Heterocyclic compounds having a dibenzofuran and / or dibenzothiophene structure

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] This invention describes dibenzofuran and / or dibenzothiophene derivatives substituted with electron transport groups, particularly for use in electronic devices. The invention further relates to methods for producing the compounds of the present invention and to electronic devices comprising these compounds.

[0002] The structure of organic electroluminescent devices (OLEDs) that use organic semiconductors as functional materials is described, for example, in US4539507, US5151629, EP0676461, and WO98 / 27136. The light-emitting materials used are often phosphorescent organometallic complexes. For quantum mechanical reasons, using organometallic compounds as phosphorescent emitters can result in up to four times higher energy efficiency and power efficiency. Generally, there is still a need for improvement in OLEDs, especially phosphorescent OLEDs, in terms of efficiency, operating voltage, and lifetime.

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

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

[0005] Generally, for these materials used as matrix materials, there is still a need for improvements in the devices, particularly in terms of lifespan, as well as efficiency and operating voltage.

[0006] The object of the present invention is to provide compounds suitable for use in phosphorescent or fluorescent OLEDs, particularly as matrix materials. More specifically, the object of the present invention is to provide matrix materials suitable for red, yellow, and green phosphorescent OLEDs, and possibly blue phosphorescent OLEDs, that result in long lifetime, good efficiency, and low operating voltage. In particular, the properties of the matrix material have an essential impact on the lifetime and efficiency of organic electroluminescent devices.

[0007] Furthermore, the compound must be able to be processed by a very simple method and, in particular, must exhibit good solubility and film-forming properties. For example, the compound must exhibit oxidative stability upon heating and an improved glass transition temperature.

[0008] A further object is to provide an electronic device that is very inexpensive, has a constant quality, and has excellent performance.

[0009] In addition, the electronic device must be able to be used or adapted for many purposes. More particularly, the performance of the electronic device must be maintained over a wide temperature range.

[0010] Surprisingly, it has been found that an element comprising a compound comprising a compound of the following formula (I) provides an improvement compared to the prior art, particularly when used as a matrix material for a phosphorescent dopant.

[0011] Thus, the present invention provides a compound comprising a structure of the following formula (I):

Chemical formula

[0012] In the context of this invention, adjacent carbon atoms are carbon atoms that are directly bonded to each other. Furthermore, in the definition of a radical, “adjacent radicals” means that these radicals are bonded to the same carbon atom or adjacent carbon atoms. These definitions also apply, in particular, to the terms “adjacent group” and “adjacent substituent.”

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

[0014] Furthermore, however, the above expression can also be interpreted as meaning that if one of the two radicals is hydrogen, the second radical will bond to the hydrogen atom at its bonded position, forming a ring. This is illustrated by the following scheme: [ka]

[0015] In the context of the present invention, a condensed aryl group is a group in which two or more aromatic groups are fused together, i.e., ring-fused, via a common edge, such as two carbon atoms belonging to at least two aromatic or heteroaromatic rings, as in naphthalene. In contrast, fluorene, for example, is not a condensed aryl group in the context of the present invention because the two aromatic groups in fluorene do not have a common edge.

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

[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 has 1 to 40 carbon atoms and at least one heteroatom in the ring system, wherein the total 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 in which two or more aryl or heteroaryl groups may be blocked by nonaromatic units (preferably less than 10% of atoms other than H), such as carbon, nitrogen or oxygen atoms or carbonyl groups, rather than necessarily containing only aryl or heteroaryl groups. For example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, and stilbenes are also considered aromatic ring systems in the context of the present invention, as are systems in which two or more aryl groups are blocked, for example, by linear or cyclic alkyl groups or silyl groups. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to each other, such as biphenyl, terphenyl, quarterphenyl, or bipyridine, are similarly considered aromatic or heteroaromatic ring systems.

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

[0019] In the context of the present invention, each of the C1-C groups therein may be substituted with the aforementioned groups. 20The alkyl groups include, 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-hexa-1-yl, 1,1-dimethyl-n-hepta- 1-yl, 1,1-dimethyl-n-octa-1-yl, 1,1-dimethyl-n-decey-1-yl, 1,1-dimethyl-n-dodecey-1-yl, 1,1-dimethyl-n-tetradecey-1-yl, 1,1-dimethyl-n-hexadece-1-yl, 1,1-dimethyl-n-octadecey-1-yl, 1,1-diethyl-n-hexa-1-yl, 1,1-diethyl-n-hepta-1-yl, 1,1-diethyl-n-octa-1-yl, 1,1-diethyl-n-decey-1-yl, 1, The terms are understood to mean 1-diethyl-n-dodecé-1-yl, 1,1-diethyl-n-tetradecé-1-yl, 1,1-diethyl-n-hexadece-1-yl, 1,1-diethyl-n-octadecé-1-yl, 1-(n-propyl)cyclohexa-1-yl, 1-(n-butyl)cyclohexa-1-yl, 1-(n-hexyl)cyclohexa-1-yl, 1-(n-octyl)cyclohexa-1-yl, and 1-(n-decyl)cyclohexa-1-yl radicals. The alkenyl group is understood to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, or cyclooctadienyl.The alkynyl group is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, or octinyl. C1-C. 40 The alkoxy group is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, or 2-methylbutoxy.

[0020] The aromatic or heteroaromatic ring system, having 5 to 40 aromatic ring atoms, which may be substituted by the radicals described above in each case, and which may be bonded to the aromatic or heteroaromatic system at any desired position, is understood to mean a group derived from, for example, the following: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluorantene, benzofluorantene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terpheni Lu, tarphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, torxene, isotorxene, spirotorxene, spiroisotorxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, Carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthidine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, Isooxazole, 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-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorbin, naphthyrizine, azacarbazole, benzocarborin, 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, tetrazol, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purines, pteridines, indoridines, and benzothiadiazole.

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

[0022] Furthermore, in formula (I) or (II), two or fewer X groups are N, preferably one or fewer X groups are N, and preferably all X are CR. 1 And here X represents CR 1 A compound is preferred in which, of the groups, preferably up to 4, more preferably up to 3, and particularly preferably up to 2 are not CH groups.

[0023] Furthermore, in formula (I) and / or (II), the R of the X group 1 The radical may not form a fused ring system with the ring atom of the benzofuran and / or benzothiophene structure. 1 Any R which may be bound to a radical 2 , R 3 This includes the formation of a fused ring system with substituents. In formula (I) and / or (II), the R of the X group 1It is preferred that the radical does not form a ring system with the ring atoms of the benzofuran and / or benzothiophene structure. This concerns any R 1 which may be attached to the radical, any R 2 R 3 and includes the formation of a ring system with substituents.

[0024] Preferably, the compounds of the invention may comprise the structure of formula (Ia).

Chemical formula

[0025] In a further configuration, the compounds of the invention may comprise the structure of formula (IIa).

Chemical formula

[0026] Furthermore, in formula (Ia) and / or (IIa), the R 1 substituent of the benzofuran and / or benzothiophene structure may be a case where it does not form a fused ring system with the ring atoms of the benzofuran and / or benzothiophene structure. This concerns any R 1 which may be attached to the R 2 radical, any R 3 and includes the formation of a fused ring system with substituents. In formula (Ia) and / or (IIa), the R of the benzofuran and / or benzothiophene structure1 It is preferred that the substituent does not form a ring system with the ring atoms of the benzofuran and / or benzothiophene structure. This includes the formation of a ring system with any R 1 substituent, which may be attached to the radical R 2 、R 3 substituent.

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

[0028] Furthermore, a preferred feature of the compounds of the present 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 groups are electron transport groups. These groups are well known in the art and facilitate the compound to transport and / or conduct electrons.

[0030] Furthermore, the compound of formula (I) exhibits surprising advantages when, in formula (I), (II), (Ia) and / or (IIa), the Q 1 and / or Q 2 group comprises at least one structure selected from the group consisting of pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole, and / or benzimidazole.

[0031] Even more preferably, preferably Q 1 and / or Q2 At least one, preferably both, of the groups is a heteroaromatic ring system having 5 to 24 ring atoms (where each ring atom contains at least one nitrogen atom and the ring system has 1 or more R 1 Radical (R 1 The compound is characterized in that (which may be substituted with the above, particularly formula (I), having the meaning described above).

[0032] In further construction, in particular Q as described in formulas (I), (II), (Ia) and / or (IIa) 1 and / or Q 2 At least one, preferably both, of the groups is a heteroaromatic ring system (where the ring atoms contain 1 to 4 nitrogen atoms and the ring system has 1 or more R 1 Radical (R 1 This may be a case where is replaced by (which has the meaning described above, in particular formula (I)).

[0033] Furthermore, Q as described in formulas (I), (II), (Ia) and / or (IIa) in particular 1 and / or Q 2 At least one, preferably both, of the groups has 6 to 10 ring atoms and 1 or more R 1 Radical (R 1 The case may also be a heteroaromatic ring system in which is substituted by the above, in particular formula (I), which has the meaning described above.

[0034] Preferably, Q as described in formulas (I), (II), (Ia) and / or (IIa). 1 and / or Q 2 The base may be selected from the structures of formulas (Q-1), (Q-2), and / or (Q-3). [ka] In the formula, the symbols X and R 1 However, it has the meaning described above, especially in formula (I), the dotted line indicates the connection point, and Ar 1It has 6 to 40 carbon atoms, and in each case, it has 1 or more R 2 Aromatic or heteroaromatic ring systems, which may be substituted by radicals, having 5 to 60 aromatic ring atoms, and having 1 or more R 2 An aryloxy group, or having 5 to 60 aromatic ring atoms, which may be substituted by a radical, and in each case, having 1 or more R 2 An aralkyl group (where 2 or more adjacent R groups may be substituted by a radical) 1 and / or R 2 The substituents may optionally be monocyclic or polycyclic aliphatic ring systems (this is one or more R 3 It may also be substituted with a radical, where R 2 and R 3 This may form the meaning described above, particularly in formula (I).

[0035] In further forms, particularly as shown in formulas (I), (II), (Ia) and / or (IIa), Q 1 and / or Q 2 The base is selected from the structures of formulas (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 The terms have the meanings described above, particularly in formulas (I) and (Q-1), where the dotted line indicates the connection point, 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 equations (I), (II), (Ia) and / or (IIa) in particular 1and / or Q 2 The base may be selected from the structures of formulas (Q-14), (Q-15), (Q-16), and / or (Q-17). [ka] In the formula, the symbol Ar 1 and R 1 The terms have the meanings described above, particularly in formulas (I) and (Q-1), where the dotted line indicates the connection point, 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 These are aryl or heteroaryl radicals, in which an aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is directly (i.e., via an aromatic or heteroaromatic group) bonded to each atom of a further group (e.g., the carbon or nitrogen atom of the (Q-1) to (Q-17) groups shown above).

[0038] In a more preferred embodiment of the present invention, Ar 1 Each occurrence may be the same or different, and is 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, with 1 or more R in each case. 2 It may be substituted with a radical, but is preferably unsubstituted. Here, R 2 The appropriate Ar may have the meaning described above, particularly in formula (I). 1The group is selected from the group consisting of phenyl, ortho-, meta-, or para-biphenyl, terphenyl, especially branched terphenyl, quarter-terphenyl, especially branched quarter-terphenyl, 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 has 1 or more R 2 It may be substituted with radicals, but is preferably unsubstituted.

[0039] For advantage, the Ar in equations (Q-1) to (Q-17) 1 It has 6 to 12 aromatic ring atoms and 1 or more R 2 The aromatic ring system may be substituted with radicals, but is preferably unsubstituted. Here, R 2 This may have the meaning described above, particularly in formula (I).

[0040] Preferably, R in equations (Q-1) to (Q-17) 2 Radicals are R 2 Ar aryl or heteroaryl group to which the radical is bonded. 1 It does not form a major fused ring with the ring atoms. This is because R 2 Any R which may be bound to a radical 3 This includes forming a fused ring system with substituents.

[0041] Furthermore, compounds of formulas (I), (II), (Ia) and / or (IIa) are Q 1 and / or Q 2 The basis exhibits remarkable advantages where it is selected from the structures of formulas (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 1The terms have the meanings described above, particularly in equation (I), and the dotted lines indicate connection points.

[0042] In a preferred form, in the aforementioned formulas, particularly formulas (I), (Ia), (II), and / or (IIa), Q 1 Base and Q 2 The base is selected from the bases of equations (Q-1) to (Q-13).

[0043] In a further configuration, in the aforementioned equations, particularly equations (I), (Ia), (II), and / or (IIa), Q 1 Base and Q 2 The base is selected from the bases of equations (Q-14) to (Q-17).

[0044] Furthermore, in the aforementioned equations, particularly equations (I), (Ia), (II), and / or (IIa), Q 1 Base and Q 2 The base may be selected from the bases of equations (Q-18) to (Q-28).

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

[0046] Furthermore, in the aforementioned equations, particularly equations (I), (Ia), (II), and / or (IIa), Q 1 Q 2 One of the bases is selected from the bases of equations (Q-1) to (Q-13), and Q 1 Q 2 One of the bases may be selected from the bases of equations (Q-18) to (Q-28).

[0047] Furthermore, in the aforementioned equations, particularly equations (I), (Ia), (II), and / or (IIa), Q 1 Q2 One of the bases is selected from the bases of equations (Q-14) to (Q-17), and Q 1 Q 2 One of the bases may be selected from the bases of equations (Q-18) to (Q-28).

[0048] In a further configuration, electron transport base Q 1 and Q 2 However, these are the same in the aforementioned equations, particularly equations (I), (Ia), (II), and / or (IIa).

[0049] Furthermore, electron transport base Q 1 and Q 2 However, the aforementioned formulas, particularly formulas (I), (Ia), (II), and / or (IIa), may not be identical.

[0050] X is CR 1 is either an aromatic and / or heteroaromatic group R 1 If substituted by substituents, 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 linear 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 (where each of these is 1 or more R 2 It may be substituted with radicals, where one or more non-adjacent CH2 groups may be replaced by O, and one or more hydrogen atoms may be replaced by D or F), and has 5 to 24 aromatic ring atoms, with one or more R in each case. 2 Aromatic or heteroaromatic ring systems that may or may not be substituted by radicals, are preferable to being unsubstituted, or have 5 to 25 aromatic ring atoms and 1 or more R 2Selected from the group consisting of aralkyl or heteroaralkyl groups which may be substituted with radicals; and simultaneously, two R groups bonded to the same carbon atom or adjacent carbon atoms 1 The substituent is monocyclic or polycyclic, with one or more R 1 It is possible, if desired, to form aliphatic, aromatic, or heteroaromatic ring systems, which may be substituted with radicals. 1 The base may have the meaning described above, particularly in the structure (Q-1). Preferably, the symbol Ar 1 This represents an aryl or heteroaryl radical, and the aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is further represented by each atom of the group (e.g., N(Ar)). 1 )2, C(=O)Ar 1 , P(=O)(Ar 1 ) are directly bonded to two carbon, nitrogen, or phosphorus atoms, that is, via an aromatic or heteroaromatic group.

[0051] Comfortably, these R 1 The substituents are H, D, F, CN, N(Ar 1 ) A linear alkyl group having 2, 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3 or 4 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms (each of these has 1 or more R 2 Aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, and more preferably 6 to 13 aromatic ring atoms (each of which has 1 or more R 2 Selected from the group consisting of (which may be substituted by radicals, but are preferably unsubstituted); and at the same time, possibly two R 1 The substituent is bonded to the same carbon atom or an adjacent carbon atom, resulting in 1 or more R 2They may form a monocyclic or polycyclic aliphatic ring system, which may be substituted by radicals, but preferably unsubstituted. 1 The base may have the meaning described above, and in particular, it has the structure of (Q-1). Preferably, the symbol Ar 1 This represents an aryl or heteroaryl radical, and the aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is further represented by each atom of the group (e.g., N(Ar)). 1 They are directly bonded to (two nitrogen atoms), that is, via aromatic or heteroaromatic groups.

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

[0053] Furthermore, in the structures of equations (I), (Ia), (II), (IIa) and / or (Q-1) to (Q-28), at least one R 1 and / or Ar 1 The radical is given by equation (R 1 -1)~(R 1 It may also be a case where the base is selected from -79). [ka] [ka] [ka] [ka] [ka] The symbols used in the formula are as follows: Y is O, S, or NR 2 , preferably O or S; i is independently 0, 1, or 2 in each occurrence; j is 0, 1, 2, or 3, independently of each occurrence; h is 0, 1, 2, 3, or 4, independently of each occurrence; g is independently 0, 1, 2, 3, 4, or 5 in each occurrence; R 2 This may have the meaning described above, particularly in formula (I), and The dotted lines indicate connection points.

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

[0055] Preferably, L and / or L 2 The base is the electron transport base Q 1 and / or Q 2They may also form through-conjugation with the dibenzofuran structure (Y=O) of formulas (I), (Ia), (II), and / or (IIa). Through-conjugation of aromatic or heteroaromatic systems is formed as soon as a direct bond is formed between adjacent aromatic or heteroaromatic rings. Further bonds between the aforementioned conjugated groups, for example, via sulfur, nitrogen, or oxygen atoms or carbonyl groups, do not impair the conjugation. In the case of fluorene systems, two aromatic rings are directly bonded, where a sp at position 9 is present. 3 -Hybridized carbon atoms prevent the condensation of these rings, but conjugation is possible. This is the SP at position 9. 3 - Hybrid carbon atoms are not necessarily electron transport group Q 1 and / or Q 2 This is because it is not necessarily located between the dibenzofuran structure (Y=O) and / or the dibenzothiophene structure (Y=S). In contrast, in the case of the spirobifluorene structure, the electron transport group Q 1 and / or Q 2 Direct conjugation may be formed if the bond between the dibenzofuran structure (Y=O) and / or dibenzothiophene structure (Y=S) of formulas (I), (Ia), (II), and / or (IIa) is via the same phenyl group in the spirobifluorene structure, or via (multiple) phenyl groups in the spirobifluorene structure that are directly bonded to each other and coplanar. Electron transport group Q 1 and / or Q 2 The bond between the dibenzofuran structure (Y=O) and / or dibenzothiophene structure (Y=S) of formulas (I), (Ia), (II) and / or (IIa) is the sp at position 9 of the spirobifluorene structure. 3 - Conjugation is hindered when the bonds are mediated by different (multiple) phenyl groups connected via hybrid carbon atoms.

[0056] In a more preferred embodiment of the present invention, L 1 and / or L 2 Each instance may be identical or different, and each element has a single bond or 5-24 aromatic ring atoms, and one or more R 2Aromatic or heteroaromatic ring system which may be substituted with radicals. More preferably, L 1 and / or L 2 Each occurrence may be the same or different, and is an aromatic ring system having a single bond or 6-12 aromatic ring atoms, or a heteroaromatic ring system having 6-13 aromatic ring atoms, and in each case, there is 1 or more R 2 It may be substituted with a radical, but is preferably unsubstituted, where R 2 The symbol L may have the meaning described above, particularly in formula (I). Furthermore, preferably, the symbol L 1 and / or L 2 Each occurrence may be identical or different, and may be a single bond or an aryl or heteroaryl radical, and the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is bonded directly to each atom of the other group, i.e., via the atoms of the aromatic or heteroaromatic group. Most preferably, L 1 and / or L 2 It is a single bond. Suitable aromatic or heteroaromatic ring system L 1 and / or L 2 Examples include ortho-, meta-, or para-phenylene, biphenyl, fluorene, pyridine, pyrimidine, triazine, dibenzofuran, and dibenzothiophene (each of these being one or more R 2 Selected from the group consisting of (which may be substituted by radicals, but are preferably unsubstituted).

[0057] Preferably, a compound comprising the structure of formula (I), (II), (Ia) and / or (IIa), wherein at least one L of formula (I), (IIa) and / or (IIb) 1 and / or L 2 The group is either a bond or / or a group selected from formulas (L-1) to (L-70). [ka] [ka] [ka] [ka] [ka] In the formula, in each case, the dotted line indicates the connection point, the subscript l is 0, 1, or 2, the subscript g is 0, 1, 2, 3, 4, or 5, j is 0, 1, 2, or 3 independently each time it appears; h is 0, 1, 2, 3, or 4 independently each time it appears; Y is O, S, or NR 2 , preferably O or S; and R 2 This has the meaning described above, particularly in formula (I).

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

[0059] Advantageously, the compounds of the present invention comprising at least one structure of formula (I), (Ia), (II), and / or (IIa) may not contain a carbazole and / or triarylamine group. More preferably, the compounds of the present invention do not contain a hole transport group. Hole transport 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 more preferred embodiment of the present invention, R 2Each occurrence may be the same or different and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 10 carbon atoms, preferably 1, 2, 3, or 4 carbon atoms, and an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms, more preferably 5 to 13 aromatic ring atoms (which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, but are preferably unsubstituted).

[0061] The compounds of the present invention are aromatic or heteroaromatic R 1 or R 2 or Ar 1 When substituted with groups, it is preferable that these groups do not have aryl or heteroaryl groups having two or more aromatic six-membered rings directly condensed with each other. More preferably, the substituents do not contain any aryl or heteroaryl groups having six-membered rings directly condensed with each other. This is preferred because their structures have low triplet energies. Despite being fused aryl groups having two or more aromatic six-membered rings directly condensed with each other, phenanthrene and triphenylene are suitable in the present invention because they have high triplet energy levels.

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

[0063] Preferred forms of the compounds of the present 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 present invention.

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

[0065] The compounds of the present invention can, in principle, be produced by various methods. However, the methods described below have been found to be particularly suitable.

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

[0067] Suitable compounds having electron transport groups are often commercially available, in which case 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, and the conditions required for this purpose are well known to those skilled in the art, and the detailed description in the examples will assist those skilled in the art in carrying out these reactions.

[0069] All coupling reactions that result in CC bond formation and / or CN bond formation, which are particularly suitable and preferred, are described by Buchwald, Suzuki, Yamamoto, Stille, Heck, Negishi, Sonogashira, and Hiyama. These reactions are well known, and the examples will provide further guidance to those skilled in the art.

[0070] In all of the following synthetic schemes, compounds are shown with only a few substituents for structural simplification. This does not preclude the presence of any further substituents desired in the method.

[0071] Exemplary forms are shown in the following scheme, without any intention of imposing any limitations. The construction steps of each scheme can be combined with one another as desired. [ka]

[0072] In schemes 1 and 2, Q 1 and / or Q 2 Under this definition, the radical described is an electronically conductive group, as described above.

[0073] The methods shown for the synthesis of the compounds of the present invention should be understood as illustrative examples. Those skilled in the art can develop alternative synthetic routes within the scope of the common knowledge of those skilled in the art.

[0074] The basic principles of the manufacturing method detailed above are, in principle, known from literature on similar compounds and can be easily applied to the production of the compound of the present invention by those skilled in the art. Further information can be found in the examples.

[0075] These methods, if necessary, involve purification, such as recrystallization or sublimation, to obtain the compound of the present invention comprising the structure of formula (I) in high purity, preferably above 99%. 1 It can be obtained by measuring (H-NMR and / or HPLC).

[0076] The compounds of the present invention may also have suitable substituents, such as relatively long alkyl groups (about 4 to 20 carbon atoms), particularly branched alkyl groups, or optionally substituted aryl groups, such as xylyl, mesityl, or branched terphenyl or quarterphenyl groups, that result in solubility in standard organic solvents, such as toluene or xylene, at room temperature and in sufficient solubility concentrations, enabling the compounds to be treated in solution. These soluble compounds are particularly suitable for treatment in solution, for example, by printing. Furthermore, it should be emphasized that the compounds of the present invention comprising at least one structure of formula (I) already exhibit increased solubility in these solvents.

[0077] The compounds of the present invention can also be mixed with polymers. Similarly, these compounds can be covalently incorporated into polymers. This is particularly possible for compounds substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acids, or boronic acid esters, or with reactive polymerizable groups such as olefins or oxetanes. These are found to be used as monomers for producing the corresponding oligomers, dendrimers, or polymers. Oligomerization or polymerization is preferably carried out via halogen functional groups 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 uncrosslinked layers.

[0078] The present invention further provides polymers, oligomers, or dendrimers comprising one or more structures of formula (I) or the compounds of the present invention as detailed above, wherein one or more bonds exist to the compounds of the present invention or to the structures of formula (I). By linking to the structures of formula (I) or the compounds, they thus form side chains of the polymer or oligomer or are linked within the main chain. The polymers, oligomers, or dendrimers may be conjugated, partially conjugated, or unconjugated. The oligomers or polymers may be linear, branched, or dendritic. The same preferred forms apply to repeating units of the compounds of the present invention in the oligomers, dendrimers, and polymers as described above.

[0079] In producing oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with further monomers. It is preferable that the unit of formula (I), or the preferred form of the unit described above and below, be present in an amount of 0.01 to 99.9 mol%, preferably 5 to 90 mol%, more preferably 20 to 80 mol%. Suitable and preferred comonomers that form the polymer basic skeleton include fluorenes (e.g., according to EP842208 or WO2000 / 022026), spirobifluorenes (e.g., according to EP707020, EP894107 or WO2006 / 061181), paraphenylenes (e.g., according to WO92 / 18552), carbazoles (e.g., according to WO2004 / 070772 or WO2004 / 113468), thiophenes ( For example, by EP1028136), dihydrophenanthrenes (e.g., WO2005 / 014689), cis- and trans-indenofluorenes (e.g., by WO2004 / 041901 or WO2004 / 113412), ketones (e.g., by WO2005 / 040302), phenanthrenes (e.g., by WO2005 / 104264 or WO2007 / 017066), or a selection of these units. The polymers, oligomers and dendrimers may also contain further units, e.g., hole transport units, particularly those based on triarylamines, and / or electron transport units.

[0080] Furthermore, of particular interest are the compounds of the present invention characterized by a high glass transition temperature. In this regard, preferred are the compounds of the present invention comprising a structure of formula (I) or one of the preferred forms described above and below, having a glass transition temperature of at least 70°C, more preferably at least 110°C, even more preferably at least 125°C, and especially preferably 150°C (measured according to DIN 51005 (2005-08 edition)).

[0081] To treat the compounds of the present invention in the liquid phase, for example, by spin coating or printing, a formulation of the compounds according to the present invention is required. These formulations may be, for example, solutions, dispersions, or emulsions. For this purpose, it is preferable to use a mixture of two or more solvents. Suitable and preferred solvents include, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fencone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinene, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohex Silbenzene, decalin, dodecylbenzene, ethyl benzoate, indan, methyl benzoate, NMP, p-cymene, phenethole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindan, or mixtures of these solvents.

[0082] Accordingly, the present invention further relates to formulations 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 solvents or a mixture thereof. Alternatively, the further compound may be an organic or inorganic compound, such as a luminescent compound, in particular a phosphorescent dopant, and / or further matrix material, which are similarly used in electronic devices. This further compound may also be a polymer.

[0083] Accordingly, the present invention further provides a composition comprising the compound of the present invention and at least one further organic functional material. The functional material is generally an organic or inorganic material introduced between the anode and the cathode. Preferably, the organic functional material is selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conduction materials, hole injection materials, n-dopants, wide bandgap materials, electron blocking materials, and hole blocking materials.

[0084] Accordingly, the present invention also relates to a composition comprising at least one compound comprising at least one structure of formula (I), or one of the preferred forms described above and below, and at least one further matrix material. In a special aspect of the present invention, the further matrix material has hole transport properties.

[0085] The present invention further provides a composition comprising at least one compound comprising at least one structure of formula (I), or a preferred form described above and below, and at least one wide-bandgap material, where the wide-bandgap material is understood to mean the material disclosed in US7,294,849. These systems exhibit 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 very preferably 3.5 eV or more. One method for calculating the band gap is to use the energy levels of the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO).

[0087] The molecular orbitals, particularly the highest occupied orbital (HOMO) and lowest unoccupied 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 materials, structural optimization is first performed using the "ground state / semi-empirical / initial spin / AM1 / charge 0 / spin singlet" method. Subsequently, energy calculations are performed based on the optimized structure. Here, the "TD-SCF / DFT / initial spin / B3PW91" method is used together with the "6-31G(d)" ground 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. Energy calculations are performed in the same manner as for organic materials, except that the "LanL2DZ" basis set is used for metals and "6-31G(d)" is used for ligands. The HOMO energy level HEh or LUMO energy level LEh is obtained from the energy calculations in Hartree units. This is used to determine the HOMO and LUMO energy levels in electron volts by calibrating them using 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 this 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 lowest energy triplet state, which is evident from the quantum chemical calculations described.

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

[0091] The methods described herein are independent of the software packages used and always produce the same results. Examples of programs frequently used for this purpose include "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 a preferred form described above and below, and at least one phosphorescent material. Herein, the term “phosphorescent material” 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 that has a 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 that has a larger proportion in the mixture.

[0094] The phosphorescent dopants preferred for use in matrix systems, preferably mixed matrix systems, are the preferred phosphorescent dopants described below.

[0095] The term "phosphor dopant" typically refers to compounds in which luminescence occurs through spin-forbidden transitions, such as from an excited triplet state, or from a state with a higher spin quantum number, such as a quintet state.

[0096] A suitable phosphorescent compound (=triplet emitter) is a compound that emits light when properly excited, particularly preferably in the visible region, and further comprises at least one atom having an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, and especially a metal having 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, and especially compounds containing iridium or platinum. In the context of the present invention, all luminescent compounds containing the above metals are considered phosphorescent compounds.

[0097] Examples of the above-mentioned luminescent objects are 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 This can be found in the applications 2010 / 099852, WO2010 / 102709, WO2011 / 032626, WO2011 / 066898, WO2011 / 157339, WO2012 / 007086, WO2014 / 008982, WO2014 / 023377, WO2014 / 094961, WO2014 / 094960, as well as in the unpublished applications EP13004411.8, EP14000345.0, EP14000417.7, and EP14002623.8. In general, all phosphorescent complexes, such as those used in the prior art for phosphorescent OLEDs, and those 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 inventiveness.

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

change

change

change

change

change

change

change

[0099] The compounds described above, comprising the structure of formula (I) or the preferred form detailed above, can preferably be used as active components in electronic devices. An electronic device is understood to comprise an anode, a cathode, and at least one layer between the anode and the cathode, wherein the layer comprises at least one organic or organometallic compound. Accordingly, the electronic device of the present invention comprises an anode, a cathode, and a layer comprising at least one compound comprising the structure of formula (I). Preferred electronic devices are selected here 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 electric field quenching devices (O-FQDs), organic electrical sensors, light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic plasmon light-emitting devices (DM Koller et al., Nature Phonics 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. The active component is generally an organic or inorganic material introduced between the anode and cathode, such as a charge injection, charge transport, or charge blocking material, but especially a light-emitting material and a matrix material.

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

[0101] Here, the organic electroluminescent element comprises one light-emitting layer or may comprise multiple light-emitting layers. If multiple light-emitting layers are present, preferably, various light-emitting compounds capable of fluorescence or phosphorescence are used in the light-emitting layers, having multiple emission maxima across the entire 380 nm to 750 nm range, so as to produce white light overall. Particularly preferred are a three-layer system in which three layers exhibit blue, green, and orange or red emission (see, for example, WO2005 / 011013 for the basic structure), or a system having three or more light-emitting layers. The system may also 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 element comprises a compound of the present invention having the structure of formula (I) or one of the preferred embodiments described above, as a matrix material, preferably as an electron-conducting matrix material, in one or more light-emitting layers, preferably in combination with a further matrix material, preferably a hole-conducting matrix material. In a further preferred embodiment of the present invention, the further matrix material is an electron-transport compound. In a further preferred embodiment, the further matrix material is a compound having a large band gap that is not involved in or significantly involved in hole and electron transport in the layer. The light-emitting layer comprises at least one light-emitting compound.

[0103] Suitable matrix materials that can be used in combination with compounds of formula (I) or in a preferred form include: aromatic ketones; aromatic phosphine oxides; or aromatic sulfoxides or sulfones (e.g., according to WO2004 / 013080, WO2004 / 093207, WO2006 / 005627 or WO2010 / 006680); triarylamines, especially monoamines (e.g., according to WO2014 / 015935); carbazole derivatives (e.g., CBP(N,N-biscarbazolylbiphenyl), and Carbazole derivatives disclosed in WO2005 / 039246, US2005 / 0069729, JP2004 / 288381, EP1205527, or WO2008 / 086851); indolocarbazole derivatives (e.g., according to WO2007 / 063754 or WO2008 / 056746); indenocarbazole derivatives (e.g., according to WO2010 / 136109 and WO2011 / 000455); azacarbazole derivatives (e.g., according to EP1617710, EP1617711, EP1731584, JP 2005 / 347160; bipolar matrix materials (e.g., WO2007 / 137725); silanes (e.g., WO2005 / 111172); azabolols or boronic acid esters (e.g., WO2006 / 117052); triazine derivatives (e.g., WO2010 / 015306, WO2007 / 063754 or WO2008 / 056746); zinc complexes (e.g., EP652273 or WO2009 / 062578); diazasilol or tetraazalol derivatives Diazaphosphor derivatives (e.g., according to WO2010 / 054729); diazaphosphor derivatives (e.g., according to WO2010 / 054730); cross-linked carbazole derivatives (e.g., according to US2009 / 0136779, WO2010 / 050778, WO2011 / 042107, WO2011 / 088877 or WO2012 / 143080); triphenylene derivatives (e.g., according to WO2012 / 048781); lactams (e.g., according to WO2011 / 116865, WO2011 / 137951 or WO2013 / 064206);Alternatively, 4-spirocarbazole derivatives (e.g., according to WO2014 / 094963 or unpublished application EP14002104.9) may be present. Similarly, further phosphorescent materials emitting at shorter wavelengths than the actual emitter may be present in the mixture as co-hosts.

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

[0105] Preferred triarylamine derivatives used as co-host materials in conjunction with the compounds of the present invention are selected from the compounds of the following formula (TA-1): [ka] In the formula, Ar 1 Each occurrence may be the same or different and have the meaning described above. Preferably, Ar 1 The base is either the same or different each time it appears, and the bases mentioned above, R 1 -1~R 1 -79, comfortable R 1 -1~R 1 Selected from -51.

[0106] In a preferred form of the compound represented by formula (TA-1), at least one Ar 1 The group is selected from biphenyl groups, which may be ortho-, meta-, or para-biphenyl groups. In a more preferred form of the compound represented by formula (TA-1), at least one Ar group is selected from fluorene groups or spirobifluorene groups, where these groups may be bonded to the nitrogen atom at the 1-, 2-, 3-, or 4-position, respectively. In a further preferred form of the compound represented by formula (TA-1), at least one Ar group 1The group is selected from phenylene or biphenyl groups, where these groups are ortho-, meta-, or para-bonded and are substituted with a dibenzofuran group, a benzothiophene group, or a carbazole group, particularly 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 form of the compound of formula (TA-1), one Ar 1 The group is selected from fluorene or spirobifluorene groups, particularly from 4-fluorene or 4-spirobifluorene groups, and one Ar 1 The group is selected from biphenyl groups, particularly para-biphenyl groups, or fluorene groups, particularly 2-fluorene groups, and also a third Ar 1 The group is selected from a para-phenylene group or a para-biphenyl group, substituted with a dibenzofuran group, particularly a 4-dibenzofuran group, or a carbazole group, particularly an N-carbazole group or a 3-carbazole group.

[0108] The indenocarbazole derivative used as a co-host material together with the compound of the present invention is selected from the compounds of the following formula (TA-2): [ka] In the formula, Ar 1 and R 1 It has the meaning shown above. 1 The preferred form of the base is the structure R described above. 1 -1~R 1 -79, comfortable, R 1 -1~R 1 It is -51.

[0109] The 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 This has the meaning described above. Here, two R atoms bonded to the indeno carbon atom 1 The groups are preferably the same or different alkyl groups having 1 to 4 carbon atoms, particularly methyl groups, or aromatic ring systems having 6 to 12 carbon atoms, particularly phenyl groups. More preferably, these two R groups are bonded to the indeno carbon atom. 1 The group is a methyl group. More preferably, the R group bonded to the indenocarbazole basic skeleton in formula (TA-2a) 1 The substituent is a carbazole group that can be attached to the indenocarbazole basic skeleton via H, or via the 1-, 2-, 3- or 4-position, or via a nitrogen atom, particularly via the 3-position.

[0110] A preferred 4-spirocarbazole derivative to be used as a co-host material together with the compound of the present invention is selected from the compounds of the following formula (TA-3): [ka] In the formula, Ar 1 and R 1 It has the meaning described above. 1 The preferred form of the base is the structure described above (R 1 -1)~(R 1 -79), more comfortable, R 1 -1~R 1 It is -51.

[0111] The preferred form of the compound of formula (TA-3) is the compound of formula (TA-3a) below: [ka] In the formula, Ar 1 and R 1 It has the meaning described above. 1 The preferred form of the base is the structure described above (R 1-1)~(R 1 -79), more comfortable, R 1 -1~R 1 It is -51.

[0112] A preferred lactam to be used as a co-host material with the compound of the present invention is selected from the following compounds of formula (LAC-1): [ka] In the formula, R has the meaning described above.

[0113] A preferred form of the compound of formula (LAC-1) is the compound of formula (LAC-1a) below: [ka] In the formula, R 1 It has the meaning described above. 1 Preferably, each occurrence is the same or different, and has H, or 5 to 40 aromatic ring atoms, and one or more radicals R 2 An aromatic or heteroaromatic ring system which may be substituted with, where R 2 This has the meaning described above, particularly formula (I). It can be. Most preferably, R 1 The substituent has H and 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, each of which is one or more non-aromatic radicals R 2 A suitable 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 include phenyl, ortho-, meta- or para-biphenyl, terphenyl, especially branched terphenyl, quarterphenyl, especially branched quarterphenyl, 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 these has one or more R2 Selected from the group consisting of (which may be substituted with radicals, but are preferably unsubstituted). Appropriate structure R 1 R-1 to R-79, comfort R 1 -1~R 1 This is the same structure as shown for -51.

[0114] Furthermore, it is preferable to use a mixture of multiple different matrix materials, particularly at least one electron-conducting matrix material and at least one hole-conducting matrix material. Similarly, it is also preferable to use a mixture of a charge-transporting matrix material and an electrically inert matrix material that is not significantly involved in charge transport, if any, as described in WO2010 / 108579.

[0115] Furthermore, the use of a mixture of two or more triplet emitters and a matrix is ​​preferred. Here, the triplet emitters having shorter wavelength emission spectra act as co-matrixes for the triplet emitters having longer wavelength emission spectra.

[0116] More preferably, the compound of the present invention comprising the structure of formula (I) in a preferred form can be used as a matrix material in the light-emitting layer of an organic electronic device, in particular an organic electroluminescent device, such as an OLED or OLEC. In this case, the matrix material comprising the structure of formula (I), or the preferred form of the structure 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 proportion of 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%, relative to the fluorescent light-emitting layer, and 85.0 to 97.0 volume%, relative to the phosphorescent light-emitting layer.

[0118] Accordingly, 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%, relative to the fluorescent luminescence layer, and 3.0 to 15.0 volume%, relative to the phosphorescent luminescence layer.

[0119] The light-emitting layer of an organic electroluminescent device may also be a system comprising multiple matrix materials (mixed matrix system) and / or multiple dopants. In this case as well, dopants are generally materials that make up a smaller proportion in the system, and matrix materials are materials that make up 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 more preferred embodiment of the present invention, a compound comprising formula (I), or a structure of the preferred form 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 preferable that one of the two materials is a material having hole transport properties and the other material is a material having electron transport properties. However, the desired electron transport and hole transport properties of the mixed matrix component may also be incorporated primarily or entirely into a single mixed matrix component, in which case a further mixed matrix component(s)

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

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

[0123] The anode is preferably a material having a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, metals with high redox potentials, 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 irradiation of an organic material (O-SC) or 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). Even more preferred are doped, conductive organic materials, in particular, doped, conductive polymers, such as PEDOT, PANI, or derivatives of these polymers. It is even more preferable when a p-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. Even more preferred p-dopants are HAT-CN (hexacyanohexazatriphenylene) or the compound NPD9 manufactured by Novaled. Such layers facilitate hole injection into materials with low HOMO, i.e., materials with large HOMO in size.

[0124] In further layers, any material used in the prior art can generally be used in those layers, and those skilled in the art can combine any of these materials with the material according to the present invention in electronic devices without inventive features.

[0125] Since the lifespan of such elements is significantly shortened by the presence of water and / or air, the elements are appropriately structured (depending on the application), equipped with contacts, and finally sealed.

[0126] More preferably, the electronic device, particularly an organic electroluminescence device, is characterized in that one or more layers are applied by a sublimation method. In this case, the material is applied by vacuum evaporation in a vacuum sublimation system at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 mbar. The initial pressure can be even lower or higher, for example, less than 10 -7 mbar is also possible.

[0127] Similarly preferably, the electronic device, particularly an organic electroluminescence device, is characterized in that one or more layers are applied by an OVPD (organic vapor phase deposition) method or by using sublimation of a carrier gas. In this case, the material is applied at a pressure of 10 -5 mbar to 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, in which the material is directly applied through a nozzle and further structured (for example, M.S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0128] More preferably, the electronic device, particularly an organic electroluminescence device, is characterized in that one or more layers are made from a solution by any printing method such as, for example, spin coating or, for example, screen printing, flexographic printing, offset printing, or nozzle printing, but more preferably 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 appropriate substitution.

[0129] The electronic device, particularly an organic electroluminescence device, can also be manufactured as a hybrid system by applying one or more layers from a solution and further applying one or more other layers by vacuum evaporation. For example, a light-emitting layer comprising a compound of formula (I) and a matrix material can be applied from a solution, and then a hole-blocking layer and / or an electron-transporting layer can be applied by vacuum evaporation under reduced pressure.

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

[0131] The electronic devices, particularly organic electroluminescent devices, according to the present invention are worthy of attention due to the following surprising advantages over the prior art:

[0132] 1. An electronic device, particularly an organic electroluminescent device, comprising a compound, oligomer, polymer or dendrimer having the structure of formula (I) or the preferred forms described above and below, particularly as an electron-conducting material, has a very good lifespan.

[0133] 2. An electronic device, particularly an organic electroluminescent device, comprising a compound, oligomer, polymer or dendrimer having the structure of formula (I) or the preferred forms described above and below as an electron-conducting material has excellent efficiency. More specifically, it has even higher efficiency compared to 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 having a very long lifespan.

[0135] 4. By using a compound, oligomer, polymer or dendrimer having the structure of formula (I) or the preferred forms described above and below, the formation of light loss channels in electronic devices, particularly organic electroluminescent devices, can be avoided. As a result, these devices are characterized by high PL efficiency and thereby high EL efficiency of the emitter, as well as excellent 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 any preferred form described above and below, within layers of electronic devices, particularly organic electroluminescent devices, results in high mobility of the electronically conductive structure.

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

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

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

[0140] 9. Compounds, oligomers, polymers, or dendrimers comprising formula (I), or any preferred form of structure described above and below, have a remarkably high triplet level T1, which is especially true for compounds used as electronically conductive materials.

[0141] These advantages, as described above, do not come with any degradation of other electronic properties.

[0142] The compounds and mixtures of the present invention are suitable for use in electronic devices. An electronic device is understood to mean a device comprising at least one layer containing at least one organic compound. The device may also contain an inorganic material or a layer formed entirely from an inorganic material.

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

[0144] The present invention further provides the use of compounds according to the present invention, and / or oligomers, polymers, or dendrimers according to the present invention, as hole-blocking materials, electron-injection materials, and / or electron-transport materials in electronic devices.

[0145] The present invention further provides an electronic element comprising at least one of the compounds or mixtures of the present invention described above. In this case, the preferred compounds described above are also applicable to the electronic element.

[0146] In a further embodiment of the present invention, the organic electroluminescent element of the present invention does not include individual hole injection layers and / or hole transport layers and / or hole blocking layers and / or electron transport layers, meaning that the light-emitting layer is directly adjacent to the hole injection layer or anode and / or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode, as described, for example, in WO2005 / 053051. Furthermore, as described, for example, in WO2009 / 030981, the same or similar metal complex in the light-emitting layer may also be used as a hole transport or hole injection material directly adjacent to the light-emitting layer.

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

[0148] Any material commonly used in the prior art can be used in a further layer of the organic electroluminescent element of the present invention. Accordingly, those skilled in the art can use any material known for organic electroluminescent elements in combination with the compound of the present invention according to formula (I) or a preferred embodiment, without inventive effort.

[0149] When the compounds of the invention are generally used in organic electroluminescent devices, they have very good properties. In particular, when the compounds of the invention are used in organic electroluminescent devices, the lifespan is significantly better compared to similar compounds according to the prior art. At the same time, other properties of the organic electroluminescent devices, especially efficiency and voltage, are similarly better or at least equivalent.

[0150] It should be noted that modifications to the forms described in the present invention are included within the scope of the present invention. Each feature disclosed in the present invention can be replaced with alternative features that serve the same purpose or equivalent or similar purposes, unless it is explicitly excluded. Therefore, each feature disclosed in the present invention should be regarded 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 each other in any way, provided that the special features and / or procedures are not mutually exclusive. This is especially true for the preferred features of the present invention. Similarly, non-essential combination features can be used separately (without combination).

[0152] It should be noted that many features, and especially the features of the preferred forms of the present invention, are not to be considered as inventive only in themselves and as only part of the forms of the present invention. For these features, independent protection can be sought in addition to or instead of the invention described in the current claims.

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

[0154] The present invention will be described in detail by the following examples, but it does not limit the present invention thereby.

[0155] Those skilled in the art can, without inventive modifications, further manufacture the electronic elements of the present invention using the following detailed description, thereby carrying out the present invention throughout the entire scope of the claims.

[0156] Examples The following synthesis is carried out in a dry solvent under a protective gas atmosphere unless otherwise specified. Solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. For compounds known from the literature, the corresponding CAS number is listed in each case.

[0157] Example of synthesis 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 then 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 washed repeatedly with water with the addition of toluene, and then dried and concentrated. The product is purified by column chromatography on silica gel using toluene / heptane (1:2). Yield: 155 g (553 mmol), 83% of theoretical yield.

[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 is dissolved in 2 L of dichloromethane and cooled to 5°C. 41.01 ml (431 mmol) of boron tribromide is added dropwise to this solution within 90 minutes, and the mixture is stirred overnight. The mixture is then gradually mixed with water, the organic phase is washed three times with water, dried over Na2SO4, concentrated in a rotary evaporator, and purified by chromatography. Yield: 104 g (397 mmol), 98% of the theoretical yield.

[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 is dissolved in 2 L of DMF (maximum 0.003% water) SeccoSolv® and cooled to 5°C. 20 g (449 mmol) of sodium hydride (60% suspension in mineral oil) is added to this solution in portions. Once the addition is complete, the mixture is stirred for 20 minutes, and then heated to 100°C for 45 minutes. After cooling, 500 ml of ethanol is slowly added to the mixture, which is then completely concentrated by rotary evaporator and purified by chromatography. Yield: 90 g (367 mmol), 88.5% of the theoretical yield.

[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 filtered by suction 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 the theoretical yield. The following compounds are prepared in a similar manner: [ka]

[0164] e) Dibenzofuran-1-boronic acid [ka] 180 g (728 mmol) of 1-bromodibenzofuran is 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 is added within approximately 5 minutes, and the mixture is stirred at -78°C for a further 2.5 hours. At this temperature, 151 g (1456 mmol) of trimethyl borate is added very rapidly, and the reaction mixture is slowly returned to room temperature (approximately 18 hours). The reaction solution is washed with water, and the precipitated solid and organic phase are azeotropically dried with toluene. The crude product is extracted from toluene / methylene chloride at approximately 40°C with stirring and filtered by suction. Yield: 146 g (690 mmol), 95% of theoretical yield.

[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 tetrakisphenylphosphine palladium(0) is 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 then dried and concentrated. The residue is recrystallized with heptane / dichloromethane. The yield is 13 g (41 mmol), 59% of the theoretical yield.

[0167] The following compounds can be obtained by a similar method: [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 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 and dried. The residue is recrystallized from toluene and from dichloromethane / heptane. The yield is 32 g (86 mmol), which is 80% of the theoretical yield.

[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 is suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulfuric acid (95-98%). 34 g (190 mmol) of NBS is added to the suspension, and the mixture is stirred in the dark for 2 hours. Water / ice is then added, the solid is removed, and the mixture is washed with ethanol. The residue is recrystallized with toluene. The yield is 59 g (130 mmol), which corresponds to 69% of the theoretical yield.

[0171] In the case of thiophene derivatives, nitrobenzene is used instead of sulfuric acid, and elemental bromine is used 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. 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 and dried. The residue is recrystallized from toluene and from dichloromethane / heptane. The yield is 37 g (94 mmol), which corresponds to 87% of the theoretical yield.

[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 is suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulfuric acid (95-98%). 34 g (190 mmol) of NBS is added to this suspension, and the mixture is stirred in the dark for 2 hours. Then, water / ice is added, the solid is removed, and the mixture is washed with ethanol. The residue is recrystallized with toluene. The yield is 80 g (167 mmol), which corresponds to 87% of the theoretical yield. The following compounds are prepared in a similar manner: [ka]

[0176] In the case of thiophene derivatives, nitrobenzene is used instead of sulfuric acid, and elemental bromine is used 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 was dissolved in 900 ml of dry DMF along with 39 g (1051 mmol) of bis(pinacolato)diborane (CAS 73183-34-3), and the mixture was degassed for 30 minutes. Subsequently, 37 g (376 mmol) of potassium acetate and 1.9 g (8.7 mmol) of palladium acetate were added, and the mixture was heated to 80°C overnight. After the reaction was complete, the mixture was diluted with 300 ml of toluene and extracted with water. The solvent was removed using a rotary evaporator, and the mixture was recrystallized with heptane. Yield: 61 g (117 mmol), 94% of theoretical yield.

[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]triazine-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 and dried. The product was purified by column chromatography using toluene / CHCl3 (1:1) on silica gel, and finally, under high vacuum (p=5x10). -7 It sublimes at mbar (99.9% purity). The yield is 51 g (81 mmol), which corresponds to 74% of the theoretical yield.

[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]triazine-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 were suspended in 100 ml of degassed DMF, and the reaction mixture was heated under reflux at 120°C for 40 hours. After cooling, the solvent was removed under reduced pressure, the residue was dissolved in dichloromethane, and water was added. The organic phase was then removed and filtered through silica gel. The yield was 27.9 g (54 mmol), which corresponds to 86% of the theoretical yield.

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

[0183] n)1-[9-(4,6-diphenyl-[1,3,5]triazine-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]triazine-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 under reflux at 140°C for 24 hours. After cooling, the solvent is removed under reduced pressure, and 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 by column chromatography using toluene / heptane (1:2) on silica gel, and finally, under high vacuum (p=5x10⁻¹⁰ -7 It sublimes at mbar (99.9% purity). The yield is 18.6 g (31 mmol), which corresponds to 63% of the theoretical yield.

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

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

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

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

[0188] All materials are coated by thermal deposition in a vacuum chamber. Here, the light-emitting layer always consists of at least one matrix material (host material) and a light-emitting dopant (light-emitting body) that is mixed in a specific volume ratio with the matrix material(s) by simultaneous deposition. Details such as INV-1:IC3:TEG1(60%:35%:5%) mean that material INV-1 is present in the layer at a volume ratio of 60%, IC3 at a volume ratio of 35%, and TEG1 at a volume ratio of 5%. Similarly, the electron transport layer may also consist of a mixture of two materials.

[0189] OLEDs are characterized by a standard method. For this purpose, the external quantum efficiency (EQE, measured in %) is determined as a function of the luminous flux density calculated from the current-voltage-luminous flux density characteristic line (IUL characteristic line), assuming Lambert radiation characteristics. The parameter U1000 in Table 2 corresponds to 1000 cd / m². 2 This represents the voltage required for a given luminous flux density. Finally, the EQE1000 has an operating luminous flux density of 1000 cd / m². 2 This represents the external quantum efficiency. The lifetime LT is defined as the time it takes for the luminous flux density to decrease by a certain percentage L1 from the initial luminous flux density when driven with a constant current. In Table X2, the values ​​for L0;j0=4000cd / m and L1=70% represent the lifetime reported in the LT column, where the initial luminous flux density is 4000cd / m 2 From 2800 cd / m² 2 This means it corresponds to the time it takes for the current to decrease. Similarly, L0;j0 = 20mA / cm 2 L1=80% is 20mA / cm 2 When in operation, this means that the luminous flux density decreases to 80% of its initial value after time LT has elapsed.

[0190] Table 2 summarizes data for various OLEDs. Examples C1 to C4 are comparative examples using the prior art and show OLEDs containing materials of the prior art. Examples I1 to I10 show data for OLEDs containing materials according to the present invention.

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

[0192] Use of the compound of the present invention as an electron transport material Examples and comparative examples demonstrate that the substituents of the present invention provide clear improvements in voltage and lifetime without significant losses in other characteristics.

[0193] When comparing material INV-7 with OLEDs used in ETL, in the case of using preferred materials INV-2, INV-3, INV-4, and INV-5, slight improvements in voltage are observed in some cases, and improvements in lifespan are also observed in some cases.

[0194] Use of the compound of the present invention as a matrix material in phosphorescent OLEDs The examples and comparative examples demonstrate that inventive substitutions result in significant improvements in voltage and lifespan without significant loss of other characteristics.

[0195] When material INV-6 is compared to OLEDs used in EML, in the case of using preferred materials INV-1, INV-2, INV-3, and INV-4, slight improvements in voltage and EQE are observed in some cases, and particularly significant improvements in lifetime are observed in some cases. [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 (Ia). 【Chemistry 1】 (The symbols used in the formula are as follows: q is 2, Y is either O or S, Q １ Q ２ In each case, is an electron transporter independently selected from the structures of formulas (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9), (Q-10), (Q-11), (Q-10a), (Q-11a), (Q-12), (Q-13), (Q-14), (Q-15), (Q-16), (Q-17), (Q-18), (Q-19), (Q-20), (Q-21), (Q-22), (Q-23), (Q-25), (Q-26), (Q-27), and / or (Q-28): 【Chemistry 2-1】 【Chemistry 2-2】 [Chemistry 2-3] [Chemistry 2-4] In the formula, the dotted line indicates the connection point. l is 0, 1, 2, 3, 4, or 5; m is 0, 1, 2, 3, or 4; n is 0, 1, 2, or 3; Ar １ has 6 to 40 carbon atoms and, in each case, is an aromatic or heteroaromatic ring system optionally substituted by one or more R ２ radicals, an aryloxy group having 5 to 60 aromatic ring atoms and optionally substituted by one or more R ２ radicals, or an aralkyl group having 5 to 60 aromatic ring atoms and optionally substituted by one or more R ２ radicals, where two or more adjacent R １ and / or R ２ substituents may, if desired, form an aliphatic ring system, which may be monocyclic or polycyclic and optionally substituted by one or more R ３ radicals; L １ , L ２ It has a bond or 5 to 30 aromatic ring atoms, and one or more R １ Aromatic ring system which may be substituted by radicals; R １ Each occurrence is either the same or different, D, F, Cl, Br, I, B (OR ２ ) ２ , CHO, C(=O)R ２ CR 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 these having 1 or more R ２ They may be substituted with radicals, where there is one or more non-adjacent CHs ２ The base 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 -, NR ２ , P(=O)(R ２ ), -O-, -S-, SO or SO ２ It may be replaced by, and here one or more hydrogen atoms are D, F, Cl, Br, I, CN or NO ２ (may be replaced by), or having 5 to 40 aromatic ring atoms, and in each case having 1 or more R ２ Aromatic or heteroaromatic ring systems that may be substituted with radicals, or having 5 to 40 aromatic ring atoms and 1 or more R ２ An aryloxy or heteroaryloxy group, or a combination thereof, which may be substituted with a radical; and simultaneously, two or more adjacent R １ The substituents may together form monocyclic or polycyclic aliphatic or aromatic ring systems; R ２ Each occurrence is either the same or different, H, D, F, Cl, Br, I, B (OR ３ ) ２ , CHO, C(=O)R ３ CR 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 these having 1 or more R ３ They may be substituted with radicals, where there is one or more non-adjacent CHs ２ The base 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 -, NR ３ , P(=O)(R ３ ), -O-, -S-, SO or SO ２ It may be replaced by, and here one or more hydrogen atoms are D, F, Cl, Br, I, CN or NO ２ (may be replaced by), or having 5 to 40 aromatic ring atoms, and in each case having 1 or more R ３ Aromatic or heteroaromatic ring systems that may be substituted with radicals, or having 5 to 40 aromatic ring atoms and 1 or more R ３ An aryloxy or heteroaryloxy group, or a combination thereof, which may be substituted with a radical; and simultaneously, two or more adjacent R ２ The substituents may together form monocyclic or polycyclic aliphatic or aromatic ring systems; R ３ Each occurrence may be the same or different, and may consist of H, D, F, or 1 to 20 carbon atoms. an aliphatic, aromatic and / or heteroaromatic hydrocarbyl radical having (where a hydrogen atom may be replaced by F); simultaneously, two or more adjacent R ３ substituents may together form a monocyclic or polycyclic, aliphatic or aromatic ring system)

2. The compound according to claim 1, characterized in that the compound is represented by formula (IIa). 【Transformation 3】 (In the formula, the symbols Y and L) １ , L ２ Q １ Q ２ , R １ (and q have the meanings described in claim 1)

3. The compound according to claim 1 or 2, characterized in that l is 0, 1 or 2, m is 0, 1 or 2, and n is 0 or 1.

4. Ar １ has 6 to 12 aromatic ring atoms and is optionally substituted by one or more R ２ radicals (where the R ２ radicals have the meaning as defined in claim 1), and is an aromatic ring system, a compound according to any one of claims 1 to 3.

5. The compound according to any one of claims 1 to 4, characterized in that the compound does not contain a carbazole and / or triarylamine group.

6. The compound according to any one of claims 1 to 5, characterized in that the compound does not contain a carbazole, indenocarbazole, indolocarbazole, arylamine, or diarylamine structure.

7. An oligomer, polymer, or dendrimer comprising one or more compounds according to any one of claims 1 to 6, wherein one or more bonds of the compound exist to the polymer, oligomer, or dendrimer.

8. A composition comprising at least one compound according to any one of claims 1 to 6 and / or an oligomer, polymer, or dendrimer according to claim 7, 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 conduction materials, hole injection materials, n-dopants, wide bandgap materials, electron blocking materials, and hole blocking materials.

9. A formulation comprising at least one compound according to any one of claims 1 to 6, an oligomer, polymer, or dendrimer according to claim 7, and / or at least one composition according to claim 8, and at least one solvent.

10. A method for preparing a compound according to any one of claims 1 to 6 or an oligomer, polymer, or dendrimer according to claim 7, characterized in that, in a coupling reaction, a compound comprising at least one electron transport group is coupled with a compound comprising at least one benzofuran and / or benzothiophene radical.

11. Use of a compound according to any one of claims 1 to 6, an oligomer, polymer, or dendrimer according to claim 7, or a composition according to claim 8, as a hole-blocking material, electron-injection material, and / or electron-transport material in an electronic device.

12. An electronic element comprising at least one compound according to any one of claims 1 to 6, an oligomer, polymer, or dendrimer according to claim 7, or the composition according to claim 8.

13. The electronic element according to claim 12, wherein the electronic element is selected from the group consisting of an organic electroluminescent element, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, an organic photodetector, an organic photoreceptor, an organic electric field quenching element, a light-emitting electrochemical cell, and an organic laser diode.

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