Material for electronic element

Abstract

To provide, in particular, as a matrix material for phosphorescent emitters, as a hole block material, as an electron transport material, or as desired as a material for charge generation layers, compounds suitable for use in OLEDs.SOLUTION: At one or more of 1-, 1'-, 4-, or 4'-positions, in any combination, fluorene derivatives bonded to the carbon atoms of diaryl-substituted triazinyl or pyrimidinyl derivatives are provided. Its fluorene derivative is not a spirobifluorene derivative.SELECTED DRAWING: None

Description

Detailed Description of the Invention

[0001] The present invention relates to the use of materials in electronic devices, in particular organic electroluminescent devices, and to electronic devices, in particular organic electroluminescent devices, comprising these materials.

[0002] The structure of organic electroluminescent devices (OLEDs) using organic semiconductors as functional materials is described, for example, in US4539507, US5151629, EP0676461 and WO98 / 27136. The emitting materials used therein are increasingly organometallic complexes that exhibit phosphorescence rather than fluorescence emission. On quantum mechanical grounds, the use of organometallic compounds as phosphorescence emitters allows for up to four times the energy increase and power efficiency. However, in the case of OLEDs in general, and in the case of OLEDs that exhibit triplet emission (phosphorescence) in particular, there is still a need for improvements, for example with regard to efficiency, operating voltage and lifetime.

[0003] The properties of phosphorescent OLEDs are not only determined by the triplet emitters used. In particular, the other materials used (e.g. matrix materials, hole-blocking materials, electron-transporting materials, hole-transporting materials, and electron or exciton-blocking materials) are of particular importance here. Improvements in these materials can also lead to significant improvements in the properties of the OLEDs (especially with regard to efficiency, lifetime, and heat resistance of the materials).

[0004] It is an object of the present invention to provide compounds suitable for use in OLEDs, in particular as matrix materials for phosphorescent emitters, as hole-blocking materials, as electron-transporting materials or, optionally, as materials for charge generating layers. It is a further object of the present invention to provide further organic semiconductors for organic electroluminescent devices, so that the skilled person has a wider choice of materials to manufacture the OLED.

[0005] The use of compounds containing both non-spirofluorenyl and triazinyl groups is known. For example, US7651790 discloses the use of OLEDs containing compounds of the formula ACB, where A is a hole transport group (including, inter alia, a non-spirofluorenyl group), B is an electron transport group (including, inter alia, a triazinyl group), and C is a single bond or a linking group.

[0006] Commonly assigned WO2010 / 015306 and WO2005 / 053055 disclose OLEDs containing fluorenes substituted at any position on the nitrogen, including 9,9-(dimethyl or diphenyl), as well as examples of bis-9,9'-spiro-, including triazine and pyrimidine-containing heterocycles.

[0007] US6821643, US6229012 and US6225467 disclose fluorenes substituted at the 2-position with a triazinyl group. US2004 / 0147742 and Wu, Appl. Phys. Lett., 81(4), 577-592 disclose fluorenes substituted at the 2-position with pyrimidines.

[0008] WO2015 / 073343 discloses an OLED comprising a triazine compound, 9,9-diphenylfluorene, substituted with at least two fluorene groups. Examples of both 3- and 4-triazinyl-substituted fluorenes are given. KR2013115161 discloses an OLED comprising 1-triazinyl-9,9-dimethylfluorene (wherein the triazine is substituted at the 4-position with 1-benzofuran and at the 6-position with an N-indene derivative). KR2013061371 discloses an OLED comprising a 1-(4-phenyl)triazinyl-9,9-dimethylfluorene derivative.

[0009] US20100045170 discloses an OLED comprising 1-(9-(10-(2-diazinyi)anthracenyl)diazine)-9,9-dimethylfluorene.

[0010] Commonly assigned WO 2014 / 023388 discloses OLEDs that include 9,9'-spirobifluorenes monosubstituted at the 1- or 4-positions with triazinyl or pyrimidinyl groups.Commonly assigned WO 2011 / 006574 discloses OLEDs that include 9,9'-spirobifluorenes disubstituted at the 4,4'-positions with triazinyl or pyrimidinyl groups.

[0011] Surprisingly, it has been found that certain compounds, as disclosed in detail below, achieve this objective, are highly suitable for use in OLEDs, and lead to improvements in organic electroluminescent devices. The improvements also relate in particular to lifetime and / or operating voltage. The present invention therefore relates to these compounds, and to electronic devices, in particular organic electroluminescent devices, comprising compounds of the type disclosed below.

[0012] The compounds of the present invention are general fluorene derivatives that are bonded to the carbon atoms of triazinyl or pyrimidinyl derivatives at one or more of the 1-, 1'-, 4- or 4'-positions by any bond. In the present invention, the fluorene derivatives of the present invention adopt the following numbering: [ka]

[0013] In particular, the present invention relates to compounds of formula (I): [ka] In the formulae, the following applies to the symbols and subscripts used: Z1 and Z2 are identical or different at each occurrence and are selected from the group consisting of H, D, F, Cl, Br, I, CHO, N(Ar1)2, C(=O)Ar1, P(=O)(Ar1)2, S(=O)Ar1, S(=O)2Ar1, CR2=CR2Ar1, CN, NO2, Si(R1)3, B(OR1)2, B(R1)2, B(N(R1)2)2, OSO2R1, linear alkyl, alkoxy or thioalkoxy groups having 1 to 40 C atoms, linear alkenyl or alkynyl groups having 2 to 40 C atoms, branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy groups having 3 to 40 C atoms, each of which may be substituted by one or more radicals R1, where one or more wherein the preferably non-adjacent CH2 groups are (R1)C=C(R1), C≡C, Si(R1)2, Ge(R1)2, Sn(R1)2, C=O, C=S, C=Se, C=N(R1)2, P(=O)(R1), SO, SO2, N(R1)2, O, S or CON(R1)2 and one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN or NO2), or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, in each case optionally substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more radicals R1.

[0014] The fluorene derivatives according to the invention are not bis-9,9'-spirobifluorenes, i.e. the groups Z1 and Z2 at the 9-position do not represent another fluorene group. Thus, the heterocycle-substituted fluorene rings of the invention are bis-9,9-spirobifluorene groups, which may be further substituted or linked as shown below: [ka] It is understood that in some embodiments, Z1 and Z2 may be spiro saturated ring systems. For example, Z1 and Z2 may represent cyclopentyl or cyclohexyl ring systems. However, it is preferred that Z1 and Z2 are separate substituents and are not bonded to each other at any position other than the 9-position of the fluorene ring.

[0015] Y1 and Y2 are identical or different at each occurrence and are selected from the group consisting of D, F, Cl, Br, I, CHO, N(Ar1)2, C(=O)Ar1, P(=O)(Ar1)2, S(=O)Ar1, S(=O)2Ar1, (R1)C=C(R1)Ar1, CN, NO2, Si(R1)3, B(OR1)2, B(R1)2, B(N(R1)2)2, OSO2R1, linear, alkyl, alkoxy or aryl having 1 to 40 C atoms. a thioalkoxy group, or a linear alkenyl or alkynyl group having 2 to 40 C atoms, a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R1, in which one or more, preferably non-adjacent CH2 groups are selected from the group consisting of (R1)C=C(R1), C≡C, Si(R1)2, Ge(R1)2, Sn(R1)2, C=O, C=S, C=Se, C=N(R1)2, P(=O(R1)2, SO, SO2, N(R1)2, O, S or CON(R1)2 and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2), or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, in each case optionally substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more radicals R1, or a combination of these systems, where two or more adjacent substituents Y1 or Y2 may form a fused, monocyclic or polycyclic, aliphatic or aromatic or heteroaromatic ring system with respect to each other.

[0016] Ar1 and Ar2 are identical or different at each occurrence and are aromatic or heteroaromatic ring systems having 5 to 23 aromatic ring atoms, optionally substituted in each case by one or more radicals R1, preferably non-aromatic radicals R1, provided that the heteroaromatic ring systems are linked via carbon-carbon bonds.

[0017] R1 is identical or different at each occurrence and is selected from the group consisting of H, D, F, Cl, Br, I, CN, Si(R2)3, linear alkyl, alkoxy or thioalkoxy groups having 1 to 40 C atoms, branched or cyclic alkyl, alkoxy or thioalkoxy groups having 3 to 40 C atoms, which may be substituted by one or more radicals R2, in which one or more non-adjacent CH2 groups may be replaced by C(R2)=C(R2), Si(R2)2, C=NR2, P(=O)(R2), SO, SO2, NR2, O, S or CONR2, and one or more H atoms may be replaced by D, F, Cl, Br or I, aromatic or heteroaromatic rings having 6 to 40 carbon atoms, which may be substituted by one or more radicals R2. or an aryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more radicals R2; an aralkyl group having 5 to 60 aromatic ring atoms, optionally substituted by one or more radicals R2, whereby, if desired, two or more adjacent substituents R1 together form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, optionally substituted by one or more radicals R2, whereby R2 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 C atoms, whereby two or more adjacent substituents R2 together may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system. X is the same or different at each occurrence and is CR1 or N, with the proviso that at least one X is N. L is identical or different at each occurrence and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, optionally substituted by one or more non-aromatic radicals R1. a, b, c and d are each the same or different and are 0 or 1, with the proviso that at least one of a, b, c or d is 1. e and f are the same or different and are each 0, 1, 2 or 3. n is the same or different at each occurrence and is 0 or 1.

[0018] In a preferred form of the invention, the compound of formula (I) is not [ka]

[0019] Unless otherwise specified, an aryl group in the sense of the present invention contains 6 to 24 carbon atoms, and a heteroaryl group in the sense of the present invention contains 2 to 24 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. Here, an aryl or heteroaryl group is either a single aromatic ring, i.e. benzene, or a single heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused, aryl or heteroaryl, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

[0020] Unless otherwise specified, an aromatic ring system, within the meaning of the present invention, comprises 6 to 40 carbon atoms in the ring system. Unless otherwise specified, a heteroaromatic ring system, within the meaning of the present invention, comprises 1 to 40 carbon atoms and at least one heteroatom in the ring system, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and S. Unless otherwise specified, an aromatic or heteroaromatic ring system, within the meaning of the present invention, is understood to mean not only systems containing aryl or heteroaryl groups, but also systems in which several aryl or heteroaryl groups are linked by non-aromatic units, such as C, N or O atoms, or carbonyl groups. For example, unless otherwise specified, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, stilbene, etc., are aromatic ring systems for the purposes of the present invention. Also included are systems in which two or more aryl groups are linked, for example, by linear or cyclic alkylene groups or by silylene groups. Additionally, systems in which two or more aryl or heteroaryl groups are directly bonded to each other, for example, biphenyl, terphenyl, quaterphenyl, are also understood to be aromatic or heteroaromatic ring systems, unless otherwise specified.

[0021] For the purposes of this invention, cyclic, alkyl, alkoxy or thioalkoxy means monocyclic, bicyclic or polycyclic groups.

[0022] In the present invention, examples of the C1-C40 alkyl group (wherein each hydrogen atom or CH2 group may be replaced by the above-mentioned group) include 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, neo-hexyl, cyclopentyl, 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, or 2,2,2-trifluoroethyl, 1, 1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl, 1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-oct-1-yl, Examples of the alkenyl group include 1,1-diethyl-n-dec-1-yl, 1,1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl, 1,1-diethylnn-hexadeca-1-yl, 1,1-diethyl-n-octadec-1-yl, 1-(n-propyl)cyclohex-1-yl, 1-(n-butyl)cyclohex-1-yl, 1-(N-hexyl)cyclohex-1-yl, 1-(n-octyl)cyclohex-1-yl and 1-(n-decyl)cyclohex-1-yl. The alkenyl group is, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl.Alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. Alkoxy groups having 1 to 40 C atoms are preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. A thioalkyl group having 1 to 40 C atoms is understood to mean, in particular, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. Generally, an alkyl, alkoxy or thioalkyl group according to the present invention may be linear, branched or cyclic, in which one or more non-adjacent CH groups may be replaced by the above groups, and in addition, one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO, preferably by F, Cl or CN, more preferably by F or CN, and particularly preferably by CN.

[0023] Unless otherwise specified, aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, each of which may be substituted by the above radicals and which may be linked at any position to an aromatic or heteroaromatic compound, include, for example, benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoracene, benzofluoracene, naphthacene, pentacene, benzopyrene, biphenyl, biphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, fluorene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isopropyl alcohol, soquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridine imidazole, pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole azole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazapyrylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxazole, 1,2,It is understood to mean radicals derived from 4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiazole.

[0024] In the above, R1 is a first substituent and R2 is a further optional substituent of R1, as well as L, Z1, Z2, Y1 and Y2. Both R1 and R2 can be independently selected from the same group described. In the sense of the present invention, adjacent radicals or adjacent substituents are understood to mean substituents that are attached to C atoms that are directly bonded to each other or that are attached to the same C atom.

[0025] In compounds processed by vacuum deposition, the alkyl groups preferably have 5 C atoms, particularly preferably 4 C atoms, and even more particularly preferably 1 C atom or less. For compounds processed from solution, suitable compounds are those substituted with alkyl groups, especially branched alkyl groups, or oligoarylene groups (e.g. ortho-, meta-, para- or branched terphenyl groups), up to 10 C atoms. It should be understood that for compounds processed by vacuum deposition, one or more compounds can be co-deposited to form a mixed layer at the same time. For example, a mixture of two or more different host compounds (one of which is a compound according to the invention) is mixed in a predetermined ratio and the solid mixture is co-deposited to form a mixed matrix layer (together with the luminescent material). Alternatively, two (or more) compounds can be deposited separately and the resulting vapors can form a mixed layer in the appropriate ratio.

[0026] When the compound of formula (I) or preferred forms is used as a matrix material for phosphorescent emitters or in a layer directly adjacent to a phosphorescent light-emitting layer, R1, R2, Z1, Z2, Y1, Y2, Ar1 and Ar2 and L of the compound more preferably do not include fused aryl or heteroaryl groups in which more than two 6-membered rings are directly fused to each other. However, one exception is the triphenylene group, which has more than two 6-membered rings, but is suitable and preferred as a triplet matrix material. In general, it is advantageous that the triplet energy of the compound used as a matrix material or in an adjacent layer is equal to or greater than the triplet energy of the phosphorescent material of the light-emitting layer.

[0027] The compounds according to the present invention described above, especially those substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic acid ester, or reactive polymerizable groups such as olefins, styrenes, acrylates or oxetanes, may be used as monomers for the preparation of the corresponding oligomers, dendrimers or polymers. Here, oligomerization or polymerization is preferably achieved by halogen or boronic acid functionality or by polymerizable groups. Furthermore, the polymers can also be crosslinked via such groups. The compounds and polymers according to the present invention may be used in the form of crosslinked or non-crosslinked layers.

[0028] Therefore, the present invention further relates to an oligomer, polymer or dendrimer comprising one or more of the above-mentioned compounds according to the invention, in which one or more bonds from the compounds according to the invention to the polymer, oligomer or dendrimer are present in one or more positions instead of a substituent. According to the bonds of the compounds according to the invention, they form the side chains of the oligomer or polymer, are attached to the main chain or form the core of the dendrimer. The polymer, oligomer or dendrimer may be conjugated, partially conjugated or not conjugated. The oligomer or polymer may be linear, branched or dendritic. For the repeat units of the compounds of the invention in oligomers, dendrimers and polymers, the same preferences apply as above.

[0029] To prepare oligomers or polymers, the monomers of the invention are homopolymerized or copolymerized with further monomers. It is preferred that the units of formula (I) or the preferred forms mentioned above are present in the range of 0.01 to 99.9 mol %, preferably 5 to 90 mol %, more preferably 20 to 80 mol %. Suitable and preferred comonomers forming the polymer backbone are fluorene (e.g. EP842208 or WO2000 / 022026), spirobifluorene (e.g. EP707020, EP894107 or WO2006 / 061181), paraphenylene (e.g. WO92 / 18552), carbazole (e.g. WO2004 / 070772 or WO2004 / 113468), thiophene ( For example, EP1028136), dihydrophenanthrenes (for example WO2005 / 014689), cis- and trans-indenofluorenes (for example WO2004 / 041901 or WO2004 / 113412), ketones (for example WO2005 / 040302), phenanthrenes (for example WO2005 / 104264 or WO2007 / 017066) or other multiples of these units. The polymers, oligomers and dendrimers may also contain further units, for example electron transport units. Furthermore, the polymers may also contain triplet emitters, copolymerized or mixed as a mixture. In particular, the combination of the oligomers, polymers or dendrimers according to the invention with triplet emitters shows particularly good results.

[0030] In the following formulae characterizing compounds of formula (I), Q represents a triazine / pyrimidine subunit of formula (I). [ka]

[0031] The groups Z1 and Z2 at the 9-position of the fluorene ring are preferably the same or different and are linear or branched groups having 1 to 12 atoms, or aromatic or heterocyclic ring systems having 5 to 40 aromatic ring atoms. More preferably, Z1 and Z2 are the same or different and are linear alkyl groups having 1 to 6 atoms, or aromatic ring systems having 6 to 24 aromatic ring atoms. Examples of particularly preferred alkyl groups are methyl and ethyl. Examples of particularly preferred aromatic ring systems are phenyl, pt-butylphenyl, p-(heteroaromatic)phenyl, m- or p-biphenyl or naphthyl. Of course, most preferred are methyl or phenyl. The groups Z1 and Z2 may be the same or different, but it is preferred that they are the same. Some examples of suitable substituents Z1 and Z2 of the fluorene ring of the compounds of the present invention are given below, but are not limited thereto. [ka] Y1 and Y2 represent the substituents of the two different fluorene rings of the compounds of the invention. Whenever a, b, c or d is 0 (no Q group), it is understood that this position may or may not be occupied by a group Y1 or Y2. Whenever e or f is 0, there is no group Y1 or Y2 present in the ring and the vacant position is H. This is most preferred. Whenever e or f is not 0, Y1 and Y2 are the same or different, and are preferably aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms. Some examples of preferred aromatic groups include substituted or unsubstituted phenyl, naphthyl, anthracenyl, each of which may be further substituted by one or more groups R1. Examples of preferred heteroaromatic groups include N-arylcarbazoyl, benzimidazole, dibenzofuran, dibenzothiophene or fluorene, including 9,9'-spirobifluorene. Whenever e or f is 2, it is preferred that two adjacent substituents Y1 or Y2 form a fused, monocyclic or polycyclic, aliphatic or aromatic or heteroaromatic ring system with each other. Some examples of suitable substituents Y1 and Y2 of the fluorene ring of the compounds of the present invention are listed below, but are not limited thereto. [ka]

[0032] In the above structure, R1 is as described above and each g is independently 0, 1, 2, 3, or 4.

[0033] In the following examples of suitable Y1 and Y2 adjacent to each other and forming a fused ring system, in the compound of formula (I), only one of a, b, c and d is 1, and the others are 0. It is understood that the present invention is not limited to these illustrated examples, and that similar examples are also possible in which a, b, c or d are 0 or 1 in any combination. [ka]

[0034] In the compound of the present invention, the fluorene ring is preferably such that only one of a or b substituted by 1 to 4 Q groups at the 1-, 1'-, 4-, 4'-positions in any combination is 1, and only one of c or d is 1. It is more preferred that b is 1 (a is 0) and either c or d is 1. It is even more preferred that one of a or b is 1, and c and d are both 0. It is most preferred that only b is 1, and a, c and d are 0.

[0035] L is a linking group that connects (directly or indirectly) the carbon atom in the triazine or pyrimidine group to the fluorene ring. When n is 0, there is no linking group, and the carbon atom in the triazine or pyrimidine group is directly connected to the fluorene ring at the 1-, 1'-, 4- or 4'-position by a single bond. For example, when a, b, c and d are each 1 and the corresponding n is 0, the compound of formula (I) would be: [ka]

[0036] It is understood that n may be the same or different in each Q group. For example, in the case where b and d are both 1 (a and c are 0), the corresponding n may be 0 and 1, as shown below. [ka]

[0037] When n is 1, L is a linking group that indirectly bonds a carbon atom in the triazine or pyrimidine group to any 1-, 1'-, 4-, or 4'-position of the fluorene ring through at least one other atom that is not part of the triazine / pyrimidine group or fluorene ring. Both the bonds from L to the fluorene ring as well as the triazine / pyrimidine to L are through single bonds. Preferably, L is an aromatic ring system having 6-30 aromatic ring atoms, which may be the same or different at each occurrence and may be further substituted. Some examples of preferred L include phenyl, biphenyl, or anthracenyl. Of these, phenyl is most preferred, desirably through the 1,4- or 1,3-positions of the phenyl. L may be the same or different for each Q group. For example, in the following compound, b and d are 1 (a and c are 0) and the corresponding L groups are different. [ka] Most preferably, n is 0.

[0038] In formula (I), at least one X, which is the same or different at each occurrence, is N. In the sense of the present invention, in each Q group, in each heteroaromatic ring, at least one X is N. When both X in the same ring are N (which is preferred), the Q group is a 2,4-disubstituted 1,3,5-triazine (triazinyl group). [ka]

[0039] When exactly one of X is N and the other X is CR1, the Q group is a 2,4-disubstituted 1,5- or 1,3-pyrimidine(pyrimidinyl) group. [ka]

[0040] In either of these pyrimidine groups, it is preferred that the radical R1 present on X does not form a ring with any adjacent substituent (Ar1, Ar2, L or the fluorene ring or any substituent Y when n is 0). In particular, it is preferred that the triazinyl or pyrimidinyl group is a single ring system and has no fused rings. Most preferably, R1 is H.

[0041] It is understood that the selection of X is independent for each Q group. That is, the compound of formula (I) may have 1-4 triazinyl groups, 1-4 pyrimidinyl groups, or 1-4 groups in any combination of the two. For example, the following compound of formula (I) in which b and d are both 1, a and c are both 0, and n is 0 in both Q groups indicates that Q may be the same or mixed. [ka]

[0042] Not limited to the examples shown above, similar examples are possible in which the 4- and 1'-positions are swapped, or in which the 1- and 4'-, 1- and 4-, 1'- and 4'-positions are located.Similar examples of 3 or 4Q groups consisting of mixtures of the same or any combination of triazinyl or pyrimidinyl groups are also envisioned.

[0043] In the meaning of the triazinyl or pyrimidinyl group Q, preferred groups Ar1 and Ar2 are identical or independently aromatic or heteroaromatic ring systems having 5 to 23 aromatic ring atoms, which in each case may be substituted by one or more radicals R1. The sum of the aromatic ring atoms (carbon or heteroatoms) includes all the respective aromatic ring atoms (for this purpose, all sp 2 Hybridized carbon atoms and heteroatoms have at least two different sp 2(including divalent or trivalent heteroatoms when bonded to carbon atoms, but excluding non-aromatic tetrahedral carbon and nitrogen atoms). For example, suitable groups for Ar1 and Ar2 (sum of aromatic ring atoms) include benzene (6), ortho-, meta-, or para-biphenyl (12), ortho-, meta-, para-, or branched terphenyl (18), 1-, 2-, 3-, or 4-9,9-dialkylfluorenyl (12), 1- or 2-naphthyl (10), pyrrole (5), furan (5), thiophene (5), indole (9), benzofuran (9), benzothiophene (9), 1-, 2-, or 3-N-alkylcarbazole (13), 1-, 2-, or 3-N-phenylcarbazole (19) (which may be bonded to an N-phenyl group), 1-, 2-, or Examples include 3-dibenzofuran (13), 1-, 2- or 3-dibenzothiophene (13), indenocarbazole (19), indolocarbazole (20), 2-, 3- or 4-pyridine (6), 2-, 4- or 5-pyrimidine (6), pyrazine (6), pyridazine (6), triazine (6), anthracene (14), phenanthrene (14), triphenylene (18), pyrene (16), benzoanthracene (18), N-phenylphenanthridinone (20), or combinations of two or three of these groups (each of which may be substituted with one or more radicals R1, so long as the total is 23 or less aromatic ring atoms). Some examples of non-inventive substituents of more than 23 aromatic ring atoms include quaterphenyl (24), 9,9-diphenylfluorene (24) and 9,9'-spirobifluorene (24). Ar1 and Ar2 are in particular selected from the group consisting of benzene, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, naphthyl, triphenylene, 9,9-dialkylfluorenyl or derivatives, N-phenylcarbazole, dibenzofuran and dibenzothiophene. This preferred group is understood to include not only the basic unsubstituted structures but also their derivatives, e.g., further substituted by the substituent R1.In particular, 9,9-dialkylfluorenyl, N-phenylcarbazole, dibenzofuran and dibenzothiophene derivatives may have fused rings or be linked to Q via a linking phenyl group, as long as there are no more than 23 aromatic ring atoms in the entire substituent, including any aromatic ring atoms in R1. The substituents R1 of Ar1 and Ar2 are preferably non-aromatic. Ar1 and Ar2 are linked to the triazinyl or pyrimidinyl group via a single bond, and do not form a ring system or have any other bond to the triazinyl or pyrimidinyl group. Furthermore, Ar1 and Ar2 are different from the linking group L. That is, the triazinyl or pyrimidinyl group is not linked to the fluorene via Ar1 or Ar2. In a preferred embodiment of the invention, Ar1 and Ar2 are identical.

[0044] In a further preferred form of the invention, the aromatic groups in the groups Ar1 and Ar2, when either contains one or more aryl groups, are not para-linked, i.e., they are preferably not para-biphenyl or para-terphenyl, but instead are, for example, ortho- or meta-linked structures, respectively.

[0045] However, when Ar1 or Ar2 (or both) are or contain a nitrogen-containing heteroaromatic group, such as a carbazole, pyrrole, imidazole or benzimidazole group, the heteroaromatic group is not directly bonded to the triazine or pyrimidine ring through a nitrogen atom, but instead is bonded to a carbon atom in the triazine or pyrimidine through a carbon atom of the heteroaromatic group. For example, when Ar1 or Ar2 is an N-phenylcarbazole group, it can be bonded to the triazine or pyrimidine backbone through a carbon atom of the carbazole or a carbon atom of the N-phenyl group (see examples below), but when Ar1 or Ar2 is a carbazole group, it is not bonded directly to the triazine or pyrimidine ring by the nitrogen atom of the carbazole group.

[0046] Some non-limiting examples of Ar1 and Ar2 are as follows: [ka]

[0047] As mentioned above, in the compound of formula (I), it is preferred that Z1 and Z2 are the same, which corresponds to formula (II). [ka]

[0048] As stated above, it is preferred that in compounds of formula (I), e or f are both 0, the substituents Y1 or Y2 are absent and the vacant position is H. This corresponds to formula (III). [ka] As stated above, in compounds of formula (I), it is preferred that exactly one of a or b is 1 and exactly one of c or d is 1. This corresponds to formulae (IV) and (V). [ka]

[0049] As stated above, it is preferred that in compounds of formula (I), b is 1, a is 0, and either c or d is 1 and the other is 0. This corresponds to formulae (VI) and (VII). [ka]

[0050] As stated above, in compounds of formula (I), it is preferred that b is 1 and a, c and d are 0. This corresponds to formula (VIIIa). [ka]

[0051] Alternatively, it is also preferred that in the compound of formula (I), a is 1 and b, c and d are 0. This corresponds to formula (VIIIb). [ka]

[0052] The above preferred embodiments can be combined with each other if desired. In a particularly preferred embodiment of the present invention, the above preferred aspects occur simultaneously. For example, the following formulae (IX) to (XVII) are some preferred combinations of the features in which Q is located at the 4-position. [ka]

[0053] Also contemplated are analogous compounds of formulae (IX)-(XVII) in which Q is in position 1 rather than position 4. Of course, formulae XII, XV, XVI and XVII in which both X are nitrogen and are triazine groups (or the corresponding compounds in which the triazine group is in position 1) are most preferred.

[0054] The following examples are some of the compounds of formula (I). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

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[0055] In order to process the compounds of the present invention from liquid phase, for example by spin coating or printing, a formulation of the compounds of the present invention is required.These formulations can be, for example, solutions, dispersions or emulsions.For this purpose, it is preferred to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methylbenzoic acid, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexanol ... Examples of the solvent include cyclohexane, cyclohexanediol ...

[0056] The present invention therefore also relates to a formulation comprising the compound according to the invention and at least one further compound.The further compound is, for example, a solvent, in particular one of the above-mentioned solvents or a mixture of these solvents.However, the further compound can also be an organic or inorganic compound, for example a light-emitting compound and / or a further matrix material, which are also used in electronic devices.Suitable light-emitting compounds and further matrix materials are described below in connection with organic electroluminescent devices.This further compound can also be a polymer.

[0057] The compound according to the present invention is suitable for use in electronic devices, particularly organic electroluminescent devices.Therefore, the present invention further relates to the use of the compound according to the present invention in electronic devices, particularly organic electroluminescent devices.The present invention further relates to an electronic device comprising at least one compound according to the present invention.

[0058] An electronic device in the sense of the present invention is a device comprising at least one layer comprising at least one organic compound. The components may comprise inorganic materials or may be layers entirely formed from inorganic materials. The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs), 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), dye-sensitized organic solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and "organic plasma light emitting devices", more preferably organic electroluminescent devices (OLEDs), particularly preferably phosphorescent OLEDs.

[0059] The organic electroluminescent device comprises a cathode, an anode, and at least one light-emitting layer. Besides these layers, it may also comprise further layers, for example, in each case, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generating layers. For example, an intermediate layer having an exciton blocking function may also be introduced between two light-emitting layers. However, it should be pointed out that each of these layers does not necessarily have to be present. It is possible for the organic electroluminescent device to comprise one light-emitting layer, or multiple light-emitting layers. If multiple light-emitting layers are present, they preferably have multiple emission maxima in the range of 380 nm to 750 nm as a whole, resulting in a white light emission as a whole, i.e., various light-emitting compounds capable of emitting fluorescence or phosphorescence are used in the light-emitting layers. Particularly preferred are systems with two emitting layers (two layers exhibiting blue and orange or yellow emission) or three emitting layers (three layers exhibiting blue, green and / or orange or red emission (see, for example, WO2005 / 011013)). The organic electroluminescent device according to the invention may be a series OLED, in particular for white emission.

[0060] The compounds of the invention according to the above forms can be used in various layers of electronic devices, depending on the exact structure. Organic electroluminescent devices comprising compounds of formula (I) or the above preferred forms as phosphorescent or fluorescent emitters, especially phosphorescent emitters, and / or in electron blocking or exciton blocking layers and / or in charge generating layers and / or in hole blocking or electron transport layers, depending on the appropriate substitution, are preferred.

[0061] In a preferred embodiment of the present invention, the compounds according to the invention are used as matrix materials for phosphorescent compounds in an emitting layer, where the organic electroluminescent device may comprise one or more emitting layers, at least one emitting layer comprising at least one compound according to the invention as matrix material.

[0062] When the compound according to the invention is used as a matrix material for phosphorescent compounds in the emitting layer, it is preferred to use it in combination with one or more phosphorescent materials (triplet emitters).In the sense of the present invention, phosphorescence is meant to mean light emission from excited states, especially excited triplet states, with relatively high spin multiplicity, i.e. spin state>1.In the sense of the present application, all luminescent complexes, including transition metals or lanthanides, especially all iridium, platinum and copper complexes, are considered as phosphorescent compounds.

[0063] The mixture of the compound according to the invention and the light-emitting compound comprises 99-1% by volume, preferably 98-10% by volume, more preferably 97-60% by volume, in particular 95-80% by volume, of the compound according to the invention, based on the total mixture of light emitters and matrix materials. Correspondingly, the mixture comprises 1-99% by volume, preferably 2-90% by volume, more preferably 3-40% by volume, in particular 5-20% by volume, of the light emitter, based on the total mixture of light emitters and matrix materials. A further preferred embodiment of the invention is the use of the compound according to the invention as a matrix material for phosphorescent emitters in combination with a further matrix material.Particularly suitable matrix materials which may be used in combination with the compounds of the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones (for example according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680), triarylamines, carbazole derivatives (for example CBP (N,N-biscarbazonylbiphenyl)) or carbazole derivatives (WO 2005 / 039246, US 2005 / 006972). 9, JP2004 / 288381, EP1205527, WO2008 / 086851 or WO2013 / 041176), indolocarbazole derivatives (for example, according to WO2007 / 063754 or WO2008 / 056746), indenocarbazole derivatives (for example, according to WO2010 / 136109, WO2011 / 000455, WO2013 / 041176 or WO2013 / 056776), azacarbazoles (for example, according to EP1617710, EP1617711, EP17315 84, JP2005 / 347160), bipolar matrix materials (for example, according to WO2007 / 137725), silanes (for example, according to WO2005 / 111172), azaboroles or boronic acid esters (for example, according to WO2006 / 117052), triazine derivatives (for example, according to WO2007 / 063754, WO2008 / 056746, WO2010 / 015306, WO2011 / 057706, WO2011 / 060859 or WO2011 / 060877), zinc complexes (for example according to EP 652273 or WO 2009 / 062578), diazasilol or tetraazasilol derivatives (for example according to WO 2010 / 054729), diazaphosphole derivatives (for example according to WO 2010 / 054730), bridged carbazole derivatives (for example according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080), or triphenylene derivatives (for example according to WO 2012 / 048781).Further phosphorescent emitters that emit at shorter wavelengths than the actual emitter may also be present as co-hosts or as compounds that do not participate to any significant extent, if at all, in charge transport (as disclosed, for example, in WO2010 / 108579). It is well within the capabilities of a person skilled in the art to determine the appropriate relative proportions of all materials present, as well as to select the appropriate matrix material and emitter of the emissive layer.

[0064] Suitable phosphorescent compounds (triplet emitters) are in particular compounds which emit light, preferably in the visible range, upon suitable excitation, and further comprise at least one atom with an atomic number greater than 20, more preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. The phosphorescent emitters used are preferably compounds which comprise copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds which comprise iridium or platinum.

[0065] Examples of the above mentioned phosphors are disclosed in WO2000 / 70655, WO2001 / 41512, WO2002 / 02714, WO2002 / 15645, EP1191613, EP1191612, EP1191614, WO2005 / 033244, WO2005 / 019373, US2005 / 0258742, WO2010 / 086089, WO2011 / 157339, WO2012 / 007086, WO2012 / 163471, WO2013 / 000531, WO2013 / 020631, WO2014 / 008982 and WO2014 / 023377. Generally, any phosphorescent complex as used in the prior art of phosphorescent OLEDs and as known to a person skilled in the art in the field of organic electroluminescent devices is suitable, and a person skilled in the art will be able to use further phosphorescent complexes without inventive ingenuity.

[0066] The compounds according to the invention are also particularly suitable as matrix materials for phosphorescent emitters in organic electroluminescent devices, as disclosed, for example, in US2011 / 0248247 and US2012 / 0223633.In these multicolor display components, an additional blue light-emitting layer is applied by vapor deposition to all areas and to all pixels, including colors other than blue.Surprisingly, it has been found that the compounds according to the invention, when used as matrix materials for red and / or green pixels, together with the blue light-emitting layer applied by vapor deposition, result in very good luminescence.

[0067] In a further embodiment of the invention, the organic electroluminescent device according to the invention does not comprise a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, i.e. the light emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode (for example as disclosed in WO2005 / 053051).Furthermore, in the light emitting layer, it is also possible to use a metal complex identical or similar to the metal complex as the hole transport or hole injection material directly adjacent to the light emitting layer (for example as disclosed in WO2009 / 030981).

[0068] In a further aspect of the invention, the compounds according to the invention are used in an exciton blocking layer.

[0069] In a further preferred embodiment of the invention, the compounds according to the invention are used as electron transport materials in electron transport or electron injection layers, where the emitting layer may be phosphorescent or fluorescent. When the compounds are used as electron transport materials, they are preferably doped, for example with an alkali metal or an alkali metal complex, for example with Li or LiQ (lithium quinolinate).

[0070] In a further preferred embodiment of the invention, the compounds according to the invention are used in a hole blocking layer, which is taken to mean the layer directly adjacent to the cathode side of the light emitting layer. Another preferred embodiment uses the compounds as part of a charge generating layer. A charge generating layer (CGL) acts as an injector of electron-hole pairs in voltage applications. Typically, a CGL consists of an electron rich layer (e.g., an n-doped electron transport layer) adjacent to an electron deficient layer (e.g., a p-doped hole transport layer). However, in some cases, the CGL may be only a single layer. In other cases, one or both layers of the CGL may be doped or undoped.

[0071] In the further layers of the organic electroluminescent device according to the present invention, all materials used can be used as they are usually used according to the prior art.Therefore, a person skilled in the art can use all materials for organic electroluminescent devices known in the prior art without inventive ingenuity, in combination with the compound of formula (I) according to the present invention or the above-mentioned preferred forms.

[0072] Furthermore, preferred organic electroluminescent devices are characterized in that one or more layers are applied by sublimation. In this case, the materials are generally applied in a range of 10 -5 Less than mbar, preferably less than 10 -6 The vacuum deposition is carried out in a vacuum sublimation unit at an initial pressure of less than 10 mbar. The initial pressure can be even lower, for example 10 -7 It is also possible to go below mbar.

[0073] Also preferred are organic electroluminescent devices characterized in that one or more layers are applied by the OVPD (organic vapor phase deposition) method or by means of sublimation of a carrier gas. -5The material is applied at pressures between mbar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied and structured directly through a nozzle (eg, MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0074] Furthermore, preferred organic electroluminescent devices are characterized in that one or more layers are produced from solutions, for example by spin-coating or by printing methods (for example screen printing, flexographic printing, offset printing), LITI (Light Induced Thermal Imaging, thermal transfer printing), inkjet printing or nozzle printing, etc. Soluble compounds, obtainable for example by suitable substitution, are necessary for this purpose.

[0075] Hybrid processes are also possible, for example, in which one or more layers are applied from solution and one or more further layers are applied by vapor deposition. These processes are known to those skilled in the art and can be applied to organic electroluminescent devices comprising the compounds according to the invention without inventive effort.

[0076] The compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished by one or more of the following surprising advantages over the prior art: 1. The compounds according to the invention used as matrix materials for fluorescent or phosphorescent emitters provide long lifetimes. This is especially true when the compounds are used as matrix materials for phosphorescent emitters. 2. The compounds according to the invention provide very high efficiencies, in particular when the compounds are used as matrix materials for phosphorescent emitters or as hole transport materials. 3. In some embodiments, the compounds according to the invention result in low voltage devices, especially when the compounds are used as matrix materials for phosphorescent emitters or in electron transport layers.

[0077] These above mentioned advantages are not accompanied by degradation of other electronic properties.

[0078] The present invention is described in detail by the following examples, but is not intended to be limited thereto. Those skilled in the art will be able to use the details described to carry out the invention throughout the disclosed scope, and to prepare further compounds according to the present invention and use them in electronic devices or apply them in the methods according to the present invention without inventive ingenuity.

[0079] Working Example Synthesis Example The following syntheses are carried out in dry solvents under a protective gas atmosphere unless otherwise stated. Solvents and reagents can be purchased from ALDRICH or ABCR. The numbers indicated for commercially available starting materials are the corresponding CAS numbers.

[0080] The materials of the present invention can generally be prepared according to the following synthetic scheme 1 (Note: in scheme 1, 2 or 3 X will be N. When two nitrogens are present, the other X will be CR1. R3 is preferably, but not limited to, a fluorene skeleton. In some embodiments, the fluorene skeleton may be added in step 1 or 2a / b). [ka]

[0081] Step 1: 295 g (1.6 mol, 1.0 eq) of 2,4,6-trichloro-1,3,5-triazine [108-77-0]1 is dissolved in 800 ml of dry THF in a 4-neck flask under inert atmosphere. The solution is cooled to about 0 °C in an ice bath and 800 ml (1.6 mol, 1.0 eq) of a 2 mol / l phenylmagnesium chloride solution is added slowly while keeping the temperature below 10 °C. The mixture is then stirred overnight at room temperature and after the reaction is complete, 800 ml of toluene and 1.2 L of HCl 2% are added. The organic phase is separated, extracted three times with water and dried over sodium sulfate. The solvent is distilled under reduced pressure until the product precipitates. After washing the solid with ethanol, 242 g (1.1 mol, 67%) of the desired product 3a is obtained.

[0082] Other examples are available as well. [ka] [ka]

[0083] Step 2a: 1.5 g (61 mmol, 1.12 eq) of magnesium turnings are heated in a 4-neck flask for a few minutes. Then, a few ml of 19 g (60 mmol, 1.10 eq) of 1-bromo-3,5-diphenylbenzene [103068-20-8] in 100 ml of dry THF are added until the Grignard reaction starts. Then, the solvent is added slowly under reflux to continue the Grignard reaction. After the addition is complete, the mixture is cooled to about 0 °C in an ice bath. In a second apparatus, 12.3 g (54 mmol, 1.0 eq) of 2,4-dichloro-6-phenyl-[1,3,5]-triazine 3a is dissolved in 60 ml of dry THF and cooled in an ice bath. The Grignard reagent is transferred to a dropping funnel and slowly added to the solution of 3a. After stirring overnight at room temperature, the mixture was diluted with 100 ml of THF and 50 ml of 1M HCl was added. The precipitate formed was washed with water, ethanol and heptane. After purification by hot extraction from toluene, the desired product 5a was obtained.

[0084] Other examples are available as well. [ka]

[0085] Step 2b: 35 g (150 mmol, 1.0 eq) of 2,4-dichloro-6-phenyl-[1,3,5]triazine, 35 g (150 mmol, 1.0 eq) of dibenzothiophene-4-boronic acid [108847-20-7] and 18 g (170 mmol, 1.10 eq) of sodium carbonate are dissolved in 300 ml of 1,4-dioxane, 300 ml of water and 120 ml of toluene under inert atmosphere. Then, 1.8 g (1.5 mmol, 0.01 eq) of tetrakis(triphenylphosphine)palladium are added and the mixture is refluxed at 110 °C overnight. After the reaction is complete, 100 ml of water is added and the precipitated solid (48 g) is filtered. The organic phase is separated, washed with water and dried over sodium sulfate. After evaporating the solvent, another 13 g of crude product is obtained. The combined solids were recrystallized twice from toluene to give 32 g (86 mmol, 56%) of the desired product 7a.

[0086] Other examples are possible as well. [ka] [ka]

[0087] Step 3b: 30 g (80 mmol, 1.0 eq) of 7a, 21 g (88 mmol, 1.1 eq) of 9,9-dimethyl-9H-fluoren-4-yl-boronic acid [1246022-50-3] and 17 g (160 mmol, 2.0 eq) of sodium carbonate are dissolved in 400 ml of toluene, 250 ml of water and 170 ml of ethanol under inert atmosphere. Then, 0.93 g (0.80 mmol, 0.01 eq) of tetrakis(triphenylphosphine)palladium is added and the mixture is refluxed at 110 °C overnight. After completion of the reaction, 300 ml of water is added and the precipitated solid (36 g) is filtered. The organic phase is separated, washed with water and dried over sodium sulfate. After evaporating the solvent, another 5.1 g of crude product is obtained. The combined solids were purified by hot extraction from toluene / heptane, recrystallized twice from toluene / heptane, and sublimed to give 20 g (38 mmol, 47%) of the desired product 9a.

[0088] Other examples are possible as well. [ka] [ka] [ka] [ka] [ka]

[0089] The present invention further relates to a method for the preparation of compounds of formula (I), comprising the following reaction steps: synthesis of the skeleton of compound (I) not yet containing a triazinyl or pyrimidinyl group; and reaction of the skeleton (preferably in a first step) with a CC coupling, including Suzuki, Negishi, Yamamoto, Grignard-Cross or Stille coupling, or a CN coupling, including Buchwald or Ullmann coupling.

[0090] OLED manufacturing The following Examples V1-V7 and E1-E22 (see Tables 1 and 2) show data from a variety of OLEDs.

[0091] Substrate pretreatment for Examples V1-V7 and E1-E22: A glass substrate with structured ITO (50 nm, indium tin oxide) is coated with 20 nm of PEDOT:PSS (Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ PVP AI 4083 from Heraeus Precious Metals GmbH, Germany, spin-coated from a water-based solution) to form the substrate on which the OLEDs are processed.

[0092] An OLED basically has the following layer structure: substrate / hole transport layer (HTL) / optional interlayer (IL) / electron blocking layer (EBL) / emissive layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The detailed structure of the OLED is shown in Table 1. The materials required for the manufacture of the OLED are shown in Table 3.

[0093] All materials are applied by thermal vacuum 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 (emitter), the emitter being mixed with the matrix material by co-evaporation in a certain volume ratio. Here, the designation IC1:M1:TEG1 (55%:35%:10%) means that in the layer, the material IC1 is present in a volume ratio of 55%, M1 is present in a volume ratio of 35%, and TEG1 is present in a volume ratio of 10%. Similarly, the electron transport layer may consist of a mixture of two materials.

[0094] OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, current efficiency (CE1000, 1000 cd / m2 cd / A at 1000 cd / m 2 lm / W at 1000 cd / m 2 % at 1000 cd / m 2 The electroluminescence (EL) spectrum is determined from the current / voltage / luminous flux density characteristic curve (IUL characteristic curve) assuming Lambertian emission characteristics. 2 and the CIE 1931 x and y color coordinates are calculated from the EL spectrum.

[0095] The lifetime is determined by the selected experiment. The lifetime is determined as the time after which the luminous flux density drops at a constant rate from a constant initial bound density L1 when the OLED is driven at a constant current. In Table 2, the initial state L0;j0=4000cd / m 2 And at L1=70%, the LT column shows the initial OLED brightness of 4000cd / m 2 from 2800 cd / m 2 The lifetime corresponds to the time (h) required for the charge to drop to 0. Therefore, in the initial state, L0;j0=20mA / cm 2 , L1=80% life is 20mA / cm 2 This is the time required for an OLED operated at a constant current of 1000 mA to drop to 80% of its initial luminous flux density.

[0096] Device data for various OLEDs are summarized in Table 2. Examples V1-V7 are state-of-the-art comparative examples. Examples E1-E22 show data for OLEDs of the present invention.

[0097] In the following sections, some examples are disclosed in more detail to demonstrate the advantages of the OLED of the present invention.

[0098] Use of the Compounds of the Present Invention as Electron-Transport Layers and Host Materials in Phosphorescent OLEDs The use of the compounds according to the present invention as electron-transport layers and as host materials leads to significantly improved OLED devices, especially in lifetime, compared to state-of-the-art materials.

[0099] The use of the materials (1) and (187) of the present invention mixed with LiQ in the ETL shows LT improvement compared to devices using materials CE1 and CE2 (compare examples V1 and V2 with E1 and E3, respectively). Furthermore, compared to CE3 (which is a 3-(9,9-dimethylfluorenyl)triazine material), compound (186) of the present invention (which is identical to CE3 except that it is 4-(9,9-dimethylfluorenyl)triazine) provides a significant improvement in LT efficiency when tested as a host in a triplet green OLED (see V3 vs E2). It should be noted that CE6 (sample V6), which is a 4-(9,9-dimethylfluorene)triazine with 9,9'-spirobifluorene substitution of the triazine, shows little improvement compared to CE1 (sample V1), which is like CE6 but with the 4-(9,9-dimethylfluorene) group of the triazine replaced by phenyl. [Table 1-1] [Table 1-2] [Table 2] [Table 3-1] [Table 3-2] [Table 3-3] [Table 3-4]

Claims

1. A compound of formula (I). 【Chemistry 1】 (In the formula, Z １ and Z ２ are the same or different at each occurrence, and are H, D, F, Cl, Br, I, CHO, N(Ar １ ) ２ , C(=O)Ar １ , P(=O)(Ar １ ) ２ , S(=O)Ar １ , S(=O) ２ Ar １ , C.R. ２ =CR ２ Ar １ , C.N., N.O. ２ , Si(R １ ) ３ , B(OR １ ) ２ , B(R １ ) ２ , B(N(R １ ) ２ ) ２ , OSO ２ R １ , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or a linear alkenyl or alkynyl group having 2 to 40 C atoms, a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be linked to one or more radicals R １ where one or more of CH ２ The group is (R １ ) C=C(R １ ), C≡C, Si(R １ ) ２ , Ge(R １ ) ２ , Sn(R １ ) ２ , C=O, C=S, C=Se, C=N(R １ ), P(=O)(R １ ), SO, SO ２ , N(R １ ) ２ , O, S or CON(R １ ) ２ and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ２ or in each case one or more radicals R １ an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, optionally substituted by one or more radicals R １ an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by Y １ and Y ２ are the same or different at each occurrence, and are D, F, Cl, Br, I, CHO, N(Ar １ ) ２ , C(=O)Ar １ , P(=O)(Ar １ ) ２ , S(=O)Ar １ , S(=O) ２ Ar １ , (R １ ) C=C(R １ ) Ar １ , C.N., N.O. ２ , Si(R １ ) ３ , B(OR １ ) ２ , B(R １ ) ２ , B(N(R １ ) ２ ) ２ , OSO ２ R １ , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or a linear alkenyl or alkynyl group having 2 to 40 C atoms, a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be linked to one or more radicals R １ where one or more of CH ２ The group is (R １ ) C=C(R １ ), C≡C, Si(R １ ) ２ , Ge(R １ ) ２ , Sn(R １ ) ２ , C=O, C=S, C=Se, C=N(R １ ) ２ , P(=O(R １ ) ２ , SO, SO ２ , N(R １ ) ２ , O, S or CON(R １ ) ２ and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ２ , or in each case one or more radicals R １ an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, optionally substituted by one or more radicals R １ or a combination of these systems, having 5 to 60 aromatic ring atoms, optionally substituted by two or more adjacent substituents Y １ Or Y ２ may together form a fused, monocyclic or polycyclic, aliphatic or aromatic or heteroaromatic ring system, Ar １ and Ar ２ is different, Ar １ and Ar ２ one of which is an aromatic ring having 5 to 23 aromatic ring atoms and the other is a heteroaromatic ring system having 5 to 23 aromatic ring atoms, in each case the ring system is bound to one or more radicals R １ provided that the heteroaromatic ring system is attached via a carbon-carbon bond; R １ are the same or different for each occurrence, H, D, F, Cl, Br, I, CN, Si(R ２ ) ３ , linear alkyl, alkoxy or thioalkoxy groups having 1 to 40 C atoms, branched or cyclic alkyl, alkoxy or thioalkoxy groups having 3 to 40 C atoms (which are ２ each of which may be substituted by one or more non-adjacent CH ２ The group is C(R ２ ) = C(R ２ ), Si(R ２ ) ２ , C=NR ２ , P(=O)(R ２ ), SO, SO ２ , N.R. ２ , O, S or CONR ２ and one or more H atoms may be replaced by D, F, Cl, Br or I), one or more radicals R ２ an aromatic or heteroaromatic ring system having 6 to 40 carbon atoms, optionally substituted by one or more radicals R ２ an aryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more radicals R ２ and optionally, two or more adjacent substituents R １ may together form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be formed by one or more radicals R ２ where R ２ is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 C atoms, and two or more adjacent substituents R ２ may together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system, X is the same or different at each occurrence, CR １ or N, with the proviso that at least one X is N; L is identical or different in each occurrence and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and one or more non-aromatic radicals R １ may be substituted by a, b, c and d are each the same or different and 0 or 1, with the proviso that at least one of a, b, c or d is 1; e and f are the same or different and each is 0, 1, 2 or 3; and n is the same or different at each occurrence and is 0 or 1.

2. Z １ and Z ２ 2. The compound of claim 1, wherein: are the same substituents and are not bonded to each other at any position other than the 9-position of the fluorene ring.

3. 3. The compound according to claim 1 or 2, according to formula (III), wherein e and f are both 0. 【Chemistry 2】 (wherein the symbols and indices have the meanings given in claim 1 )

4. 3. The compound according to claim 1 or 2, according to formula (IV) and (V), wherein one of a or b is 1 and exactly one of c or d is 1. 【Chemistry 3】 (wherein the symbols and indices have the meanings given in claim 1 )

5. 3. A compound according to claim 1 or 2, according to formula (VIIIa), wherein b is 1, a, c and d are 0, or according to formula (VIIIb), wherein a is 1, b, c and d are 0. 【Chemistry 4】 (wherein the symbols and indices have the meanings given in claim 1 )

6. The compound according to claim 5, according to any one of formulas IX to XVII. 【Chemistry 5】 (wherein the symbols and indices have the meanings given in claim 1 )

7. The compound of claim 6, according to any of formulas IX to XVII, wherein both X's are nitrogen.

8. 8. The compound according to any one of claims 4, 5 and 7, wherein both e and f are 0.

9. The compound according to any one of claims 2 to 5 and 7, wherein n is 0.

10. A compound according to any one of claims 2 to 5 and 7, wherein whenever a, b, c or d is not 0, both X are nitrogen.

11. Whenever a, b, c or d is not 0, one of X is nitrogen and the other is CR. １ The compound according to any one of claims 2 to 5 and 7,

12. Ar １ and Ar ２ is selected from the group consisting of benzene, ortho-, meta-, or para-biphenyl, ortho-, meta-, para-, or branched terphenyl, naphthyl, triphenylene, 9,9-dialkylfluorenyl, N-phenylcarbazole, dibenzofuran, and dibenzothiophene.

13. A method for preparing a compound according to any one of claims 1 to 12, comprising the following reaction steps: synthesis of the backbone of compound (I) not yet containing a triazinyl or pyrimidinyl group; and reaction of the backbone with C-C coupling, including Suzuki, Negishi, Yamamoto, Grignard-Cross or Stille coupling, or C-N coupling, including Buchwald or Ullmann coupling.

14. 13. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 12, wherein one or more bonds from the compounds to the polymer, oligomer or dendrimer are present in one or more positions in place of a substituent.

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

16. 15. An electronic device comprising at least one compound according to any one of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 14, selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, dye sensitized organic solar cells, organic optical inspectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells, organic laser diodes and organic plasma light emitting devices.

17. 15. An organic electroluminescent device, characterized in that a compound according to any one of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 14 is used as one or more matrix materials for a phosphorescent or fluorescent emitter, an electron blocking or exciton blocking layer, a charge generating layer, a hole blocking layer or an electron transport layer.

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