two R bonded to the same carbon atom or adjacent carbon atoms are selected from the group consisting of aralkyl and heteroaralkyl groups, each of which may be substituted by a radical; 1 The substituents are monocyclic or polycyclic, and one or more R 1 It is optionally possible to form an aliphatic, aromatic, or heteroaromatic ring system, which may be substituted with the radical. 1 The radicals may have the meanings described above, in particular in structure (Q-1). 1 denotes an aryl or heteroaryl radical, and the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system may be a ring system having a respective atom of a further group (e.g., N(Ar 1 )2, C(=O)Ar 1 , P(=O)(Ar 1 ) is bonded directly to two carbon, nitrogen, or phosphorus atoms) through an aromatic or heteroaromatic group.

[0051] More preferably, these R 1 The substituents are H, D, F, CN, N(Ar 1 ) 2, a straight-chain alkyl group having 1 to 8 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably having 3 or 4 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably having 2, 3 or 4 carbon atoms (each of which may be selected from the group consisting of one or more R 2 an aromatic or heteroaromatic ring system (each of which may be substituted by one or more R radicals, but is preferably unsubstituted) having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, and more preferably having 6 to 13 aromatic ring atoms; 2 radicals, but preferably unsubstituted; and at the same time, optionally, two R 1 The substituents may be one or more R 2The radicals may form a monocyclic or polycyclic, aliphatic ring system which may be substituted, but is preferably unsubstituted. Ar 1 The radicals may have the meanings given above, in particular the structure (Q-1). 1 denotes an aryl or heteroaryl radical, and the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system may be a ring system having a respective atom of a further group (e.g., N(Ar 1 ) is bonded directly to the nitrogen atoms of the two groups, that is, via an aromatic or heteroaromatic group.

[0052] Most preferably, R 1 The substituents are H and an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably having 6 to 13 aromatic ring atoms (each of which may be one or more R 2 The suitable R 1 Examples of substituents are selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, especially branched terphenyl, quaternary phenyl, especially branched quaternary phenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, 1-, 2-, 3- or 4-carbazolyl, each of which may be selected from the group consisting of one or more R 2 The radicals may be substituted, but are preferably unsubstituted.

[0053] Furthermore, in the structures of formulae (I), (Ia), (II), (IIa) and / or (Q-1) to (Q-28), at least one R 1 and / or Ar 1 The radical is of the formula (R 1 -1)~(R 1 -79). [ka] [ka] [ka] [ka] [ka] where the symbols used are as follows: Y is O, S or NR 2 , preferably O or S; i, independently at each occurrence, is 0, 1, or 2; j is independently at each occurrence 0, 1, 2 or 3; h is, independently at each occurrence, 0, 1, 2, 3, or 4; g, independently at each occurrence, is 0, 1, 2, 3, 4, or 5; R 2 may have the meaning given above, in particular in formula (I), and The dotted lines indicate the connection locations.

[0054] Preferably, the formula (R 1 -1)~(R 1 -79) such that the sum of the indices g, h, i and j in the structure is in each case 3 or less, preferably 2 or less, and more preferably 1 or less.

[0055] Preferably, L and / or L 2 The group is an electron transport group, Q 1 and / or Q 2and may form a through-conjugation with the dibenzofuran structure (Y=O) of formula (I), (Ia), (II) and / or (IIa). The direct conjugation of an aromatic or heteroaromatic system is formed as soon as a direct bond is formed between adjacent aromatic or heteroaromatic rings. Further bonds between the above-mentioned conjugated groups, for example via sulfur, nitrogen or oxygen atoms or carbonyl groups, do not impair the conjugation. In the case of a fluorene system, two aromatic rings are directly bonded, where the SP at the 9-position is 3 The -hybridized carbon atom prevents fusion of these rings, but conjugation is possible. This is because the 9-SP 3 -hybridized carbon atom is not necessarily an electron transport group Q 1 and / or Q 2 and dibenzofuran structures (Y=O) and / or dibenzothiophene structures (Y=S). In contrast, in the case of spirobifluorene structures, the electron transport group Q 1 and / or Q 2 Direct conjugation can be formed when the bond between the dibenzofuran structures (Y=O) and / or dibenzothiophene structures (Y=S) of formula (I), (Ia), (II) and / or (IIa) is via the same phenyl group in the spirobifluorene structure or via phenyl groups in the spirobifluorene structure that are directly bonded to each other and are in the same plane. Electron transport group Q 1 and / or Q 2 and the bond between the dibenzofuran structure (Y=O) and / or the dibenzothiophene structure (Y=S) of the formula (I), (Ia), (II) and / or (IIa) is a bond between the 9-position SP 3 When the phenyl groups are bonded via different -hybridized carbon atoms, conjugation is prevented.

[0056] In a further preferred embodiment of the invention, L 1 and / or L 2 are the same or different at each occurrence, have a single bond or 5 to 24 aromatic ring atoms, and are one or more R 2More preferably, L is an aromatic or heteroaromatic ring system, optionally substituted by a radical. 1 and / or L 2 are identical or different at each occurrence and are a single bond or an aromatic ring system having 6 to 12 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 aromatic ring atoms, and in each case, 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, in particular in formula (I). Furthermore, the symbol L 1 and / or L 2 are the same or different at each occurrence and are a single bond or an aryl or heteroaryl radical, and the aromatic or heteroaromatic groups of the aromatic or heteroaromatic ring system are bonded to the respective atoms of the other groups directly, i.e. via an atom of the aromatic or heteroaromatic group. Most preferably, L 1 and / or L 2 is a single bond. A suitable aromatic or heteroaromatic ring system L 1 and / or L 2 Examples of are ortho-, meta-, or para-phenylene, biphenyl, fluorene, pyridine, pyrimidine, triazine, dibenzofuran, and dibenzothiophene (each of which may contain one or more R 2 The radicals may be substituted, but are preferably unsubstituted.

[0057] Preferably, the compound comprises a structure of formula (I), (II), (Ia) and / or (IIa), wherein at least one L of formula (I), (IIa) and / or (IIb) is 1 and / or L 2 The group is a bond and / or a group selected from the formulae (L-1) to (L-70). [ka] [ka] [ka] [ka] [ka] wherein in each case the dotted line indicates the point of attachment, subscript l is 0, 1 or 2, subscript g is 0, 1, 2, 3, 4 or 5, j is independently 0, 1, 2 or 3 at each occurrence; h is independently 0, 1, 2, 3 or 4 at each occurrence; and Y is O, S or NR 2 is preferably O or S; and R 2 has the meaning given above, especially in formula (I).

[0058] Preferably, the sum of the subscripts l, g, h and j in the structures of formulae (L-1) to (L-70) may be in each case up to 3, preferably up to 2, more preferably up to 1.

[0059] Advantageously, the compounds of the invention comprising at least one structure of formula (I), (Ia), (II) and / or (IIa) may be in the case of not containing carbazole and / or triarylamine groups. More preferably, the compounds of the invention do not contain hole transporting groups. Hole transporting groups are known to those skilled in the art and in many cases these groups are carbazole, indenocarbazole, indolocarbazole, arylamine or diarylamine structures.

[0060] In a further preferred embodiment of the invention, R 2are 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 10 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms, more preferably 5 to 13 aromatic ring atoms, which may be substituted, but are preferably unsubstituted, by one or more alkyl groups each having 1 to 4 carbon atoms.

[0061] The compounds of the present invention are preferably aromatic or heteroaromatic R 1 or R 2 or Ar 1 When substituted by groups, it is preferred that they do not have aryl or heteroaryl groups with two or more aromatic 6-membered rings directly fused to each other. More preferably, the substituents do not contain any aryl or heteroaryl groups with 6-membered rings directly fused to each other. The reason for this is that the triplet energy of these structures is low. Although fused aryl groups with two or more aromatic 6-membered rings directly fused to each other, phenanthrene and triphenylene are suitable in the present invention because they have high triplet levels.

[0062] Examples of suitable compounds of the present invention are those of formulas 1-111 shown below: [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0063] Preferred forms of the compounds of the invention are described in detail and specifically in the Examples, and these compounds can be used alone or in combination with further compounds for all purposes of the invention.

[0064] The preferred embodiments described above can be combined with one another if desired, provided that the conditions specified in claim 1 are met. In a particularly preferred embodiment of the invention, the preferred embodiments described above are applied simultaneously.

[0065] The compounds of the invention can in principle be prepared in a variety of ways, however the methods described below have been found to be particularly suitable.

[0066] Accordingly, the present invention further provides a method for preparing a compound comprising the structure of formula (I) in which a compound comprising at least one electron transport group is combined with a compound comprising at least one benzofuran and / or benzothiophene radical in a coupling reaction.

[0067] Suitable compounds having an electron transport group are often commercially available, whereby the starting compounds detailed in the examples can be obtained by known methods, as referenced therein.

[0068] These compounds can be reacted with further aryl compounds in known coupling reactions, the conditions necessary 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.

[0069] Particularly suitable and preferred all coupling reactions leading to CC and / or CN bond formation are those due to Buchwald, Suzuki, Yamamoto, Stille, Heck, Negishi, Sonogashira and Hiyama. These reactions are well known and the examples provide further guidance to the skilled artisan.

[0070] In all of the synthetic schemes that follow, the compounds are shown with a small number of substituents to simplify the structures, and this does not preclude the presence of additional substituents as desired in the process.

[0071] Exemplary embodiments are shown in the following schemes, without these being intended to be limiting in any way: The constituent steps of the individual schemes can be combined with each other if desired. [ka]

[0072] In Schemes 1 and 2, Q 1 and / or Q 2 The radicals listed under the definition are electron conducting groups as described above.

[0073] The methods shown for the synthesis of the compounds of the present invention should be considered as illustrative only: a person skilled in the art may develop alternative synthetic routes within the scope of his / her common knowledge in the art.

[0074] 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 the preparation of the compounds of the invention. Further information can be found in the Examples.

[0075] By these methods, optionally followed by purification, such as recrystallization or sublimation, the compounds of the present invention comprising the structure of formula (I) can be obtained in high purity, preferably greater than 99% ( 1 H-NMR and / or HPLC).

[0076] The compounds of the invention may also have suitable substituents, such as relatively long alkyl groups (about 4 to 20 carbon atoms), especially branched alkyl groups, or optionally substituted aryl groups, such as xylyl, mesityl or branched terphenyl or quaterphenyl groups, which provide solubility in standard organic solvents, such as toluene or xylene, at room temperature and at sufficient solubility concentrations to allow the compounds to be processed in solution. These soluble compounds are particularly suitable for processing in solution, for example by printing methods. Moreover, it must be emphasized that the compounds of the invention, which comprise at least one structure of formula (I), already have increased solubility in these solvents.

[0077] The compounds of the present invention can also be mixed with polymers. It is also possible to covalently incorporate these compounds into polymers. This is especially 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 find use as monomers for producing the corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably carried out via halogen or boronic acid functional groups, or via polymerizable groups. It is possible to further crosslink the polymer via such groups. The compounds and polymers of the present invention can be used in the form of crosslinked or non-crosslinked layers.

[0078] The present invention further provides polymers, oligomers or dendrimers comprising one or more structures of formula (I) or compounds of the invention as detailed above, in which there are one or more bonds to the compounds of the invention or to the structures of formula (I) to the oligomer, polymer or dendrimer. By linking the structures or compounds of formula (I), they therefore 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 not conjugated. The oligomers or polymers may be linear, branched or dendritic. For the repeat units of the compounds of the invention in the oligomers, dendrimers and polymers, the same preferred forms apply as described above.

[0079] To prepare oligomers or polymers, the monomers of the 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 the range of 0.01 to 99.9 mol %, preferably 5 to 90 mol %, more preferably 20 to 80 mol %. Suitable and preferred comonomers forming the polymer backbone are fluorenes (for example according to EP 842208 or WO 2000 / 022026), spirobifluorenes (for example according to EP 707020, EP 894107 or WO 2006 / 061181), paraphenylenes (for example according to WO 92 / 18552), carbazoles (for example according to WO 2004 / 070772 or WO 2004 / 113468), thiophenes ( For example, according to EP1028136), dihydrophenanthrenes (for example, according to WO2005 / 014689), cis- and trans-indenofluorenes (for example, according to WO2004 / 041901 or WO2004 / 113412), ketones (for example, according to WO2005 / 040302), phenanthrenes (for example, according to WO2005 / 104264 or WO2007 / 017066), or a plurality of these units. The polymers, oligomers and dendrimers may also contain further units, for example hole transport units, in particular those based on triarylamine, and / or electron transport units.

[0080] Furthermore, of particular interest are compounds of the invention characterized by a high glass transition temperature. In this connection, preference is given to compounds of the 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 especially preferably at least 150°C.

[0081] To process the compounds of the invention in liquid phase, for example by spin-coating or printing methods, a formulation of the compounds of the invention is required. These formulations can 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 ... Examples of the solvent include cyclohexane, cyclohexanediol ...

[0082] Therefore, the present invention also relates to a formulation comprising the compound of the present invention and at least one further compound.The further compound is, for example, a solvent, in particular one of the above-mentioned solvents or a mixture of these solvents.Alternatively, the further compound can be an organic or inorganic compound, for example a light-emitting compound, in particular a phosphorescent dopant, and / or a further matrix material, which are also used in electronic devices.This further compound can also be a polymer.

[0083] 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 that is introduced between the anode and the cathode.Preferably, the organic functional material is selected from the group consisting of fluorescent emitter, phosphorescent emitter, host material, matrix material, electron transport material, electron injection material, hole conducting material, hole injection material, n-dopant, wide band gap material, electron blocking material, and hole blocking material.

[0084] The present invention therefore also relates to a composition comprising at least one compound comprising a structure of formula (I) or the preferred forms described above and below, the preferred forms of which are described above and below, and at least one further matrix material, in a particular embodiment of the present invention, the further matrix material having hole transport properties.

[0085] The present invention further provides compositions comprising at least one compound comprising at least one of the structures of formula (I) or preferred forms described above and below, and at least one wide band gap material, where wide band gap material is understood to mean the material disclosed in US 7,294,849. These systems show particularly advantageous performance data in electroluminescent devices.

[0086] Preferably, the additional compound has a band gap of 2.5 eV or more, preferably 3.0 eV or more, and most preferably 3.5 eV or more. One method of calculating the band gap uses the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

[0087] Molecular orbitals, especially the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), their energy levels and the energy of the lowest triplet state T1 or the lowest excited singlet state S1 of the material are determined using quantum chemical calculations. To calculate metal-free organic substances, first, the structure optimization is performed using the "ground state / semi-empirical / initial spin / AM1 / charge 0 / spin singlet" method. Then, the energy calculation is performed based on the optimized structure. Here, the "TD-SCF / DFT / initial spin / B3PW91" method is used with the "6-31G(d)" basis set (charge 0, spin singlet). For metal-containing compounds, the structure is optimized using the "ground state / Hartree-Fock / initial spin / LanL2MB / charge 0 / spin singlet" method. The energy calculations are performed similarly to the method for organic materials described above, except that the "LanL2DZ" basis set is used for the metal and "6-31G(d)" for the ligand. The HOMO energy level HEh or LUMO energy level LEh is obtained from the energy calculation in Hartree units. This is used to determine the HOMO and LUMO energy levels in electron volts by calibrating with cyclic voltammetry measurements as follows: HOMO(eV)=((HEh*27.212)-0.9899) / 1.1206 LUMO(eV)=((LEh*27.212)-2.0041) / 1.385

[0088] In the context of the present invention, these values ​​are considered to be the HOMO and LUMO energy levels of the material.

[0089] The lowest triplet state T1 is defined as the energy of the triplet state with the lowest energy evident from the quantum chemical calculations given.

[0090] The lowest excited singlet state S1 is defined as the energy of the excited singlet state with the lowest energy evident from the described quantum chemical calculations.

[0091] The method described here is independent of the software package used and will always give the same results. Examples of programs frequently used for this purpose are "Gaussian09W" (Gaussian) and Q-Chem4.1 (Q-Chem).

[0092] The present invention further provides a composition comprising at least one compound comprising at least one structure of formula (I) or the preferred forms described above and below, and at least one phosphorescent emitter, where the term "phosphorescent emitter" is also understood to mean a phosphorescent dopant.

[0093] In a system comprising a matrix material and a dopant, the dopant is understood to mean the component which has the smaller proportion in the mixture. Correspondingly, in a system comprising a matrix material and a dopant, the matrix material is understood to mean the component which has the greater proportion in the mixture.

[0094] Preferred phosphorescent dopants for use in the matrix system, preferably the mixed matrix system, are the preferred phosphorescent dopants specified below.

[0095] The term "phosphorescent dopant" typically encompasses compounds in which emission occurs via a spin-forbidden transition, such as from an excited triplet state, or a state with a higher spin quantum number, such as a quintet state.

[0096] Suitable phosphorescent compounds (= triplet emitters) are compounds that emit light, preferably in the visible range, when appropriately excited, and furthermore contain at least one atom with atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, in particular a metal with this atomic number. The phosphorescent emitters used are preferably compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum. In the context of the present invention, all luminescent compounds containing the above metals are considered as phosphorescent compounds.

[0097] Examples of the above-mentioned illuminants are described in 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, WO No. 6,393,992, filed on May 23, 2012. These can be found in applications WO2010 / 099852, WO2010 / 102709, WO2011 / 032626, WO2011 / 066898, WO2011 / 157339, WO2012 / 007086, WO2014 / 008982, WO2014 / 023377, WO2014 / 094961, WO2014 / 094960, as well as the unpublished applications EP13004411.8, EP14000345.0, EP14000417.7 and EP14002623.8. In general, all phosphorescent complexes as used in the prior art for phosphorescent OLEDs and as further 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 inventive ingenuity.

[0098] Explicit examples of phosphorescent dopants are given in the table below: [ka]

change

change

change

change

change

change

change

[0099] The above-mentioned compound comprising the structure of formula (I) or the preferred form detailed above can be preferably used as an active component in an electronic device. An electronic device is understood to be a device comprising an anode, a cathode, and at least one layer between the anode and the cathode, said layer comprising at least one organic or organometallic compound. Thus, the electronic device of the present invention comprises an anode, a cathode, and an intermediate layer comprising at least one compound comprising the structure of formula (I). Preferred electronic devices here are selected from the group consisting of organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), organic electrical sensors, light emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic plasmonic light emitting devices (DM Koller et al., Nature Pho~nics 2008, 1-4), preferably organic electroluminescent devices (OLEDs, PLEDs), in particular phosphorescent OLEDs containing at least one compound comprising the structure of formula (I). Particularly preferred are organic electroluminescent devices. Active components are generally organic or inorganic materials introduced between the anode and the cathode, such as charge-injecting, charge-transporting or charge-blocking materials, but especially light-emitting materials and matrix materials.

[0100] A preferred embodiment of the present invention is an organic electroluminescent device. The organic electroluminescent device comprises an anode, a cathode and at least one light-emitting layer. In addition to these layers, the organic electroluminescent device may also comprise further layers, for example, in each case, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generating layers and / or organic or inorganic p / n junctions. In this case, one or more hole transport layers can be p-doped, for example with metal oxides such as MoO3 or WO3 or with electron-deficient (per)fluorinated aromatic systems, and / or one or more electron transport layers can be n-doped. Similarly, an intermediate layer, which has, for example, an exciton blocking function and / or controls the charge balance in the organic electroluminescent device, may be introduced between the two light-emitting layers. However, it should be noted that each of these layers does not necessarily have to be present.

[0101] Here, the organic electroluminescent element may comprise one light-emitting layer or may comprise multiple light-emitting layers. If multiple light-emitting layers are present, they preferably have multiple emission maxima over the entire range from 380 nm to 750 nm, so as to produce white light overall, i.e., various light-emitting compounds capable of emitting fluorescence or phosphorescence are used in the light-emitting layers. Particularly preferred are three-layer systems (for basic structures, see, for example, WO2005 / 011013) in which the three layers emit blue, green and orange or red light, or systems with three or more light-emitting layers. The system may be a hybrid structure in which one or more layers emit fluorescence and one or more other layers emit phosphorescence.

[0102] In a preferred embodiment of the present invention, the organic electroluminescent device comprises the compound of the present invention comprising the structure of formula (I) or the preferred embodiments detailed above as a matrix material, preferably as an electron-conducting matrix material, in one or more light-emitting layers, preferably in combination with a further matrix material, preferably a hole-conducting matrix material. In a further preferred embodiment of the present invention, the further matrix material is an electron-transporting compound. Yet in a further preferred embodiment, the further matrix material is a compound with a large band gap that is not or not to a significant extent involved in hole and electron transport in the layer. The light-emitting layer comprises at least one light-emitting compound.

[0103] Suitable matrix materials which can be used in combination with the compounds of formula (I) or according to the preferred embodiments are aromatic ketones; aromatic phosphine oxides; or aromatic sulfoxides or sulfones (for example according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680); triarylamines, in particular monoamines (for example according to WO 2014 / 015935); carbazole derivatives (for example CBP (N,N-biscarbazolylbiphenyl) or carbazole derivatives as disclosed in WO2005 / 039246, US2005 / 0069729, JP2004 / 288381, EP1205527, or WO2008 / 086851; indolocarbazole derivatives (for example according to WO2007 / 063754 or WO2008 / 056746); indenocarbazole derivatives (for example according to WO2010 / 136109 and WO2011 / 000455); azacarbazole derivatives (for example according to EP1617710, EP1617711, EP1731584, JP 2005 / 347160; bipolar matrix materials (for example according to WO2007 / 137725); silanes (for example according to WO2005 / 111172); azaboroles or boronic esters (for example according to WO2006 / 117052); triazine derivatives (for example according to WO2010 / 015306, WO2007 / 063754 or WO2008 / 056746); zinc complexes (for example according to EP652273 or WO2009 / 062578); diazasilol or tetraazasilol derivatives. diazaphosphole derivatives (for example according to WO2010 / 054730); bridged carbazole derivatives (for example according to US2009 / 0136779, WO2010 / 050778, WO2011 / 042107, WO2011 / 088877 or WO2012 / 143080); triphenylene derivatives (for example according to WO2012 / 048781); lactams (for example according to WO2011 / 116865, WO2011 / 137951 or WO2013 / 064206);Or 4-spirocarbazole derivatives (for example according to WO2014 / 094963 or unpublished application EP14002104.9). It is also possible for further phosphorescent emitters, which emit at shorter wavelengths than the actual emitter, to be present in the mixture as co-hosts;

[0104] Preferred co-host materials are triarylamine derivatives, especially monoamines, indenocarbazole derivatives, 4-spirocarbazole derivatives, lactams, and carbazole derivatives.

[0105] Preferred triarylamine derivatives to be used as co-host materials together with the compounds of the present invention are selected from the compounds of the following formula (TA-1): [ka] In the formula, Ar 1 are identical or different at each occurrence and have the meaning given above. 1 The groups may be the same or different at each occurrence and may be any of the groups R 1 -1~R 1 -79 to preferably R 1 -1~R 1 -51 are selected.

[0106] In a preferred embodiment of the compound represented by formula (TA-1), at least one Ar 1 The group is selected from a biphenyl group, which may be an ortho-, meta- or para-biphenyl group. In a further preferred embodiment of the compound of formula (TA-1), at least one Ar group is selected from a fluorene group or a spirobifluorene group, which may be bonded to the nitrogen atom at the 1-, 2-, 3- or 4-position, respectively. In an even further preferred embodiment of the compound of formula (TA-1), at least one Ar group is selected from a fluorene group or a spirobifluorene group, which may be bonded to the nitrogen atom at the 1-, 2-, 3- or 4-position, respectively. 1is selected from a phenylene or biphenyl group which is an ortho-, meta- or para-bonded group and is substituted by a dibenzofuran, benzothiophene or carbazole group, in particular a dibenzofuran group, where the dibenzofuran or benzothiophene group is bonded to the phenylene or biphenyl group via the 1-, 2-, 3- or 4-position and where the carbazole group is bonded to the phenylene or biphenyl group via the 1-, 2-, 3- or 4-position or via a nitrogen atom.

[0107] In a particularly preferred embodiment of the compound of formula (TA-1), one Ar 1 The radical is selected from fluorene or spirobifluorene radicals, in particular from 4-fluorene or 4-spirobifluorene radicals, and one Ar 1 The group is selected from a biphenyl group, in particular a para-biphenyl group, or a fluorene group, in particular a 2-fluorene group, and a third Ar 1 The radicals are selected from para-phenylene or para-biphenyl radicals substituted with a dibenzofuran radical, in particular a 4-dibenzofuran radical, or with a carbazole radical, in particular an N-carbazole radical or a 3-carbazole radical.

[0108] The indenocarbazole derivatives used as co-host materials together with the compounds of the present invention are selected from the compounds of the following formula (TA-2): [ka] In the formula, Ar 1 and R 1 has the indicated meaning given above. 1 A preferred form of the group is the structure R 1 -1~R 1 -79, more preferably R 1 -1~R 1 It is -51.

[0109] A preferred form of the compound of formula (TA-2) is the compound of formula (TA-2a) below: [ka] In the formula, Ar 1 and R 1 has the above-mentioned meaning, where two R 1 The radicals are preferably, identical or different, alkyl radicals having 1 to 4 carbon atoms, in particular a methyl radical, or an aromatic ring system having 6 to 12 carbon atoms, in particular a phenyl radical. More preferably, the two R 1 More preferably, the R bonded to the indenocarbazole basic skeleton in formula (TA-2a) is a methyl group. 1 The substituents are H or a carbazole group which can be bonded to the indenocarbazole base skeleton via the 1-, 2-, 3- or 4-position or via a nitrogen atom, in particular via the 3-position.

[0110] Preferred 4-spirocarbazole derivatives to be used as co-host materials together with the compounds of the present invention are selected from the compounds of formula (TA-3): [ka] In the formula, Ar 1 and R 1 has the meaning given above. 1 A preferred form of the group is the structure (R 1 -1)~(R 1 -79), more preferably R 1 -1~R 1 It is -51.

[0111] A preferred form of the compound of formula (TA-3) is the compound of formula (TA-3a): [ka] In the formula, Ar 1 and R 1 has the meaning given above. 1 A preferred form of the group is the structure (R 1-1)~(R 1 -79), more preferably R 1 -1~R 1 It is -51.

[0112] Preferred lactams for use as co-host materials together with the compounds of the present invention are selected from compounds of formula (LAC-1): [ka] In the formula, R has the meaning given above.

[0113] A preferred form of the compound of formula (LAC-1) is the compound of formula (LAC-1a): [ka] In the formula, R 1 has the meaning given above. 1 is preferably identical or different at each occurrence and is H or has 5 to 40 aromatic ring atoms and one or more radicals R 2 an aromatic or heteroaromatic ring system, optionally substituted with R 2 has the meaning given above, in particular in formula (I). Most preferably, R 1 The substituents are selected from H and 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, each of which is substituted with one or more non-aromatic radicals R 2 The appropriate R is selected from the group consisting of aromatic or heteroaromatic ring systems, which may be substituted, but are preferably unsubstituted. 1 Examples of substituents are phenyl, ortho-, meta- or para-biphenyl, terphenyl, especially branched terphenyl, quaternary phenyl, especially branched quaternary phenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, 1-, 2-, 3- or 4-carbazolyl (each of which may be selected from the group consisting of one or more R2 The appropriate structure R is selected from the group consisting of: 1 R-1 to R-79, more preferably R 1 -1~R 1 It is the same structure as shown for -51.

[0114] It is also preferred to use mixtures of different matrix materials, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material, as well as mixtures of charge-transporting matrix materials with electrically inactive matrix materials which are not involved to any significant extent, if at all, in the charge transport, as described, for example, in WO 2010 / 108579.

[0115] Furthermore, the use of a mixture of two or more triplet emitters and matrices is preferred, where a triplet emitter with a shorter wavelength emission spectrum acts as a co-matrix for a triplet emitter with a longer wavelength emission spectrum.

[0116] More preferably, the compounds of the present invention comprising the structure of formula (I) in a preferred form can be used as a matrix material in an organic electronic device, in particular an organic electroluminescent device, such as an OLED or an OLEC, in an emitting layer, in which the matrix material comprising the structure of formula (I) or the preferred forms described above and below is present in the electronic device in combination with one or more dopants, preferably phosphorescent dopants.

[0117] In this case, the ratio of the matrix material in the light-emitting layer is 50.0 to 99.9 volume %, preferably 80.0 to 99.5 volume %, and more preferably 92.0 to 99.5 volume % for the fluorescent-emitting layer, and 85.0 to 97.0 volume % for the phosphorescent-emitting layer.

[0118] Correspondingly, the proportion of the dopant is 0.1 to 50.0 volume %, preferably 0.5 to 20.0 volume %, and more preferably 0.5 to 8.0 volume % for the fluorescent-emitting layer, and 3.0 to 15.0 volume % for the phosphorescent-emitting layer.

[0119] The light-emitting layer of the organic electroluminescent device may also be a system that contains several matrix materials (mixed matrix system) and / or several dopants. In this case, too, the dopant is generally the material that has a smaller proportion in the system, and the matrix material is the material that has a larger proportion in the system. However, in individual cases, the proportion of a single matrix material in the system may be smaller than the proportion of a single dopant.

[0120] In a further preferred embodiment of the invention, the compound comprising the structure of formula (I) or the preferred embodiments described above and below is used as one component of a mixed matrix system. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. In this case, it is preferred that one of the two materials is a material with hole transport properties and the other material is a material with electron transport properties. However, the desired electron transport and hole transport properties of the mixed matrix component may also be mainly or completely incorporated in a single mixed matrix component, in which case the further mixed matrix component(s) fulfills the other function. The two different matrix materials may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1 and most preferably 1:4 to 1:1. It is preferred to use the mixed matrix system in a phosphorescent organic electroluminescent device. More detailed information on the mixed matrix system is given, inter alia, in application WO2010 / 108579.

[0121] The present invention further provides an electronic device, preferably an organic electroluminescent device, comprising, as electronically conductive compound in one or more electronically conductive layers, one or more of the compounds according to the invention and / or at least one oligomer, polymer or dendrimer according to the invention.

[0122] The cathode is preferably a metal, metal alloy or multilayer structure composed of various metals, such as alkaline earth metals, alkali metals, metals of the main group or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.), having a low work function. Also suitable are alloys composed of alkali metals or alkaline earth metals and silver, for example alloys composed of magnesium and silver. In the case of multilayer structures, in addition to the metals, further metals with a relatively high work function, such as Ag, can also be used, in which case combinations of metals such as Mg / Ag, Ca / Ag or Ba / Ag are commonly used. Also, a thin intermediate layer, preferably composed of a material with a high dielectric constant, can be introduced between the metal cathode and the organic semiconductor. Examples of suitable materials for this purpose are fluorides of alkali metals or alkaline earth metals, and also the corresponding oxides or carbonates (e.g. LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Also useful for this purpose are organic alkali metal complexes, such as Liq (lithium quinolinate).The layer thickness of this layer is preferably 0.5 to 5 nm.

[0123] The anode is preferably a material with a high work function. The anode preferably has a work function greater than 4.5 eV against vacuum. Firstly, metals with high redox potential, such as Ag, Pt or Au, are suitable for this purpose. Secondly, metal / metal oxide electrodes (e.g. Al / Ni / NiOx, Al / P~x) are also preferred. For some applications, at least one electrode must be transparent or partially transparent to allow either the irradiation of the organic material (O-SC) or the emission of light (OLED / PLED, O-laser). Here, preferred anode materials are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Furthermore, preferred are doped conductive organic materials, in particular doped conductive polymers, such as PEDOT, PANI or derivatives of these polymers. It is further preferred when a p-type doped hole transport material is applied to the anode as a hole injection layer, in which case suitable p-dopants are metal oxides, such as MoO3 or WO3, or electron-deficient (per)fluorinated aromatic systems. Further suitable p-dopants are HAT-CN (hexacyanohexaazatriphenylene) or the compound NPD9 from Novaled. Such a layer simplifies hole injection into materials with a low HOMO, i.e. a large HOMO in magnitude.

[0124] In the further layers, any material used in the prior art for such layers can generally be used, and the skilled person can combine any of these materials with the materials according to the invention in an electronic device without inventive ingenuity.

[0125] Since the service life of such components is significantly shortened by the presence of water and / or air, the components are accordingly structured (depending on the application), provided with contacts and finally hermetically sealed.

[0126] Further preferred are electronic devices, in particular organic electroluminescent devices, characterized in that one or more layers are applied by sublimation. -5 Less than millibars, preferably 10 -6 It is applied by vacuum deposition in a vacuum sublimation system at an initial pressure of less than mbar. The initial pressure can be lower or higher, for example 10 -7 Submillibars are also possible.

[0127] Also preferred are electronic devices, in particular organic electroluminescent devices, characterized in that one or more layers are applied by the OVPD (organic vapor phase deposition) method or by means of sublimation of a carrier gas. -5 It is applied at pressures of mbar to 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and further structured (e.g., MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0128] Further preferred are electronic devices, in particular organic electroluminescent devices, characterized in that one or more layers are produced from solution, for example by spin coating or by any printing method, for example by screen printing, flexographic printing, offset printing or nozzle printing, but more preferably by LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble compounds are required, which can be obtained, for example, by suitable substitution.

[0129] Electronic devices, in particular organic electroluminescent devices, can also be produced as hybrid systems by coating one or more layers from solution and one or more other layers by vacuum deposition, for example an emissive layer comprising a compound of formula (I) and a matrix material can be coated from solution and thereto a hole blocking layer and / or an electron transporting layer can be coated by vacuum deposition under reduced pressure.

[0130] These methods are generally known to those skilled in the art and can be readily applied to electronic devices, particularly organic electroluminescent devices, comprising compounds of formula (I) or the preferred forms detailed above.

[0131] The electronic devices, in particular organic electroluminescent devices, according to the present invention are notable for one or more of the following surprising advantages over the prior art:

[0132] 1. Electronic devices, in particular organic electroluminescent devices, comprising a compound, oligomer, polymer or dendrimer having the structure of formula (I) or the preferred forms described above and below, in particular as an electron conducting material, have a very good life span.

[0133] 2. Electronic devices, particularly organic electroluminescent devices, comprising the compound, oligomer, polymer or dendrimer having the structure of formula (I) or the preferred forms described above and below as an electronic conducting material have excellent efficiency, more specifically, the efficiency is higher than that of similar compounds that do not contain the structural unit of formula (I).

[0134] 3. The compounds, oligomers, polymers or dendrimers of the present invention having the structure of formula (I) or the preferred forms described above and below, exhibit very high stability and result in compounds with very long lifetimes.

[0135] 4. The use of compounds, oligomers, polymers or dendrimers having the structure of formula (I) or the preferred forms described above and below makes it possible to avoid the formation of light loss channels in electronic devices, in particular in organic electroluminescent devices, so that these devices are characterized by high PL efficiency and thus high EL efficiency of the emitter, as well as good energy conduction from the matrix to the dopant.

[0136] 5. The use of compounds, oligomers, polymers or dendrimers having the structure of formula (I) or the preferred forms described above and below in layers of electronic devices, in particular organic electroluminescent devices, results in high mobility of electronically conductive structures.

[0137] 6. Compounds, oligomers, polymers or dendrimers having the structure of formula (I) or the preferred forms described above and below are characterized by excellent thermal stability, and compounds having a molecular weight of less than about 1200 g / mol have good sublimability.

[0138] 7. The compounds, oligomers, polymers or dendrimers having the structure of formula (I) or the preferred forms described above and below have excellent glass film forming properties.

[0139] 8. Compounds, oligomers, polymers or dendrimers having the structure of formula (I) or the preferred forms described above and below form very good films from solution.

[0140] 9. Compounds, oligomers, polymers or dendrimers comprising the structure of formula (I) or the preferred forms described above and below have surprisingly high triplet levels T1, in particular for compounds used as electronically conductive materials.

[0141] These above mentioned advantages are not accompanied by degradation of other electronic properties.

[0142] The compounds and mixtures of the present invention are suitable for use in electronic devices. Electronic devices are understood to mean devices that contain at least one layer that contains at least one organic compound. Devices may also contain layers that contain inorganic materials or are entirely made of inorganic materials.

[0143] The present invention therefore provides the use of the compounds or mixtures according to the invention in electronic devices, in particular organic electroluminescent devices.

[0144] The present invention further provides the use of a compound according to the invention and / or an oligomer, polymer or dendrimer according to the invention as hole blocking material, electron injection material and / or electron transport material in an electronic device.

[0145] The present invention further provides an electronic device comprising at least one of the compounds or mixtures of the invention as shown above. In this case, the preferred above-mentioned compounds also apply to the electronic device.

[0146] In a further embodiment of the present invention, the organic electroluminescent device of the present invention does not include a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, which means that the light-emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO2005 / 053051.Furthermore, the same or similar metal complex as 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 WO2009 / 030981.

[0147] The compounds of the present invention can also be used in hole blocking or electron transport layers. This is especially true for the compounds of the present invention that do not have a carbazole structure. They may also be preferably substituted with one or more further electron transport groups, such as benzimidazole.

[0148] In the further layer of the organic electroluminescent device of the present invention, any material as 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 devices in combination with the compound of the present invention according to formula (I) or preferred form without inventive ingenuity.

[0149] The compounds of the invention generally have very good properties when used in organic electroluminescent devices.In particular, when the compounds of the invention are used in organic electroluminescent devices, the lifetime is significantly better than that of similar compounds according to the prior art.At the same time, other properties of organic electroluminescent devices, especially efficiency and voltage, are also better or at least comparable.

[0150] 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 may 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.

[0151] 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 for the preferred features of the present invention. Similarly, features of non-essential combinations can be used separately (and not in combination).

[0152] It should be noted that many features, and in particular features of the preferred forms of the invention, are inventive in themselves and should not be considered as being solely part of the form of the invention, and that these features may claim independent protection in addition to or instead of the invention as currently claimed.

[0153] The technical teachings disclosed with the present invention may be abstracted and combined with other embodiments.

[0154] The present invention will now be described in more detail with reference to the following examples, without however limiting the invention thereto.

[0155] Using the following detailed description, one skilled in the art can, without inventive elaboration, further manufacture the electronic device of the present invention and thereby practice the present invention throughout the scope of the claims.

[0156] Working Example The following syntheses are carried out under a protective gas atmosphere in dry solvents unless otherwise stated. Solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. Compounds known from the literature are listed in each case with the corresponding CAS number.

[0157] Synthesis Example a) 6-bromo-2-fluoro-2'-methoxybiphenyl [ka] 200 g (664 mmol) of 1-bromo-3-fluoro-2-iodobenzene, 101 g (664 mmol) of 2-methoxyphenylboronic acid and 137.5 g (997 mmol) of sodium tetraborate are dissolved in 1000 ml of THF and 600 ml of water and degassed. 9.3 g (13.3 mmol) of bis(triphenylphosphine)palladium(II) chloride and 1 g (20 mmol) of hydrazinium hydroxide are added. The reaction mixture is then stirred for 48 hours under a protective gas atmosphere at 70 ° C. The cooled solution is added with toluene, washed repeatedly with water and concentrated to dryness. The product is purified by column chromatography on silica gel with toluene / heptane (1:2). Yield: 155 g (553 mmol), 83% of theory.

[0158] The following compounds are prepared in a similar manner: [ka]

[0159] b) 6'-bromo-2'-fluorobiphenyl-2-ol [ka] 112 g (418 mmol) of 6-bromo-2-fluoro-2'-methoxybiphenyl are dissolved in 2 L of dichloromethane and cooled to 5 ° C. 41.01 ml (431 mmol) of boron tribromide are added dropwise to this solution within 90 minutes and stirring of the mixture is carried out overnight. Then the mixture is gradually combined with water, the organic phase is washed three times with water, dried over Na2SO4, concentrated on a rotary evaporator and purified by chromatography. Yield: 104 g (397 mmol), 98% of theory.

[0160] The following compounds are prepared in a similar manner: [ka]

[0161] c) 1-Bromodibenzofuran [ka] 111 g (416 mmol) of 6'-bromo-2'-fluorobiphenyl-2-ol are dissolved in 2 L of DMF (max. 0.003% water) SeccoSolv® and cooled to 5°C. 20 g (449 mmol) of sodium hydride (60% suspension in mineral oil) are added in portions to this solution, when the addition is complete the mixture is stirred for 20 minutes and then the mixture is heated to 100°C for 45 minutes. After cooling, 500 ml of ethanol are slowly added to the mixture, which is completely concentrated by rotary evaporation and purified by chromatography. Yield: 90 g (367 mmol), 88.5% of theory.

[0162] The following compounds are prepared in a similar manner: [ka]

[0163] d) 1-Bromo-8-iodobenzofuran [ka] 20 g (80 mmol) of 1-bromodibenzofuran, 2.06 g (40.1 mmol) of iodine, 3.13 g (17.8 mmol) of iodic acid, 80 ml of acetic acid, 5 ml of sulfuric acid, 5 ml of water and 2 ml of chloroform are stirred at 65 ° C for 3 hours. After cooling, the mixture is mixed with water and the precipitated solid is suction filtered and washed three times with water. The residue is recrystallized from toluene and dichloromethane / heptane. The yield is 25.6 g (68 mmol), 85% of theory. The following compounds are prepared in a similar manner: [ka]

[0164] e) Dibenzofuran-1-boronic acid [ka] 180 g (728 mmol) of 1-bromodibenzofuran are dissolved in 1500 ml of dry THF and cooled to -78 ° C. At this temperature, 305 ml (764 mmol / 2.5 M in hexane) of n-butyllithium are added within about 5 minutes, and the mixture is stirred at -78 ° C for another 2.5 hours. At this temperature, 151 g (1456 mmol) of trimethylborate are added very rapidly, and the reaction is allowed to return slowly (about 18 hours) to room temperature. The reaction solution is washed with water, the precipitated solid and the organic phase are azeotropically dried with toluene. The crude product is extracted with toluene / methylene chloride at about 40 ° C with stirring and filtered off with suction. Yield: 146 g (690 mmol), 95% of theory.

[0165] The following compounds are prepared in a similar manner: [ka]

[0166] f) 4-biphenyl-4-yl-2-chloroquinazoline [ka] 13 g (70 mmol) of biphenyl-4-boronic acid, 13.8 g (70 mmol) of 2,4-dichloroquinazoline and 14.7 g (139 mmol) of sodium carbonate are suspended in 200 ml of toluene, 52 ml of ethanol and 100 ml of water. 800 mg (0.69 mmol) of tetrakisphenylphosphinepalladium(0) are added to this suspension and the reaction mixture is heated under reflux for 16 hours. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and concentrated to dryness. The residue is recrystallized from heptane / dichloromethane. The yield is 13 g (41 mmol), 59% of theory.

[0167] The following compounds can be obtained in a similar manner: [ka] [ka]

[0168] g) 2-Dibenzofuran-1-yl-4-phenylquinazoline [ka] 23 g (110.0 mmol) of dibenzofuran-1-boronic acid, 29.5 g (110.0 mmol) of 2-chloro-4-phenylquinazoline and 26 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and 112 mg (0.5 mmol) of palladium(II) acetate are added to the suspension and the reaction mixture is heated under reflux for 16 hours. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane / heptane. The yield is 32 g (86 mmol), 80% of theory.

[0169] The following compounds are prepared in a similar manner: [ka]

[0170] h) 2-(8-bromodibenzofuran-1-yl)-4-phenylquinazoline [ka] 70.6 g (190.0 mmol) of 2-dibenzofuran-1-yl-4-phenylquinazoline are suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulfuric acid (95-98%). 34 g (190 mmol) of NBS are added to the suspension and the mixture is stirred in the dark for 2 hours. Then water / ice is added and the solid is removed and washed with ethanol. The residue is recrystallized from toluene. The yield is 59 g (130 mmol), which corresponds to 69% of theory.

[0171] In the case of the thiophene derivatives, nitrobenzene is used rather than sulfuric acid, and elemental bromine instead of NBS:

[0172] The following compounds are prepared in a similar manner: [ka]

[0173] j) 2-Dibenzofuran-1-yl-4,6-diphenyl-[1,3,5]triazine [ka] 23 g (110.0 mmol) of dibenzofuran-1-boronic acid, 29.5 g (110.0 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 21 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and 112 mg (0.5 mmol) of palladium(II) acetate are added to this suspension and the reaction mixture is heated under reflux for 16 hours. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane / heptane. The yield is 37 g (94 mmol), corresponding to 87% of theory.

[0174] The following compounds are prepared in a similar manner: [ka]

[0175] i) 2-(8-bromodibenzofuran-1-yl)-4,6-diphenyl-[1,3,5]triazine [ka] 70 g (190.0 mmol) of 2-dibenzofuran-1-yl-4,6-diphenyl-[1,3,5]triazine are suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulfuric acid (95-98%). 34 g (190 mmol) of NBS are added to this suspension and the mixture is stirred in the dark for 2 hours. Then water / ice is added and the solid is removed and washed with ethanol. The residue is recrystallized from toluene. The yield is 80 g (167 mmol), which corresponds to 87% of theory. The following compounds are prepared in a similar manner: [ka]

[0176] In the case of thiophene derivatives, nitrobenzene is used rather than sulfuric acid, and elemental bromine instead of NBS: [ka]

[0177] k) 2,4-diphenyl-6-[8-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-dibenzofuran-1-yl]-[1,3,5]triazine [ka] In a 500 ml flask, under protective gas, 60 g (125 mmol) of 2-(8-bromodibenzofuran-1-yl)-4,6-diphenyl-[1,3,5]triazine are dissolved in 900 ml of dry DMF together with 39 g (1051 mmol) of bis(pinacolato)diborane (CAS 73183-34-3) and the mixture is degassed for 30 minutes. Subsequently, 37 g (376 mmol) of potassium acetate and 1.9 g (8.7 mmol) of palladium acetate are added and the mixture is heated to 80 ° C overnight. After the reaction is complete, the mixture is diluted with 300 ml of toluene and extracted with water. The solvent is removed on a rotary evaporator and recrystallized with heptane. Yield: 61 g (117 mmol), 94% of theory.

[0178] The following compounds are prepared in a similar manner: [ka] [ka]

[0179] l) 2,4-diphenyl-6-[8-(2,4-diphenyl-[1,3,5]triazin-2-yl)dibenzofuran-1-yl]-[1,3,5]triazine [ka] 68.7 g (110.0 mmol) of 2,4-diphenyl-6-[8-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-dibenzofuran-1-yl]-[1,3,5]triazine, 29.3 g (110.0 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 21 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. To this suspension, 913 mg (3.0 mmol) of tri-o-tolylphosphine and 112 mg (0.5 mmol) of palladium(II) acetate are added and the reaction mixture is heated under reflux for 16 hours. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and concentrated to dryness. The product was purified via column chromatography on silica gel using toluene / CHCl3 (1:1) and finally, purified under high vacuum (p=5x10 -7 It is sublimed at 1000 psi (99.9% purity) at 1000 psi (mbar). The yield is 51 g (81 mmol), which corresponds to 74% of theory.

[0180] The following compounds are prepared in a similar manner: [ka] [ka] [ka] [ka] [ka]

[0181] m) 1-[9-(4,6-diphenyl-[1,3,5]triazin-2-yl)-dibenzofuran-2-yl]-1H-benzimidazole [ka] Under protective gas, 10 g (84.7 mmol) of benzimidazole, 42 g (127.4 mmol) of CsCO3, 2.4 g (14.7 mmol) of CuI and 30 g (63 mmol) of 2-(8-bromodibenzofuran-1-yl)-4,6-diphenyl-[1,3,5]triazine are suspended in 100 ml of degassed DMF and the reaction mixture is heated under reflux at 120 ° C for 40 h. After cooling, the solvent is removed under reduced pressure, the residue is dissolved in dichloromethane and water is added. The organic phase is then removed and filtered through silica gel. The yield is 27.9 g (54 mmol), which corresponds to 86% of theory.

[0182] The following compounds are prepared in a similar manner: [ka]

[0183] n) 1-[9-(4,6-diphenyl-[1,3,5]triazin-2-yl)-dibenzofuran-2-yl]-3-phenyl-1H-benzimidazole [ka] Under protective gas, 25.7 g (50 mmol) of 1-[9-(4,6-diphenyl-[1,3,5]triazin-2-yl)-dibenzofuran-2-yl]-1H-benzimidazole, 560 mg (25 mmol) of Pd(OAc)2, 19.3 g (118 mmol) of CuI and 20.8 g (100 mmol) of iodobenzene are suspended in 300 ml of degassed DMF and the reaction mixture is heated at 140 °C under reflux for 24 h. After cooling, the solvent is removed under reduced pressure, the residue is dissolved in dichloromethane and water is added. The organic phase is then removed and filtered through silica gel. The product is purified via column chromatography on silica gel with toluene / heptane (1:2) and finally purified under high vacuum (p=5x10 -7 It is sublimed at 1000 psi (99.9% purity) at 1000 psi (mbar). The yield is 18.6 g (31 mmol), which corresponds to 63% of theory.

[0184] The following compounds are prepared in a similar manner: [ka]

[0185] OLED manufacturing Examples C1-I19 below (see Tables 1 and 2) provide data for various OLEDs.

[0186] To improve the process, cleaned glass plates (cleaned in a laboratory glass washer with Merck Extran cleaning solution) coated with 50 nm thick structured I~ (indium tin oxide) are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH, Germany, spin-coated from an aqueous solution). These coated glass plates form the substrates on which the OLEDs are applied.

[0187] An OLED basically has the following layer structure: substrate / hole transport layer (HTL) / interlayer (IL) / electron blocking layer (EBL) / emissive layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally a cathode. The cathode is formed of a 100 nm thick layer of aluminum. The exact structure of an OLED can be found in Table 1. The materials required for the manufacture of an OLED are given in Table 3.

[0188] All materials are applied by thermal evaporation in a vacuum chamber. Here, the light-emitting layer always consists of at least one matrix material (host material) and a light-emitting dopant (emitter) that is mixed in a certain volume percentage into the matrix material(s) by co-evaporation. A specification such as INV-1:IC3:TEG1 (60%:35%:5%) means here that the material INV-1 is present in the layer in a volume percentage of 60%, IC3 in the layer in a volume percentage of 35% and TEG1 in the layer in a volume percentage of 5%. Similarly, the electron-transport layer may also consist of a mixture of two materials.

[0189] The OLEDs are characterized by standard methods. For this purpose, the external quantum efficiency (EQE, measured in %) is determined as a function of the luminous density calculated from the current-voltage-luminous flux density characteristic line (IUL characteristic line) assuming a Lambertian radiation characteristic. The parameter U1000 in Table 2 is 1000 cd / m 2 Finally, EQE1000 represents the voltage required for an operating luminous density of 1000 cd / m 2 The lifetime LT is defined as the time it takes for the luminous flux density to drop to a certain percentage L1 from the initial luminous density when driven at a constant current. The values ​​for L0;j0=4000cd / m and L1=70% in Table X2 indicate that the lifetime reported in the LT column is the time it takes for the luminous flux density to drop to a certain percentage L1 when driven at a constant current. 2 from 2800 cd / m 2 Similarly, L0;j0=20mA / cm 2 , L1=80% is 20mA / cm 2 This means that when operated at , the luminous flux density drops to 80% of its initial value after a time LT.

[0190] Data for various OLEDs are summarized in Table 2. Examples C1-C4 are prior art comparative examples and show OLEDs containing prior art materials. Examples I1-I10 show data for OLEDs comprising materials according to the present invention.

[0191] In order to explain the advantages of the OLED according to the present invention, some examples are described in detail below. However, it should be pointed out that this is just a selection of the data shown in Table 2. As can be seen from the table, even when the compounds according to the present invention that are not specifically mentioned are used, in some cases significant improvements over the prior art are achieved in all parameters, while in some cases only improvements in efficiency, voltage or lifetime are observed. However, an improvement in one of the mentioned parameters is already a significant advantage, since various applications require optimization regarding different parameters.

[0192] Use of the compounds of the present invention as electron transport materials The examples and comparative examples show that the substituents of the present invention provide clear improvements in voltage and lifetime without significant loss in other properties.

[0193] Compared to OLEDs where material INV-7 is used as the ETL, in some cases there is a slight improvement in voltage and in some cases there is also an improvement in lifetime in the cases of using the preferred materials INV-2, INV-3, INV-4 and INV-5.

[0194] Use of the compounds of the present invention as matrix materials in phosphorescent OLEDs The Examples and Comparative Examples show that the inventive substitutions provide significant improvements in voltage and life without significant loss of other properties.

[0195] Compared to OLEDs where material INV-6 is used in the EML, in some cases slight improvements in voltage and EQE are seen, and in some cases particularly noticeable improvements in lifetime are seen in the cases of using the preferred materials INV-1, INV-2, INV-3 and INV-4. [Table 1-1] [Table 1-2]

Table 2

Table 3-1

Table 3-2

Table 3-3

Claims

1. A compound comprising the structure of formula (I): 【Chemistry 1】 (wherein the symbols used are as follows: Y is O or S; X is the same or different at each occurrence and is N or CR １ , preferably CR １ , with the proviso that not more than two of the X groups in one ring are N, and C is L ２ is a bonding site for the group; Q １ , Q ２ is, independently in each occurrence, an electron transport group; L １ , L ２ is a bond or has 5 to 30 aromatic ring atoms and one or more R １ an aromatic or heteroaromatic ring system, optionally substituted by radicals; R １ are the same or different for each occurrence, H, D, F, Cl, Br, I, B (OR ２ ) ２ , CHO, C(=O)R ２ , C.R. ２ = C(R ２ ) ２ ,CN,C(=O)OR ２ , C(=O)N(R ２ ) ２ , Si(R ２ ) ３ , N(R ２ ) ２ , NO ２ , P(=O)(R ２ ) ２ , OSO ２ R ２ , OR ２ , S(=O)R ２ , S(=O) ２ R ２ , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be represented by 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=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 having 5 to 40 aromatic ring atoms, and in each case one or more R ２ an aromatic or heteroaromatic ring system, or a ring system having 5 to 40 aromatic ring atoms, optionally substituted by a radical, and one or more R ２ an aryloxy or heteroaryloxy group, or a combination of these systems, optionally substituted by a radical; １ The substituents may together form a mono- or polycyclic, aliphatic or aromatic ring system; R ２ are the same or different for each occurrence, H, D, F, Cl, Br, I, B (OR ３ ) ２ , CHO, C(=O)R ３ , C.R. ３ = C(R ３ ) ２ ,CN,C(=O)OR ３ , C(=O)N(R ３ ) ２ , Si(R ３ ) ３ , N(R ３ ) ２ , NO ２ , P(=O)(R ３ ) ２ , OSO ２ R ３ , OR ３ , S(=O)R ３ , S(=O) ２ R ３ , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be represented by one or more R ３ radical, wherein one or more non-adjacent CH ２ The group is -R ３ C=CR ３ -, -C≡C-, Si(R ３ ) ２ , C=O, C=S, C=NR ３ , -C(=O)O-, -C(=O)NR ３ -, N.R. ３ , P(=O)(R ３ ), —O—, —S—, SO or SO ２ and where one or more hydrogen atoms are replaced by D, F, Cl, Br, I, CN or NO ２ or having 5 to 40 aromatic ring atoms, and in each case one or more R ３ an aromatic or heteroaromatic ring system, or a ring system having 5 to 40 aromatic ring atoms, optionally substituted by a radical, and one or more R ３ an aryloxy or heteroaryloxy group, or a combination of these systems, optionally substituted by a radical; ２ The substituents may together form a mono- or polycyclic, aliphatic or aromatic ring system; R ３ are identical or different at each occurrence and are H, D, F, or an aliphatic, aromatic and / or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, in which a hydrogen atom may be replaced by F; at the same time, two or more adjacent R ３ The substituents together may form a monocyclic or polycyclic, aliphatic or aromatic ring system.

2. The compound according to claim 1, characterized in that the structure of formula (II) is formed. 【Chemistry 2】 (In the formula, Symbols X, Y, L １ , L ２ , Q １ and Q. ２ has the meaning given in claim 1)

3. 3. The compound according to claim 1 or 2, characterized in that the compound comprises at least one structure of formula (Ia): 【Chemistry 3】 (Wherein, symbols Y, R １ , L １ , L ２ , Q １ and Q. ２ has the meaning according to claim 1 or 2 and q is 0, 1 or 2, preferably 0 or 1.

4. Q １ and / or Q ２ Compounds according to any one of claims 1 to 3, characterized in that the group comprises at least one structure selected from the group pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and / or benzimidazole.

5. The Q group has 6 to 10 aromatic ring atoms and one or more R １ may be substituted by radicals (wherein R １ Compounds according to any one of claims 1 to 4, characterized in that they are heteroaromatic ring systems, in which R is an integer from 1 to 4 and R is an integer from 1 to 4.

6. Q １ and / or Q ２ Compounds according to any one of claims 1 to 5, characterized in that the radicals are selected from the structures of formula (Q-1), (Q-2) and / or (Q-3) 【Chemistry 4】 (Wherein, the symbols X and R １ has the meaning as defined in claim 1, the dotted line indicates the connection position, and Ar １ has 6 to 40 carbon atoms and in each case has one or more R ２ an aromatic or heteroaromatic ring system, optionally substituted by a radical, having 5 to 60 aromatic ring atoms and one or more R ２ an aryloxy group, optionally substituted by a radical, or an aryloxy group having 5 to 60 aromatic ring atoms, in each case one or more R ２ an aralkyl group having 5 to 60 aromatic ring atoms, optionally substituted by a radical, where two or more adjacent R １ and / or R ２ The substituents are optionally monocyclic or polycyclic, one or more R ３ may be substituted by radicals, may form an aliphatic ring system (wherein R ２ and R ３ has the meaning given in claim 1)

7. Q １ and / or Q ２ Compounds according to any one of claims 1 to 6, characterized in that the group is selected from the structures of formula (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-12) and / or (Q-13) 【Chemistry 5-1】 【Chemistry 5-2】 (Wherein, the symbol Ar １ and R １ has the meaning according to claim 6, the dotted line indicates the point of connection and l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2, m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and n is 0, 1, 2 or 3, preferably 0 or 1.

8. Q １ and / or Q ２ Compounds according to any one of claims 1 to 7, characterized in that the group is selected from the structures of formula (Q-14), (Q-15), (Q-16) and / or (Q-17) 【Chemistry 6】 (Wherein, the symbol Ar １ and R １ has the meaning according to claim 6, the dotted line indicates the connection position and m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and n is 0, 1, 2 or 3, preferably 0 or 1.

9. Q １ and / or Q ２ Compounds according to any one of claims 1 to 8, characterized in that the group is selected from the structures of formula (Q-18), (Q-19), (Q-20), (Q-21), (Q-22), (Q-23), (Q-24), (Q-25), (Q-26), (Q-27) and / or (Q-28). 【Chemistry 7】 (Wherein, symbol R １ have the meaning as defined in claim 1 and the dotted lines indicate the connection positions)

10. Ar １ has 6 to 12 aromatic ring atoms and one or more R ２ A radical (where R ２ Compounds according to any one of claims 6 to 8, characterized in that they are aromatic ring systems, optionally substituted by radicals having the meanings according to claim 1.

11. The compound according to any one of claims 1 to 10, characterized in that the compound does not contain a carbazole and / or triarylamine group.

12. A compound according to any one of claims 1 to 11, characterised in that the compound comprises a hole transporting group.

13. 13. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 12, wherein there is one or more bonds of said compound to said polymer, oligomer or dendrimer.

14. A composition comprising at least one compound according to any one of claims 1 to 12 and / or the oligomer, polymer or dendrimer according to claim 13 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, n-dopants, wide band gap materials, electron blocking materials and hole blocking materials.

15. A formulation comprising at least one compound according to any one of claims 1 to 12, an oligomer, polymer or dendrimer according to claim 13 and / or at least one composition according to claim 14 and at least one solvent.

16. A method for preparing a compound according to any one of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13, characterized in that a compound comprising at least one electron transport group is combined with a compound comprising at least one benzofuran and / or benzothiophene radical in a coupling reaction.

17. Use of a compound according to any one of claims 1 to 12, an oligomer, a polymer or a dendrimer according to claim 13 or a composition according to claim 14 as a hole blocking material, an electron injection material and / or an electron transport material in an electronic device.

18. 15. An electronic device comprising at least one compound according to any one of claims 1 to 12, an oligomer, polymer or dendrimer according to claim 13 or a composition according to claim 14, said electronic device being preferably selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic photodetectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells and organic laser diodes.

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