Composition for organic electronic device

Abstract

To provide a host material that improves efficiency, operating voltage and lifetime in an OLED that exhibits triplet emission (phosphorescence).SOLUTION: In a composition including an electron transporting host and a hole transporting host, the electron transporting host is selected from the triazine-dibenzofuran-carbazole class or the triazine-dibenzothiophene-carbazole class, and the hole transporting host is selected from the biscarbazole class.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition comprising an electron-transporting host and a hole-transporting host, its use in an electronic device, and an electronic device comprising said composition. The electron-transporting host is more preferably selected from the class of triazine-dibenzofuran-carbazole or the class of triazine-dibenzothiophene-carbazole. The hole-transporting host is preferably selected from the class of biscarbazoles.

[0002] The structure of organic electroluminescent devices (e.g., OLED - organic light emitting diodes or OLEC - organic light emitting electrochemical cells) in which organic semiconductors are used as functional materials has been known for some time. The light-emitting materials used here, in addition to fluorescent emitters, are increasingly organic metal complexes that exhibit phosphorescence rather than fluorescence. For quantum mechanical reasons, using an organic metal compound as a phosphorescent emitter can potentially increase the energy and power efficiency by up to four times. However, generally speaking, in OLEDs, especially those that exhibit triplet emission (phosphorescence), there is still a need for improvement, for example, with regard to efficiency, operating voltage, and lifetime.

[0003] The characteristics of an organic electroluminescent device are not determined solely by the emitter used. Here, equally particularly important are, among other things, the other materials used, such as host and matrix materials, hole-blocking materials, electron-transporting materials, hole-transporting materials, and electron or exciton-blocking materials, and among these, especially the host or matrix materials. Improvement of these materials can potentially lead to a distinct improvement of the electroluminescent device.

[0004] Host materials for use in organic electronic devices are well known to those skilled in the art. The term "matrix material" is also frequently used in the prior art when it means a host material for a phosphorescent emitter. The use of this term is also applicable to the present invention. During this period, a number of host materials for both fluorescent and phosphorescent electronic devices have been developed.

[0005] A further means of improving the performance data of electronic devices, especially organic electroluminescent devices, is to use a combination of two or more materials, especially host materials or matrix materials.

[0006] US6,392,250B1 discloses the use of a mixture of an electron transport material, a hole transport material and a fluorescent emitter in the light-emitting layer of an OLED. With the help of this mixture, it was possible to improve the lifetime of the OLED compared to the prior art.

[0007] US6,803,720B1 discloses the use of a mixture containing a phosphorescent emitter, a hole transport material and an electron transport material in the light-emitting layer of an OLED. Both the hole transport material and the electron transport material are organic small molecules.

[0008] According to WO2015 / 169412, it is similarly possible to use triazine-dibenzofuran-carbazole derivatives and triazine-dibenzothiophene-carbazole derivatives, for example in a mixture. According to the description, the carbazole derivatives are not bonded to the dibenzofuran or dibenzothiophene basic skeleton via the nitrogen atom of carbazole. For example, the manufacture of an OLED designated as E34 is described, which contains the host materials EG1, IC6 and the phosphorescent emitter TEG1 in the light-emitting layer. The structures of the compounds used are shown below:

[0009]

Chemical formula

[0010] According to WO2015 / 165563, it is similarly possible to use triazine-dibenzofuran-carbazole derivatives and triazine-dibenzothiophene-carbazole derivatives, for example in a mixture. The carbazole derivatives are also understood to mean compounds such as indenocarbazole and indolocarbazole. According to the description, the carbazole derivatives are not bonded to the dibenzofuran or dibenzothiophene basic skeleton via the nitrogen atom of carbazole at the 8-position of dibenzofuran / dibenzothiophene. The triazine substituent is bonded at the 4-position of dibenzofuran / dibenzothiophene directly or via a linker. For example, the production of an OLED designated as E9 is described, which contains the host materials EG9, IC3 and the phosphorescent emitter TEG1 in the light-emitting layer. The structures of the compounds EG9 and IC3 used are shown below:

[0011] [Chemical formula]

[0012] According to WO2015 / 014435, it is possible to use triazine-dibenzofuran-carbazole derivatives and triazine-dibenzothiophene-carbazole derivatives, for example as host materials in the light-emitting layer.

[0013] CN107973786 similarly describes triazine-dibenzofuran-carbazole and triazine-dibenzothiophene-carbazole compounds. The triazine substituent is bonded at the 1-position of dibenzofuran / dibenzothiophene directly or via a linker. The carbazole derivative is bonded at the 6-position of dibenzofuran / dibenzothiophene directly or via a linker. It is further reported that these materials can be mixed with biscarbazole H2 in a ratio of 10:90 to 90:10.

[0014] KR20160046077 describes specific triazine-dibenzofuran-carbazole and triazine-dibenzothiophene-carbazole derivatives in a light-emitting layer together with further host materials.

[0015] US20160293853 describes specific dibenzofuran derivatives that can be used in combination with further host materials.

[0016] US9771373 describes an organic light-emitting device having a light-emitting layer containing two host materials, each selected from a specific group of compounds.

[0017] WO2016 / 015810 describes triazine-dibenzofuran-carbazole and triazine-dibenzothiophene-carbazole compounds in which the triazine substituent is bonded directly or via a linker at the 1-position of dibenzofuran / dibenzothiophene, and the carbazole substituent is bonded at the 8-position of dibenzofuran / dibenzothiophene via its nitrogen atom. According to the description, the compounds mentioned may be used in a mixture with a further matrix material.

[0018] KR2018010149 describes compounds similar to those described in WO2016 / 015810.

[0019] Published WO2018 / 174678 and WO2018 / 174679 disclose devices containing a mixture of carbazole-dibenzofuran derivatives and biscarbazole in an organic layer, where the bonding of the carbazole unit to the dibenzofuran skeleton is possible at any position of dibenzofuran, but preferably at the 6- or 7-position.

[0020] Publication EP3415512 describes, inter alia, dibenzofuran derivatives of formula 1-1, in which a phenyl, pyridine, pyrimidine or triazine substituent may be bonded directly or via a linker at the 1-position of the dibenzofuran, and at least two identical L 2 -Ar 3 substituents may be bonded at the 6- and 8-positions of the dibenzofuran. Here, Ar 3 may be a carbazole bonded via N. In the examples, such compounds are used in combination with specific biscarbazoles.

[0021] However, when using these materials, or mixtures of materials, there is still a need for improvement, especially with regard to the efficiency, operating voltage and / or lifetime of organic electronic devices.

[0022] Accordingly, the problems addressed by the present invention are to provide materials that are suitable for use in organic electronic devices, especially organic electroluminescent devices, especially phosphorescent OLEDs, which lead to good device properties, especially with regard to improvement of power efficiency, operating voltage and / or lifetime, and to provide corresponding electronic devices.

[0023] It has now been found that this problem is solved by a composition containing a compound of formula (1), comprising a hole-transporting host of formula (2), and by an organic electronic device containing said composition, and the drawbacks from the prior art are eliminated. Such compositions lead to very good properties of organic electronic devices, especially organic electroluminescent devices, especially with regard to power efficiency, operating voltage and / or lifetime, and especially in combination with a phosphor of formula (3) at a concentration of from 2% to 25% by weight, even in the presence of a luminescent component in the emission layer. The devices of the present invention exhibit very good power efficiency, inter alia.

[0024] Accordingly, the present invention firstly provides at least one compound of formula (1) and at least one compound of formula (2)

[0025] [Chemical formula]

[0026] (wherein the symbols and subscripts used are as follows: X 1 is the same or different in each case and is CR 0 or N, provided that at least one X 1 group is N; X is the same or different in each case and is C or N, where two adjacent Xs are of formula A

[0027] [Chemical formula]

[0028] (wherein * in each case is the bonding site to X, Y 1 is NAr 1 , C(R*) 2 , O and S (selected from)) may be bonded to the ring system of; Y is selected from O and S; L is the same or different in each case and is a single bond or an aromatic ring system having 6 to 30 aromatic ring atoms and may be substituted by one or more R 5 radicals; n and m in each case are independently 0, 1, 2 or 3, o, p and q in each case are independently 0, 1, 2, 3 or 4; Ar in each case 1 is independently an aryl or heteroaryl group having 5 to 40 aromatic ring atoms and may be substituted by one or more R 3 radicals; R A is H, -L 3 -Ar 4 or -L1 -N(Ar) 2 is; R B is Ar 3 or -L 2 -N(Ar) 2 is; L 1 、L 2 is in each case the same or different, a single bond, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and substituted by one or more R 3 radicals may be; L 3 is a single bond, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and substituted by one or more R 3 radicals may be, where one substituent R 3 is the substituent R on carbazole 2 may form a ring together with; Ar 3 is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 10 to 40 aromatic ring atoms, which may be substituted by one or more R 3 radicals may be; Ar 4 is in each case the same or different, unsubstituted or substituted 9-arylcarbazolyl, or unsubstituted or substituted carbazol-9-yl, which may be substituted by one or more R 4 radicals may be, in one or more cases, each of two R 4 radicals, or one R 4 radical may together with one R 2 radical independently form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring, where aryl has 5 to 30 aromatic ring atoms and is an aromatic or heteroaromatic ring system which may be substituted by R 3 may be; R* is the same or different in each case and is a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, where two substituents R* together form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more substituents R 5 ; R 0 , R, R 1 , R 2 is the same or different in each case and is H, D, F, Cl, Br, I, CN, NO 2 , N(Ar) 2 , N(R 3 ) 2 , C(=O)Ar, C(=O)R 3 , P(=O)(Ar) 2 , P(Ar) 2 , B(Ar) 2 , Si(Ar) 3 , Si(R 3 ) 3 , a linear alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms (each of these may be substituted by one or more R 3 radicals) (where one or more non-adjacent CH 2 groups may be replaced by R 3 C=CR 3 , Si(R 3 ) 2 , C=O, C=S, C=NR 3 , P(=O)(R 3 ), SO, SO 2 , NR 3 , O, S or CONR 3 and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 ), an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted in each case by one or more R 3 radicals, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and having one or more R3 An aryloxy or heteroaryloxy group which may be substituted by a radical, or having 5 to 40 aromatic ring atoms, and one or more Rs 3 Selected from the group consisting of an aralkyl or heteroaralkyl group which may be substituted by a radical; simultaneously, two substituents Rs bonded to the same carbon atom or adjacent carbon atoms 0 And / or R and / or R 1 And / or R 2 Are such that one or more Rs 3 May optionally form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system substituted by a radical; R 3 Are the same or different in each case, and are H, D, F, CN, N(Ar) 2 , an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, and are selected from the group consisting of an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms; simultaneously, two or more adjacent Rs 3 Substituents may together form a monocyclic or polycyclic aliphatic ring system; R 4 Are the same or different in each case, and are H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, a straight-chain or branched alkyl group having 1 to 4 carbon atoms or CN, and are selected from the group consisting of an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms; simultaneously, two or more adjacent Rs 4 Substituents may together form a monocyclic or polycyclic ring system; R 5 Are the same or different in each case, and are selected from the group consisting of D, F, CN, and an aryl group having 6 to 18 carbon atoms; simultaneously, two or more adjacent substituents Rs 5may combine together to form a monocyclic or polycyclic aliphatic ring system; Ar is, in each case, the same or different and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and may be substituted by one or more non-aromatic R 3 radicals; simultaneously, two Ar radicals bonded to the same nitrogen, phosphorus or boron atom may also be crosslinked to each other by a single bond or a crosslink selected from N(R 3 ), C(R 3 ), 2 O and S, r in each case is independently 0, 1, 2 or 3; s in each case is independently 0, 1, 2, 3 or 4) and provides a composition comprising the same.

[0029] The present invention further provides a specific combination of materials, a formulation comprising such a composition, the use of these compositions in organic electronic devices, an organic electronic device comprising such a composition, preferably comprising the composition in one layer, preferably an electroluminescent device, and a method for manufacturing such a device. Corresponding preferred embodiments as described later also form part of the subject matter of the present invention. Surprisingly advantageous effects are achieved, inter alia, through a specific selection of known materials with respect to the selection of the compounds of formula (1).

[0030] A layer comprising a composition comprising at least one compound of formula (1) and at least one compound of formula (2) as described above or preferably as described later is, inter alia, a light-emitting layer (EML), an electron transport layer (ETL), an electron injection layer (EIL) and / or a hole blocking layer (HBL).

[0031] When the layer is a light-emitting layer, the layer is a phosphorescent layer characterized by comprising a phosphorescent emitter in addition to the composition comprising the matrix materials of formula (1) and formula (2) as described above.

[0032] Adjacent carbon atoms in the context of the present invention are carbon atoms directly bonded to each other.

[0033] The expression that two or more radicals may combine together to form a ring should be understood in the context of this specification to mean, inter alia, that two radicals are bonded to each other by a chemical bond involving the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0034]

Chem.

[0035] In addition to this, the aforementioned expression should also be understood to mean that when one of the two radicals is hydrogen, the second radical bonds to the position where the hydrogen atom was bonded to form a ring. This is illustrated by the following scheme:

[0036]

Chem.

[0037] An aryl group in the context of the present invention contains 6 to 40 aromatic ring atoms, preferably carbon atoms. A heteroaryl group in the context of the present invention contains 5 to 40 aromatic ring atoms, where the ring atoms include carbon atoms and at least one heteroatom, provided that the total of carbon atoms and heteroatoms is at least 5 at most. The heteroatom is preferably selected from N, O and / or S. An aryl group or heteroaryl group here means any of a simple aromatic ring derived from benzene, i.e., phenyl, or a simple heteroaromatic ring derived from, for example, pyridine, pyrimidine or thiophene, or a fused aryl or heteroaryl group derived from, for example, naphthalene, anthracene, phenanthrene, quinoline or isoquinoline. Thus, an aryl group having 6 to 18 carbon atoms is preferably phenyl, naphthyl, phenanthryl or triphenylenyl, and there is no limitation on the bonding of the aryl group as a substituent. Thus, an arylene group having 6 to 18 carbon atoms is preferably phenylene, naphthylene, phenanthrylene or triphenylenenylene, and there is no limitation on the bonding of the arylene group as a linker.

[0038] An aromatic ring system in the context of the present invention contains 6 to 40 carbon atoms in the ring system and may be substituted by one or more R 3 radicals, where R 3 has the definitions described below. The aromatic ring system also contains an aryl group as described above.

[0039] An aromatic ring system having 6 to 18 carbon atoms is preferably selected from phenylene, biphenylene, naphthylene, phenanthrylene and triphenylenenylene, where each aromatic ring system may be substituted by one or more R 5 radicals.

[0040] A heteroaromatic ring system in the context of the present invention contains 5 to 40 ring atoms and at least one heteroatom and may be substituted by one or more R 3 radicals, where R3 has the definitions described below. Preferred heteroaromatic ring systems have 10 to 40 ring atoms and at least 1 heteroatom, and may be substituted by one or more R 3 radicals, where R 3 has the definitions described below. The heteroaromatic ring system also contains heteroaryl groups as described above. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O, and / or S.

[0041] An aromatic or heteroaromatic ring system in the context of the present invention does not necessarily contain only aryl or heteroaryl groups, and means a system in which a plurality of aryl or heteroaryl groups may be interrupted by non-aromatic units (preferably less than 10% of atoms other than H), such as carbon, nitrogen or oxygen atoms or carbonyl groups. For example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are also regarded as aromatic or heteroaromatic ring systems in the context of the present invention, and systems in which two or more aryl groups are interrupted by, for example, linear or cyclic alkyl groups or silyl groups are the same. In addition, 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 included in the definition of aromatic or heteroaromatic ring systems.

[0042] having 5 to 40 aromatic ring atoms, and in each case the aforementioned R 3The aromatic or heteroaromatic ring system, which may be substituted by radicals and may be bonded to an aromatic or heteroaromatic system via any desired position, is, for example, benzene, naphthalene, anthracene, benzoanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzofluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, torquene, isotorquene, spirotorquene, spiroisotorquene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarbazole, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,It is understood to mean groups derived from 5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.,

[0043] The abbreviation Ar is the same or different in each case and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and optionally substituted by one or more non-aromatic R 3 radicals; simultaneously, two Ar radicals bonded to the same nitrogen atom, phosphorus atom or boron atom may also be crosslinked to each other by a crosslink selected from single bonds or N(R 3 ), C(R 3 ) 2 , O and S. The substituent R 3 is described above or preferably described later.,

[0044] The cyclic alkyl, alkoxy or thioalkyl groups in the context of the present invention are understood to mean monocyclic, bicyclic or polycyclic groups.,

[0045] In the context of the present invention, individual hydrogen atoms or CH 2 groups may also be C 1 substituted by the aforementioned groups up to C 20The alkyl group is understood to mean, for example, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-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, 1,1-diethyl-n-dec-1-yl, 1,1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl, 1,1-diethyl-n-hexadec-1-yl, 1,1-diethyl-n-octadec-1-yl, 1-(n-propyl)cyclohex-1-yl, 1-(n-butyl)cyclohex-1-yl, 1-(n-hexyl)cyclohex-1-yl, 1-(n-octyl)cyclohex-1-yl and 1-(n-decyl)cyclohex-1-yl radicals.

[0046] The alkenyl group is understood to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl.

[0047] The alkynyl group is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.

[0048] C 1 ~C 20 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.

[0049] C 1 ~C 20 The thioalkyl group is understood to mean, for example, an S-alkyl group such as thiomethyl, 1-thioethyl, 1-thio-i-propyl, 1-thio-n-propyl, 1-thio-i-butyl, 1-thio-n-butyl or 1-thio-t-butyl.

[0050] An aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms means O-aryl or O-heteroaryl, meaning that the aryl or heteroaryl group is bonded via an oxygen atom.

[0051] An aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms means that the alkyl group as described above is substituted by an aryl group or a heteroaryl group.

[0052] The phosphorescent emitter in the context of the present invention is a compound that emits light from an excited state with a higher spin multiplicity, i.e., an excited state with a spin state greater than 1, particularly from an excited triplet state. In the context of this application, all luminescent complexes containing transition metals or lanthanides should be regarded as phosphorescent emitters. A more precise definition will be given later.

[0053] When a composition containing at least one compound of formula (1) described above or, preferably, as described hereinafter, and at least one compound of formula (2) described above or, preferably, as described hereinafter is used as a matrix material for a phosphorescent emitter, it is preferred that its triplet energy is not significantly lower than the triplet energy of the phosphorescent emitter. Regarding the triplet level, T 1 (emitter)-T 1 (matrix) is preferably 0.2 eV or less, more preferably 0.15 eV or less, and most preferably 0.1 eV or less. Here, T 1 (matrix) is the triplet level of the matrix material in the light-emitting layer, and this condition is applicable to each of the two matrix materials. T 1 (emitter) is the triplet level of the phosphorescent emitter. When the light-emitting layer contains more than two matrix materials, the aforementioned relationship is preferably also applicable to each of the additional matrix materials.

[0054] Hereinafter, the description of the compounds of formula (1) and their preferred embodiments, which are present, for example, as an electron-transporting host, in the composition and / or device according to the present invention, will continue.

[0055] The composition according to the present invention contains at least one compound of formula (1) as described above.

[0056] In the compound of formula (1), Y is selected from O and S.

[0057] In a preferred embodiment of the present invention, a compound of formula (1) in which Y is O is selected.

[0058] In a preferred embodiment of the present invention, a compound of formula (1) in which Y is S is selected.

[0059] In the compound of formula (1), the symbol X is N in at least one case, preferably N in two cases and CR 0 in one case, or N in three cases.

[0060] Therefore, the substituent

[0061]

Chem.

[0062] has the following definitions, where * indicates the binding site to dibenzofuran or dibenzothiophene, and R 0 and Ar 1 have one of the definitions shown above, or the definitions shown as preferred ones.

[0063]

Chem.

[0064] R 0 is the same or different in each case, and is preferably selected from the group consisting of H, D, F, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms. Each R 0 is more preferably H.

[0065] X 1 is N in each case for the compound of formula (1), and the compound of formula (1a)

[0066]

Chem.

[0067] (wherein Y, X, L, Ar 1 , R, R 1 , n, m, o and p have the definitions shown above or the definitions shown later) is represented by.

[0068] More preferably, at least one compound of formula (1a) having a substituent described above, described as preferred, or described as preferred later is selected for the composition.

[0069] Accordingly, the present invention further provides a composition as described above, wherein the compound of formula (1) preferably conforms to formula (1a) when the symbol Y is O.

[0070] Accordingly, the present invention further provides a composition as described above, wherein the compound of formula (1) preferably conforms to formula (1a) when the symbol Y is S.

[0071] In the compound of formula (1) or (1a), or in the compound of formula (1) or (1a) described as preferred, when n or m is greater than 0, the substituents R are the same or different in each case, and are preferably selected from the group consisting of D, F, an alkyl group having 1 to 40 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms. The heteroaromatic ring system having 5 to 40 aromatic ring atoms in this case of R is preferably derived from dibenzofuran or dibenzothiophene. The aromatic ring system having 6 to 40 aromatic ring atoms in this case of R is preferably phenyl, biphenyl or terphenyl, more preferably phenyl or [1,1’,2’,1”]-terphenyl-5’-yl. The alkyl group having 1 to 40 carbon atoms in this case of R is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably methyl, ethyl, n-propyl or n-butyl, and most preferably methyl.

[0072] In the compound of formula (1) or (1a), n and m are preferably 0.

[0073] In the compound of formula (1) or (1a), or in the preferred compound of formula (1) or (1a), the symbol X is preferably C in 8 cases, and is correspondingly substituted by R 1 or the symbol X is preferably C in 6 cases, and is correspondingly substituted by R 1 and the remaining two symbols X conform to formula A.

[0074] Thus, in the case where n and m are 0 and the symbol X is as preferred, the preferred compounds of formula (1) or (1a) having the definitions as described above are those of formula (1b), (1c), (1d), (1e), (1f), (1g) and (1h)

[0075]

Chemical formula

[0076]

Chemical formula

[0077] (wherein Y, Y 1 , L, Ar 1 and R 1 have the definitions shown above or the definitions shown later) are compounds of.

[0078] In the compounds of formula (1), (1a) to (1h), or preferably described compounds of formula (1), (1a) to (1h), the substituent R 1 is preferably each independently H, D, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, and in each case is selected from the group of aromatic or heteroaromatic ring systems which may be substituted by one or more R 3 radicals, where R 3 has the definition shown above or the definition shown later, and two substituents R 1 on adjacent carbon atoms form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R 3 radicals.

[0079] In one aspect of the present invention, in the compounds of formula (1), (1a) and (1b), or preferably described compounds of formula (1), (1a) and (1b), the substituent R 1 is preferably each independently H, D, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, and in each case is selected from the group of aromatic or heteroaromatic ring systems which may be substituted by one or more R 3Selected from the group of aromatic ring systems which may be substituted by radicals, where R 3 has the definitions shown above or below. In this embodiment, preferably 6 or 7 substituents R 1 are H, and the remaining substituents have the definitions as described above and are not H. In this embodiment, the carbazole in the compounds of formula (1), (1a) and (1b) preferably has a substituent R 1 which is an aromatic ring system having 5 to 40 aromatic ring atoms and is different from H.

[0080] In one embodiment of the present invention, the substituents R 1 in the compounds of formula (1), (1a) and (1b), or preferably described compounds of formula (1), (1a) and (1b) are preferably each independently H, D, or have 5 to 40 aromatic ring atoms, and in each case one or more R 3 selected from the group of heteroaromatic ring systems which may be substituted by radicals, where R 3 has the definitions shown above or below. In this embodiment, preferably 7 substituents R 1 are H, and the remaining substituents have the definitions as shown above and are not H. In this embodiment, the carbazole in the compounds of formula (1), (1a) and (1b) preferably has a substituent R 1 which is a heteroaromatic ring system having 5 to 40 aromatic ring atoms and is different from H.

[0081] In the compounds of formula (1), (1a)-(1h), or preferably described compounds of formula (1), (1a)-(1h), the substituents R 1 are more preferably each independently H, or unsubstituted or R 3 monosubstituted or polysubstituted phenyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl, triphenylenyl, 1-naphthyl, 2-naphthyl, carbazol-9-yl or 9-arylcarbazolyl, where aryl has 5 to 30 aromatic ring atoms, and in each case one or more R 3Represents an aromatic or heteroaromatic ring system which may be substituted by radicals.

[0082] In the compound of formula (1b), preferably 6 or 7 substituents R 1 are defined as being H, and 2 or 1 substituent R 1 has a definition different from that described above or as preferably described.

[0083] In the compounds of formula (1c) - (1h), the substituent R 1 is preferably all H.

[0084] In the compounds of formula (1), (1a) - (1h), or preferably the compounds of formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) as described, in each case Ar 1 is independently preferably an aryl group having 6 - 40 carbon atoms and optionally substituted by one or more R 3 radicals, or a dibenzofuranyl or dibenzothiophenyl group optionally substituted by one or more R 3 radicals, or a carbazolyl group which may be bonded either via C or via N and is optionally substituted by one or more R 3 radicals. The bonding of the carbazolyl group via carbon atoms is not restricted here. Preferably, the carbazolyl group is bonded via N and is substituted by R 3 radicals.

[0085] In the compounds of formula (1), (1a) - (1h), or preferably the compounds of formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) as described, in each case Ar 1 is independently preferably an aryl group having 6 - 40 carbon atoms and optionally substituted by one or more R 3An aryl group which may be substituted by a radical, or one or more Rs 3 A dibenzofuranyl or dibenzothiophenyl group which may be substituted by a radical.

[0086] The bond of the aryl group, or the dibenzofuranyl group or dibenzothiophenyl group is not limited herein.

[0087] Therefore, Ar 1 is preferably selected from the following Ar 1 -1 to Ar 1 -12 groups, where R 3 has the definitions specified above or as specified as preferred:

[0088]

Chemical formula

[0089] More preferably, at least one Ar 1 is Ar 1 -1, and the other aromatic substituent Ar 1 has 6 to 40 carbon atoms and is an alkyl group which may be substituted by one or more R 3 radicals, or a dibenzofuranyl or dibenzothiophenyl group, preferably selected from Ar 1 -1 to Ar 1 -12. More preferably, at least one Ar 1 is phenyl, and the other aromatic substituent is a phenyl group which may be substituted by one or more R 3 radicals, or dibenzofuranyl or dibenzothiophenyl. Most preferably, both Ar 1 groups are the same. Most preferably, both Ar 1 groups are phenyl. Preferably, both Ar 1 groups are each independently Ar 1 -5, Ar 1 -6, Ar 1 -7 or Ar 1is -11; more preferably, both Ar 1 groups are Ar 1 is -6.

[0090] In the compound of formula (1) or (1a) - (1h), or the compound of formula (1) or (1a) - (1h) described as preferred, Ar 1 is in each case independently an aryl or heteroaryl group substituted by one or more R 3 radicals as described above or as described as preferred. When the substituent R 3 is in each case the same or different, preferably selected from the group consisting of D, F, or an aromatic or heteroaromatic ring system having 5 - 40 aromatic ring atoms. The heteroaromatic ring system having 5 - 40 aromatic ring atoms in the case of this R 3 is preferably derived from dibenzofuran or dibenzothiophene. The aromatic ring system having 6 - 40 aromatic ring atoms in the case of this R 3 is preferably phenyl, biphenyl or terphenyl, more preferably phenyl. Preferably, the aryl group or heteroaryl group in Ar 1 is in each case independently substituted once by R 3 . More preferably, the aryl group or heteroaryl group in Ar 1 is substituted once by R 3 .

[0091] The substituent R 3 on dibenzofuranyl or dibenzothiophenyl is preferably H. The substituent R 3 on an aryl group having 6 - 40 carbon atoms, when it appears, is preferably phenyl or H. Most preferably, the aryl group or heteroaryl group in Ar 1 is unsubstituted.

[0092] The compounds of formula (1), (1a), (1c), (1d), (1e), (1f), (1g) and (1h), or the compounds of formula (1), (1a), (1c), (1d), (1e), (1f), (1g) and (1h) described as preferred, wherein Y 1 is NAr 1 , C(R*) 2 , O or S, wherein Ar 1 has the definitions shown previously, or the definitions shown as preferred.

[0093] Preferably, NAr 1 is defined as N-phenyl. Y 1 is preferably NAr 1 or C(R*) 2 .

[0094] In one aspect of the present invention, the compounds of formula (1), (1a) and (1c), or compounds of formula (1), (1a) and (1c) described as preferred, wherein Y 1 has the definitions shown previously, or Y 1 is NAr 1 and C(R*) 2 , more preferably C(R*) 2 .

[0095] In one aspect of the present invention, the compounds of formula (1), (1a), (1d) and (1e), or compounds of formula (1), (1a), (1d) and (1e) described as preferred, wherein Y 1 has the definitions shown previously, or Y 1 is NAr 1 and O, more preferably NAr 1 .

[0096] The compounds of formula (1), (1a), (1c), (1d), (1e), (1f), (1g) and (1h), or the compounds of formula (1), (1a), (1c), (1d), (1e), (1f), (1g) and (1h) described as preferred, in which the substituent R* is the same or different in each case and is a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, where two substituents R* together may form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more substituents R 5 as defined above. R* is preferably the same in each case, or two substituents R* together form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system. More preferably, R* is selected from methyl, ethyl and phenyl. More preferably, two substituents R* together with the carbon atom to which they are attached form a ring system selected from cyclopentyl and dibenzocyclopentyl which may be substituted by one or more substituents R 5 as defined above. The ring system formed by two substituents R* is more preferably spirobifluorene.

[0097] More preferably, Y 1 is selected from N-phenyl, C(methyl) 2 , O and S. Most preferably, Y 1 is defined as C(methyl) 2 as defined above.

[0098] In the compounds of formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h), or the compounds of formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) described as preferred, L is the same or different in each case and is a single bond or an aromatic ring system having 6 to 30 aromatic ring atoms which may be substituted by one or more R 5 radicals as defined above, where R 5 is defined as described above. Here, R5 is preferably selected from the group consisting of D and phenyl. L is preferably a single bond or an aromatic ring system having 6 to 18 carbon atoms, preferably phenylene, diphenylene, naphthylene, phenanthrenylene or triphenylene, where the attachment to further substituents is unrestricted. Here, phenylene may be attached to the dibenzofuran / dibenzothiophene unit, for example, at the ortho, meta or para position.

[0099] Thus, L is preferably unsubstituted as described above or may be substituted by R 5 and may be one of the following linkers L-1 to L-20:

[0100]

Chemical formula

[0101] and may be selected from.

[0102] Preferably, the linkers L-1 to L-20 are unsubstituted.

[0103] It is particularly preferred to use linkers L-1 to L-7.

[0104] Preferably, L is a single bond or a linker selected from the group of L-1 to L-7 or L-2 and L-3. More preferably, L is a single bond.

[0105] Particularly preferred compounds of formula (1) conform to formula (1b) and (1c) as described above.

[0106] In the compounds of formula (1), (1b) and (1c), Y is preferably O, and Y 1 is preferably C(R*) 2 and, independently in each case, Ar 1As described above, it is preferably phenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl-N-phenylenyl, dibenzofuranylphenylenyl, phenylcarbazol-N-yl, 1,3- and 1,4-biphenyl, and L is a single bond.

[0107] In the compounds of formulas (1), (1b) and (1c), Y is preferably O, and Y 1 is preferably C(R*) 2 and, in each case independently, Ar 1 As described above, it is preferably phenyl, dibenzofuranyl, dibenzothiophenyl and biphenyl, and L is a single bond.

[0108] In the compounds of formulas (1), (1b) and (1c), Y is preferably S, and Y 1 is preferably C(R*) 2 and, in each case independently, Ar 1 As described above, it is preferably phenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl-N-phenylenyl, dibenzofuranylphenylenyl, phenylcarbazol-N-yl, 1,3- and 1,4-biphenyl, and L is a single bond.

[0109] In the compounds of formulas (1), (1b) and (1c), Y is preferably S, and Y 1 is preferably C(R*) 2 and, in each case independently, Ar 1 As described above, it is preferably phenyl, dibenzofuranyl, carbazolyl-N-phenylenyl and 1,3-biphenyl, and L is a single bond.

[0110] Substituents Y, Y 1 , Ar 1 , L and R 1 in the compounds of formulas (1b) and (1c) having are preferably selected for the compositions of the present invention.

[0111] Examples of suitable compounds of formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) selected in accordance with the present invention are the structures shown in Table 1 below, or Compounds 1 to 36 and 67 to 81.

[0112] [Table 1-1]

[0113] [Table 1-2]

[0114] [Table 1-3]

[0115] [Table 1-4]

[0116] [Table 1-5]

[0117] [Table 1-6]

[0118] [Table 1-7]

[0119] [Table 1-8]

[0120] [Table 1-9]

[0121]

Table 1-10

[0122]

Table 1-11

[0123]

Table 1-12

[0124]

Table 1-13

[0125]

Table 1-14

[0126]

Table 1-15

[0127]

Table 1-16

[0128]

Table 1-17

[0129]

Table 1-18

[0130]

Table 1-19

[0131]

Table 1-20

[0132]

Table 1-21

[0133]

Table 1-22

[0134]

Table 1-23

[0135]

Table 1-24

[0136]

Table 1-25

[0137]

Table 1-26

[0138]

Table 1-27

[0139]

Table 1-28

[0140]

Table 1-29

[0141]

Table 1-30

[0142]

Table 1-31

[0143]

Table 1-32

[0144]

Table 1-33

[0145]

Table 1-34

[0146]

Table 1-35

[0147]

Table 1-36

[0148]

Table 1-37

[0149]

Table 1-38

[0150]

Table 1-39

[0151]

Table 1-40

[0152]

Table 1-41

[0153]

Table 1-42

[0154]

Table 1-43

[0155]

Table 1-44

[0156] Particularly preferred compounds of formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) selected according to the present invention are Compounds 1 to 36 and 67 to 81:

[0157]

Chemical formula

[0158]

Chemical formula

[0159]

Chemical formula

[0160]

Chemical formula

[0161]

Chemical formula

[0162] The preparation of the compound of formula (1) or the preferred compounds of formulas (1a) to (1h), as well as Compounds 1 to 36 and 67 to 81, is known to those skilled in the art. The compounds may be prepared by synthetic processes known to those skilled in the art, such as halogenation, preferably bromination, followed by an organometallic coupling reaction, such as a Suzuki coupling, a Heck coupling or a Hartwig-Buchwald coupling. The preparation of the compound of formula (1) or the preferred compounds of formulas (1a) to (1h), as well as Compounds 1 to 36 and 67 to 81, can be inferred, inter alia, from WO2016 / 015810, in particular from the synthesis examples on pages 35 and 44 to 64.

[0163] The compounds of formulas (1) to (1h) can be prepared according to Scheme 1 below, where L, X 1 , Y, R, R 1 , Ar 1 , n, m, o, p have one of the definitions shown above.

[0164]

Chemical formula

[0165] The following is a description of the compounds of formula (2) and their preferred embodiments present, for example, as a hole-transporting host in the compositions and / or devices according to the present invention.

[0166] The composition according to the present invention comprises at least one compound of formula (2)

[0167]

Chemical formula

[0168] (wherein the symbols and subscripts used are as follows: R A is H, -L 3 -Ar 4 or -L 1-N(Ar) 2 is; R B is Ar 3 or -L 2 -N(Ar) 2 is; L 1 、L 2 is, in each case, the same or different, a single bond, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and optionally substituted by one or more R 3 radicals; L 3 is a single bond, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and optionally substituted by one or more R 3 radicals, where one substituent R 3 may form a ring together with the substituent R 2 on the carbazole; Ar 3 is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 10 to 40 aromatic ring atoms, which may be optionally substituted by one or more R 3 radicals; Ar 4 is, in each case, the same or different, unsubstituted or substituted 9-arylcarbazolyl, or unsubstituted or substituted carbazol-9-yl, which may be optionally substituted by one or more R 4 radicals, and in one or more cases, each of two R 4 radicals, or one R 4 radical, may together with one R 2 radical independently form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring, where aryl is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and optionally substituted by R 3 ; R 2 is, in each case, the same or different, H, D, F, Cl, Br, I, CN, NO 2 、N(Ar) 2 、N(R3 ) 2 、 C(=O)Ar, C(=O)R 3 、 P(=O)(Ar) 2 、 P(Ar) 2 、 B(Ar) 2 、 Si(Ar) 3 、 Si(R 3 ) 3 、 a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms (each of which may be substituted by one or more R 3 radicals) (wherein one or more non-adjacent CH 2 groups may be replaced by R 3 C=CR 3 、 Si(R 3 ) 2 、 C=O, C=S, C=NR 3 、 P(=O)(R 3 )、 SO, SO 2 、 NR 3 、 O, S or CONR 3 and may be replaced by D, F, Cl, Br, I, CN or NO 2 and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 3 radicals), an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and optionally substituted in each case by one or more R 3 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and optionally substituted by one or more R 3 radicals, or an aralkyl or heteroaralkyl group having 5 to 40 ring atoms and optionally substituted by one or more R 2 radicals; simultaneously, two substituents R 3 bonded to the same carbon atom or adjacent carbon atoms may optionally form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system optionally substituted by one or more R R 3which are the same or different in each case and are H, D, F, CN, N(Ar) 2 , an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, and is selected from the group consisting of aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms; simultaneously, two or more adjacent R 3 substituents may together form a monocyclic or polycyclic aliphatic ring system; R 4 which are the same or different in each case and are H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, a straight-chain or branched alkyl group having 1 to 4 carbon atoms or CN and is selected from the group consisting of aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms; simultaneously, two or more adjacent R 4 substituents may together form a monocyclic or polycyclic ring system; Ar which are the same or different in each case, has 5 to 30 aromatic ring atoms and is an aromatic or heteroaromatic ring system which may be substituted by one or more non-aromatic R 3 radicals; simultaneously, two Ar radicals bonded to the same nitrogen atom, phosphorus atom or boron atom may also be crosslinked to each other by a crosslink selected from single bonds or N(R 3 ), C(R 3 ) 2 and may be crosslinked to each other by a crosslink selected from O and S, r in each case is independently 0, 1, 2 or 3; s in each case is independently 0, 1, 2, 3 or 4) contains a compound of

[0169] In one aspect of the present invention, a compound of formula (2) as described above is selected, which is used in a composition together with a compound of formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) as described above or preferably described, or together with the compounds in Table 1 or Compounds 1 to 36 and 67 to 81.

[0170] The compound of formula (2) is represented by the following formulas (2a), (2b), (2c) and (2d):

[0171]

Chemical formula

[0172] (wherein L 1 , L 2 , L 3 , Ar, Ar 3 , Ar 4 , R 2 , r and s have the definitions shown above or the definitions shown below) and can be represented by.

[0173] Preferred compounds of formula (2) or (2a) are of formula (2e), (2f), (2g), (2h) and (2i)

[0174]

Chemical formula

[0175]

Chemical formula

[0176]

Chemical formula

[0177] (wherein R B , Ar 3 , aryl, R 2 , R 4, r and s have the definitions shown above or the definitions shown below, and L in formulas (2h) and (2i) 3 has 5 to 30 aromatic ring atoms and is an aromatic or heteroaromatic ring system which may be substituted by one or more R 3 radicals, where one substituent R on carbazole 2 may form a ring together with substituent R 3 , Z is C(R 3 ), 2 N-Ar, O or S, and t is 0 or 1) is a compound of

[0178] Preferred compounds of formula (2) or (2c) in which at least r is 1 are of formula (2j), (2k), (2l)

[0179]

Chemical formula

[0180] (wherein Ar 3 , R 2 , R 3 and s have the definitions shown above or the definitions shown as preferred, and u, v and w in each independent case are 0 or 1) is a compound of

[0181] R in the compounds of formula (2j), (2k) and (2l) 3 is preferably H or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by R 5 . When u, v and / or w is 1, R 3 in the compounds of formula (2j), (2k) and (2l) is preferably phenyl. In the preferred compounds of formula (2j), (2k) and (2l), one of the subscripts u, v or w is 1. More preferably, u, v and w are 0

[0182] In the compounds of formulas (2a) to (2l), when r and / or s is greater than 1, H is excluded from the definition of substituent R 2 and is not included in the definition of

[0183] Accordingly, the present invention is as described above, and further provides a composition in which the compound of formula (2) corresponds to one of the compounds of formulas (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l).

[0184] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), one substituent R 2 and one substituent R 4 may form a ring defined, for example, by [Z] t in formula (2f), preferably forming the following rings Z-1 to Z-7, where the dotted line represents the bond to carbazole in each case:

[0185] [Chemical formula]

[0186] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j) and (2l), two substituents R 2 in one or more cases may combine to form a ring, and two substituents R 4 in one or more cases may combine to form a ring when present, where this ring is, independently in each case, preferably the following structures (S1) to (S9):

[0187] [Chemical formula]

[0188] selected from, wherein # and # each represent a respective bonding site to a carbon atom, and the structure is each optionally substituted with one or more substituents R 3 may be substituted by.

[0189] In substructures (S1) to (S9), R 3 is preferably H, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by R 5 and is preferably H or phenyl.

[0190] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), the linker L 1 , L 2 and L 3 , when not a single bond, are each independently linker L-2.1 to L-2.33:

[0191]

Chemical formula

[0192]

Chemical formula

[0193] (wherein W represents N-Ar, O, S or C(CH 3 ) 2 , Ar has the definition shown above, and the linkers L-2.1 to L-2.33 may be substituted by one or more R 3 radicals, and the dotted line represents the bond to the carbazole) are selected from. The linker L 3 , in the case of, the R 3 radical on one of the linkers L-2.1 to L-2.33 may form a ring with the R 2 radical of the carbazole.

[0194] Preferably, the linkers L-2.1 to L-2.33 are unsubstituted or substituted with phenyl.

[0195] L 1 The preferred linkers in the case of L are selected from the structures L-2.1 to L-2.33, where W is defined as S or O, more preferably defined as O.

[0196] L 3 The preferred linkers in the case of L are selected from the structures L-2.1 to L-2.33, where W is defined as O, S or N-Ar, more preferably defined as O or N-Ar.

[0197] In a preferred embodiment of the compounds of formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), the two carbazoles are bonded to each other at the 3-position.

[0198] In the compounds of formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), r is preferably 0, 1 or 2, where R 2 has the definitions shown above or the definitions shown below. More preferably, r is 0 or 1. Most preferably, r is 0.

[0199] In the compounds of formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), when r is greater than 0, the substituents R 2 are the same or different in each case, preferably D, F, an alkyl group having 1 to 40 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted with one or more R 3 radicals. The aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms in this R 2 is preferably an aromatic or heteroaromatic ring system having one or more R 3Derived from benzene, dibenzofuran, dibenzothiophene, 9-phenylcarbazole, indolo[3,2,1-jk]carbazole, biphenyl and terphenyl, which may be substituted by radicals. Substituent [R 2 r The preferred positions are the 1, 2, 3 or 4 positions, or the combination of the 1 and 4 positions, and the 1 and 3 positions, more preferably the 1 and 3 positions, the 2 or 3 positions, and most preferably the 3 position, where R 2 has one of the preferred definitions shown above, and r is greater than 0. [R 2 r Particularly preferred substituents R 2 in [R

[0200] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2k) and (2l), s in each case is independently preferably 0, 1 or 2, where R 2 and R 4 have the definitions shown above or the definitions shown later. More preferably, s in each case is independently 0 or 1; most preferably, s in each case is 0.

[0201] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), when s is greater than 0, the substituents R 4 are the same or different in each case, preferably D, F, an alkyl group having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, a straight-chain or branched alkyl group having 1 to 4 carbon atoms or CN. Here, two or more adjacent R 4 substituents can combine to form a monocyclic or polycyclic ring system. This R 4 ​​The aromatic or heteroaromatic ring systems having 5 to 40 aromatic ring atoms in are preferably derived from benzene, dibenzofuran, dibenzothiophene, 9-phenylcarbazole, biphenyl, terphenyl and triphenylene.

[0202] substituent [R 4 ] s Preferred positions of R are 1, 2 or 3, more preferably 3, where R 4 has one of the preferred definitions given above, and s is greater than zero.

[0203] N(Ar) 2 Ar in the formula (I) is preferably one or more substituents R 3 wherein Ar is preferably unsubstituted, and is derived from benzene, dibenzofuran, fluorene, spirobifluorene, dibenzothiophene, 9-phenylcarbazole, biphenyl and terphenyl, optionally substituted by:

[0204] Substituent R 2 are in each case the same or different and are preferably D, F, Cl, Br, I, CN, NO 2 , N(Ar) 2 , N.H. 2 , N(R 3 ) 2 , C(=O)Ar, C(=O)H, C(=O)R 3 , P(=O)(Ar) 2 , a straight chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be represented by one or more R 3 radicals), having 5 to 60 aromatic ring atoms, in each case one or more R 3 Aromatic or heteroaromatic ring systems, optionally substituted by radicals, having 5 to 60 aromatic ring atoms, in each case one or more R 3It is selected from the group consisting of an aryloxy or heteroaryloxy group which may be substituted by a radical. Substituent R 2 When present, is more preferably an aromatic or heteroaromatic ring system as described above, preferably selected from the group consisting of benzene, carbazole, 9-phenylcarbazole, dibenzofuran, dibenzothiophene, fluorene, terphenyl or spirobifluorene, and is most preferably derived from dibenzofuran.

[0205] In the compounds of formulas (2j), (2k) and (2l), when s is greater than 0, the substituent R 2 In each case, is the same or different, preferably D, F, an alkyl group having 1 to 40 carbon atoms, or having 5 to 40 aromatic ring atoms, and one or more R 3 It is selected from the group consisting of an aromatic or heteroaromatic ring system which may be substituted by a radical. Substituent [R 2 s The preferred positions of are the 1, 3 and 4 positions, more preferably the 3 position, where R 2 Has one of the definitions shown above. Preferably, s is 0 or 1. In the compounds of formulas (2j), (2k) and (2l), when s is 1, [R 2 s The R in 2 Is preferably phenyl.

[0206] Substituent R as described above 2 When one of is substituted by substituent R 3 The definition of R as described above or as preferably described is applicable. 3

[0207] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2k) and (2i) as described above, Ar 3 In each case, independently, one or more R 3 ​​An aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 10 to 40 aromatic ring atoms, which may be substituted by radicals.

[0208] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i) as described above, aryl has 5 to 30 aromatic ring atoms, and R 3 is an aromatic or heteroaromatic ring system which may be substituted by

[0209] Ar 3 and aryl are preferably derived from benzene, dibenzofuran, fluorene, spirobifluorene, dibenzothiophene, 9-phenylcarbazole, naphthalene, phenanthrene, triphenyl, biphenyl and terphenyl, which may be substituted by one or more substituents R 3 wherein R 3 has the definition shown above.

[0210] In the case of a heteroaromatic ring system having 10 to 40 carbon atoms and which may be substituted by one or more substituents R 3 an electron-rich ring system is particularly preferred, where optionally the R 3 substituted ring system preferably contains only one nitrogen atom in total, or optionally the R 3 substituted ring system contains one or more oxygen and / or sulfur atoms in total.

[0211] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l), or preferably the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l) as described, aryl and Ar in each case 3 are preferably aromatic or heteroaromatic ring systems Ar-1 to Ar-24

[0212] [Chemistry]

[0213] [Chemistry]

[0214] [Chemistry]

[0215] (wherein, in each case, Y 3 is the same or different and is O, NR # , S or C(R # ) 2 and the R # radical bonded to N is not H, and R 3 has the aforementioned definition or the following preferred definition, and the bond shown by the dotted line represents a bond to the nitrogen atom) is independently selected from

[0216] R # radicals are the same or different in each case and are H, D, F, Cl, Br, I, CN, NO 2 , N(Ar) 2 , N(R 3 ) 2 , C(=O)Ar, C(=O)R 3 , P(=O)(Ar) 2 , P(Ar) 2 , B(Ar) 2 , Si(Ar) 3 , Si(R 3 ) 3 , a linear alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms (each of these may be substituted by one or more R 3 radicals) (wherein one or more non-adjacent CH 2 groups are R3 C=CR 3 、Si(R 3 ) 2 、C=O、C=S、C=NR 3 、P(=O)(R 3 )、SO、SO 2 、NR 3 、O、S or CONR 3 may be replaced by, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 (), having 5 to 40 aromatic ring atoms, and in each case one or more R 3 radicals may optionally be substituted aromatic or heteroaromatic ring systems, having 5 to 40 aromatic ring atoms, one or more R 3 radicals may optionally be substituted aryloxy or heteroaryloxy groups, or having 5 to 40 aromatic ring atoms, one or more R 3 radicals may optionally be substituted aralkyl or heteroaralkyl groups; simultaneously, two substituents R # bonded to the same carbon atom or adjacent carbon atoms may optionally form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system substituted by one or more R 3 radicals.

[0217] Y 3 is preferably O, S or C(CH 3 ) 2 . Y 3 is most preferably O.

[0218] In structures Ar-1 to Ar-24, the substituent R 3is the same or different in each case, and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; simultaneously, two or more adjacent substituents R 3 are capable of forming together a monocyclic or polycyclic aliphatic ring system. In structures Ar-1 to Ar-22, the substituent R 3 is the same or different in each case, and is preferably selected from the group consisting of H, F, CN, an aliphatic hydrocarbyl radical having 1 to 10 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms. In structures Ar-1 to Ar-24, the substituent R 3 is the same or different in each case, and is preferably, as described above, H, or is selected from the group consisting of an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, and is preferably dibenzofuran, dibenzothiophene, 9-phenylcarbazole or spirobifluorene.

[0219] In structures Ar-1 to Ar-24, the substituent R 3 is, in each case, more preferably H.

[0220] Examples of suitable compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l) selected according to the present invention are the following structures from Table 2, or preferred compounds 37 to 66a:

[0221]

Table 2-1

[0222]

Table 2-2

[0223]

Table 2-3

[0224]

Table 2-4

[0225]

Table 2-5

[0226]

Table 2-6

[0227]

Table 2-7

[0228]

Table 2-8

[0229]

Table 2-9

[0230]

Table 2-10

[0231]

Table 2-11

[0232]

Table 2-12

[0233]

Table 2-13

[0234]

Table 2-14

[0235]

Table 2-15

[0236]

Table 2-16

[0237]

Table 2-17

[0238]

Table 2-18

[0239]

Table 2-19

[0240]

Table 2-20

[0241]

Table 2-21

[0242]

Table 2-22

[0243]

Table 2-23

[0244]

Table 2-24

[0245]

Table 2-25

[0246]

Table 2-26

[0247]

Table 2-27

[0248]

Table 2-28

[0249]

Table 2-29

[0250]

Table 2-30

[0251]

Table 2-31

[0252]

Table 2-32

[0253]

Table 2-33

[0254]

Table 2-34

[0255]

Table 2-35

[0256]

Table 2-36

[0257]

Table 2-37

[0258]

Table 2-38

[0259]

Table 2-39

[0260]

Table 2-40

[0261]

Table 2-41

[0262]

Table 2-42

[0263]

Table 2-43

[0264]

Table 2-44

[0265]

Table 2-45

[0266] Particularly preferred examples of the compounds of formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i) selected according to the present invention are compounds 37 to 66a:

[0267]

Chemical formula

[0268]

Chemical formula

[0269]

Chemical formula

[0270] The preparation of the compounds of formula (2) or the preferred compounds of formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l), as well as the compounds from Table 2 and compounds 37 to 66a, is known to those skilled in the art. The compounds may be prepared by synthetic processes known to those skilled in the art, such as halogenation, preferably bromination, followed by an organometallic coupling reaction, such as a Suzuki coupling, a Heck coupling or a Hartwig-Buchwald coupling. Some of the compounds of formula (2) are commercially available.

[0271] The host materials of the aforementioned formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) and the embodiments thereof described as preferred, or the compounds from Table 1 and Compounds 1 to 36 and 67 to 81 can be combined as necessary according to the present invention with the host materials of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l) and the embodiments thereof described as preferred, or the compounds from Table 2 or Compounds 37 to 66a.

[0272] A particularly preferred mixture of the host material of formula (1) and the host material of formula (2) for the composition of the present invention or the organic electronic device of the present invention is obtained by the combination of Compounds 1 to 36 and 67 to 81 and the compounds from Table 2.

[0273] A very particularly preferred mixture of the host material of formula (1) and the host material of formula (2) for the composition of the present invention or the organic electronic device of the present invention is obtained by the combination of Compounds 1 to 36 and 67 to 81 and Compounds 37 to 66a, as shown in Table 3 below.

[0274]

Table 3-1

[0275]

Table 3-2

[0276]

Table 3-3

[0277]

Table 3-4

[0278]

Table 3-5

[0279]

Table 3-6

[0280]

Table 3-7

[0281]

Table 3-8

[0282]

Table 3-9

[0283]

Table 3-10

[0284]

Table 3-11

[0285]

Table 3-12

[0286]

Table 3-13

[0287]

Table 3-14

[0288]

Table 3-15

[0289] The concentration of the composition or mixture of the electron-transporting host material of formula (1) as described previously or as described as preferred, or in the light-emitting layer of the device of the present invention, is in the range of 5% to 90% by weight, preferably in the range of 10% to 85% by weight, more preferably in the range of 20% to 85% by weight, even more preferably in the range of 30% to 80% by weight, very particularly preferably in the range of 20% to 60% by weight, and most preferably in the range of 30% to 50% by weight, based on the total composition / mixture or based on the total composition of the light-emitting layer.

[0290] The concentration of the composition or mixture of the hole-transporting host material of formula (2) as described previously or as described as preferred, or in the light-emitting layer of the device of the present invention, is in the range of 10% to 95% by weight, preferably in the range of 15% to 90% by weight, more preferably in the range of 15% to 80% by weight, even more preferably in the range of 20% to 70% by weight, very particularly preferably in the range of 40% to 80% by weight, and most preferably in the range of 50% to 70% by weight, based on the total composition / mixture or based on the total composition of the light-emitting layer.

[0291] In a further preferred embodiment, the composition of the present invention may further contain additional compounds, particularly organic functional materials, in addition to at least one compound of formula (1) as described previously or as described as preferred and at least one compound of formula (2) as described previously or as described as preferred. The composition according to the present invention is a physical mixture of at least one compound of formula (1), at least one compound of formula (2), and optionally further organic functional materials as components of the organic layers in the electronic devices described later.

[0292] Accordingly, the present invention also relates to a composition comprising, in addition to the aforementioned materials, at least one further compound selected from the group consisting of a hole injection material, a hole transport material, a hole blocking material, a wide band gap material, a fluorescent phosphor, a phosphorescent phosphor, a host material, an electron blocking material, an electron transport material, an electron injection material, an n-dopant and a p-dopant. Selecting these from the numerous materials known to those skilled in the art is not difficult for those skilled in the art at all.

[0293] The n-dopant is herein understood to mean a reducing agent, i.e., an electron donor.

[0294] The p-dopant is herein understood to mean an oxidizing agent, i.e., an electron acceptor.

[0295] The wide band gap material is herein understood to mean a material within the scope of the disclosure of US7,294,849, characterized by a band gap of at least 3.5 eV, and the band gap is understood to mean the gap between the HOMO and LUMO energies of the material.

[0296] Preferably, the composition of the present invention comprising at least one hole transporting host of formula (2) and at least one electron transporting host of formula (1) as described above or as preferably described further comprises at least one luminescent compound or phosphor, and a phosphorescent phosphor is particularly preferred.

[0297] The present invention also relates to a composition / mixture further containing at least one phosphorescent phosphor in addition to the aforementioned host materials 1 and 2, especially the mixtures M1 to M1597, as described above or as preferably described.

[0298] The present invention also relates to an organic electroluminescent device as described above, either before or later, preferably as described, wherein the light-emitting layer contains, in addition to the host materials 1 and 2 as described above, preferably as described, especially the material combinations M1 to M1597, at least one phosphorescent emitter.

[0299] The term "phosphorescent emitter" typically encompasses compounds in which light is emitted by a spin-forbidden transition from an excited state having a higher spin multiplicity, i.e., a spin state greater than 1, such as a triplet state or a state having an even higher spin quantum number, such as a quintet state. This is preferably understood to mean a transition from a triplet state.

[0300] Suitable phosphorescent emitters (= triplet emitters) are, inter alia, compounds which, when appropriately excited, preferably emit light in the visible region and contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially a metal having this atomic number. Preferred phosphorescent emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium or platinum. In the context of the present invention, all luminescent compounds containing the aforementioned metals are considered to be phosphorescent emitters.

[0301] Generally, all phosphorescent complexes used for phosphorescent OLEDs according to the prior art and known to those skilled in the art in the field of organic electroluminescent devices are suitable.

[0302] Examples of the above-mentioned light emitters can be found in applications WO2016 / 015815, WO00 / 70655, WO2001 / 41512, WO2002 / 02714, WO2002 / 15645, EP1191613, EP1191612, EP1191614, WO05 / 033244, WO05 / 019373, US2005 / 0258742, WO2009 / 146770, WO2010 / 015307, WO2010 / 031485, WO2010 / 054731, WO2010 / 054728, WO2010 / 086089, WO2010 / 099852, WO2010 / 102709, WO2011 / 032626, WO2011 / 066898, WO2011 / 157339, WO2012 / 007086, WO2014 / 008982, WO2014 / 023377, WO2014 / 094961, WO2014 / 094960, WO2015 / 036074, WO2015 / 104045, WO2015 / 117718, WO2016 / 015815, WO2016 / 124304, WO2017 / 032439, WO2015 / 036074, WO2015 / 117718 and WO2016 / 015815.

[0303] Preferred phosphorescent light emitters contain a dibenzofuran or azadibenzofuran structure in at least one ligand.

[0304] Preferred phosphorescent light emitters have the formula (3)

[0305]

Chemical formula

[0306] (wherein the symbols and subscripts for this formula (3) are defined as follows: n + m is 3, n is 1 or 2, m is 2 or 1, X is N or CR, R is H, D, a branched or linear alkyl group having 1 to 10 carbon atoms, or a partially or fully deuterated branched or linear alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 7 carbon atoms which may be partially or fully substituted by deuterium) is consistent with

[0307] In the phosphor of formula (3), n is preferably 1 and m is preferably 2.

[0308] In the phosphor of formula (3), preferably, one X is selected from N and the other X is CR.

[0309] In the phosphor of formula (3), at least one R is preferably different from H.

[0310] In the phosphor of formula (3), preferably two, three or four Rs are different from H and have one of the other definitions shown above for the phosphor of formula (3).

[0311] Preferred examples of the phosphorescent phosphor are listed in Table 4 below.

[0312]

Table 4-1

[0313]

Table 4-2

[0314]

Table 4-3

[0315]

Table 4-4

[0316]

Table 4-5

[0317]

Table 4-6

[0318]

Table 4-7

[0319]

Table 4-8

[0320]

Table 4-9

[0321]

Table 4-10

[0322]

Table 4-11

[0323]

Table 4-12

[0324]

Table 4-13

[0325]

Table 4-14

[0326] Preferred examples of the phosphorescent multi-legged light-emitting bodies are listed in Table 5 below.

[0327]

Table 5-1

[0328]

Table 5-2

[0329]

Table 5-3

[0330] In the composition / mixture of the present invention, preferably any of the mixtures M1 to M1597 as described above is combined with the compound of formula (3) or a compound from Table 4 or 5.

[0331] The composition of the present invention preferably comprises at least one compound of formula (1), at least one compound of formula (2), and one or two light emitters selected from the compounds of formula (3), Table 4 or Table 5.

[0332] In an organic electroluminescent device containing a composition as described above or preferably as described, and at least one phosphorescent emitter, the light emitting layer is preferably an infrared light emitting or yellow, orange, red, green, blue or ultraviolet light emitting layer, more preferably a yellow or green light emitting layer, and most preferably a green light emitting layer. Those containing at least one phosphorescent emitter preferably form an infrared light emitting or yellow, orange, red, green, blue or ultraviolet light emitting layer, more preferably a yellow or green light emitting layer, and most preferably a green light emitting layer.

[0333] The yellow light-emitting layer is understood here to mean a layer having a photoluminescence maximum within the range of 540 to 570 nm. The orange light-emitting layer is understood to mean a layer having a photoluminescence maximum within the range of 570 to 600 nm. The red light-emitting layer is understood to mean a layer having a photoluminescence maximum within the range of 600 to 750 nm. The green light-emitting layer is understood to mean a layer having a photoluminescence maximum within the range of 490 to 540 nm. The blue light-emitting layer is understood to mean a layer having a photoluminescence maximum within the range of 440 to 490 nm. The photoluminescence maximum of the layer is determined here by measuring the photoluminescence spectrum of a layer having a layer thickness of 50 nm at room temperature, and the layer has the composition of the present invention, i.e., contains a light emitter and a matrix.

[0334] The photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer.

[0335] The photoluminescence spectrum of the selected light emitter is generally measured in an oxygen-free solution of 10 -5 mol, generally at room temperature, and a suitable solvent is any one in which the selected light emitter dissolves at the concentration mentioned. Particularly suitable solvents are typically toluene or 2-methyl-THF, but dichloromethane is also suitable. The measurement is carried out using a commercially available photoluminescence spectrometer. The triplet energy T1 in eV units is determined from the photoluminescence spectrum of the light emitter. First, the peak maximum Plmax. (in nm units) of the photoluminescence spectrum is determined. Then, the peak maximum Plmax. (in nm units) is converted to eV by E (T1 in eV units) = 1240 / E (T1 in nm units) = 1240 / Plmax. (in nm units).

[0336] Accordingly, preferred phosphorescent light emitters are preferably infrared light emitters of formula (3) or from Table 4 or 5, and their triplet energy T 1 is preferably from about 1.9 eV to about 1.0 eV.

[0337] Therefore, the preferred phosphorescent emitter is preferably a red emitter of formula (3) or from Table 4 or 5, and its triplet energy T 1 is preferably from about 2.1 eV to about 1.9 eV.

[0338] Therefore, the preferred phosphorescent emitter is preferably a yellow emitter of formula (3) or from Table 4 or 5, and its triplet energy T 1 is preferably from about 2.3 eV to about 2.1 eV.

[0339] Therefore, the preferred phosphorescent emitter is preferably a green emitter of formula (3) or from Table 4 or 5, and its triplet energy T 1 is preferably from about 2.5 eV to about 2.3 eV.

[0340] Therefore, the preferred phosphorescent emitter is preferably a blue emitter of formula (3) or from Table 4 or 5, and its triplet energy T 1 is preferably from about 3.1 eV to about 2.5 eV.

[0341] Therefore, the preferred phosphorescent emitter is an ultraviolet emitter of formula (3) or from Table 4 or 5, and its triplet energy T 1 is preferably from about 4.0 eV to about 3.1 eV.

[0342] Therefore, particularly preferred phosphorescent emitters are green or yellow emitters as described above, preferably of formula (3) or from Table 4 or 5.

[0343] Therefore, highly particularly preferred phosphorescent emitters are preferably green emitters of formula (3) or from Table 4 or 5, and its triplet energy T 1 is preferably from about 2.5 eV to about 2.3 eV.

[0344] Most preferably, a green light emitter as described above, preferably of formula (3), or from Table 4 or 5, is selected for the composition of the present invention or for the light emitting layer of the present invention.

[0345] Preferred fluorescent emitters are selected from the class of arylamines. An arylamine or aromatic amine in the context of the present invention is understood to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthracene amines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines or aromatic chrysene diamines. An aromatic anthracene amine is understood to mean a compound in which a diarylamino group is directly bonded to an anthracene group, preferably at the 9-position. An aromatic anthracene diamine is understood to mean a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably at the 9,10-positions. Aromatic pyrene amines, pyrene diamines, chrysene amines and chrysene diamines are defined similarly, where the diarylamino group is bonded to pyrene, preferably at the 1-position or 1,6-positions. Further preferred fluorescent emitters are, for example, indenofluorene amines or diamines according to WO2006 / 108497 or WO2006 / 122630, for example benzoindenofluorene amines or diamines according to WO2008 / 006449, and for example dibenzoindenofluorene amines or diamines according to WO2007 / 140847, as well as indenofluorene derivatives having a fused aryl group as disclosed in WO2010 / 012328.

[0346] In a further preferred embodiment of the present invention, the composition of the present invention is used as a component of a mixed matrix system. The mixed matrix system preferably comprises 3 or 4 different matrix materials, more preferably 3 different matrix materials (in other words, one additional matrix component in addition to the composition of the present invention). Examples of suitable matrix materials that can be used as matrix components of the mixed matrix system in combination with the composition of the present invention are selected from wide bandgap materials, electron transport materials (ETMs) and hole transport materials (HTMs).

[0347] It is preferred to use a mixed matrix system in a phosphorescent organic electroluminescent device. One source of more detailed information regarding mixed matrix systems is application WO2010 / 108579. Particularly suitable matrix materials that can be used as matrix components of the mixed matrix system in a phosphorescent or fluorescent organic electroluminescent device in combination with the composition of the present invention are selected from the preferred matrix materials for phosphorescent emitters or the preferred matrix materials for fluorescent emitters specified below, depending on the type of emitter used. Preferably, the mixed matrix system is optimized for the emitter of formula (3), or from Table 4 or 5.

[0348] Various classes of substances are useful, in addition to the compositions of the present invention as described above, preferably as further host materials for fluorescent phosphors, and more preferably include mixtures of materials selected from M1 to M1597. Preferred further host materials are oligoarylenes (e.g., 2,2’,7,7’-tetraphenylspirobifluorene according to EP676461, or dinaphthylanthracene), in particular oligoarylenes containing condensed aromatic groups, oligoarylenevinylenes (e.g., DPVBi or spiro-DPVBi according to EP676461), polypodal metal complexes (e.g., according to WO2004 / 081017), hole-conducting compounds (e.g., according to WO2004 / 058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (e.g., according to WO2005 / 084081 and WO2005 / 084082), atropisomers (e.g., according to WO2006 / 048268), boronic acid derivatives (e.g., according to WO2006 / 117052), or benzanthracenes (e.g., according to WO2008 / 145239). Particularly preferred host materials are selected from the class of oligoarylenes containing naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides and sulfoxides. Highly particularly preferred matrix materials are selected from the class of oligoarylenes containing anthracene, benzanthracene, benzophenanthrene and / or pyrene or atropisomers of these compounds. It will be understood that oligoarylene in the context of the present invention means a compound in which at least three aryl or arylene groups are bonded to each other.

[0349] In addition to the composition of the present invention as described above, various classes of substances are useful, preferably as further useful matrix materials for the phosphorescent emitter, and more preferably, include a mixture of materials selected from M1 to M1597. Preferred further matrix materials are aromatic amines, such as, for example, triarylamines according to US2005 / 0069729, carbazole derivatives (such as CBP, N,N-biscarbazolylbiphenyl) or compounds according to WO2005 / 039246, US2005 / 0069729, JP2004 / 288381, EP1205527 or WO2008 / 086851, such as crosslinked carbazole derivatives according to WO2011 / 088877 and WO2011 / 128017, such as indenocarbazole derivatives according to WO2010 / 136109 and WO2011 / 000455, such as azacarbazole derivatives according to EP1617710, EP1617711, EP1731584, JP2005 / 347160, such as indolocarbazole derivatives according to WO2007 / 063754 or WO2008 / 056746, such as ketones according to WO2004 / 093207 or WO2010 / 006680, such as phosphine oxides, sulfoxides and sulfones according to WO2005 / 003253, oligophenylene, such as bipolar matrix materials according to WO2007 / 137725, such as silanes according to WO2005 / 111172, such as azaboroles or boronic esters according to WO2006 / 117052, such as triazine derivatives according to WO2010 / 015306, WO2007 / 063754 or WO2008 / 056746, such as zinc complexes, aluminum complexes according to EP652273 or WO2009 / 062578, such as BAlq, such as diazasilole derivatives and tetraazasilole derivatives according to WO2010 / 054729, such as diazaphosphole derivatives according to WO2010 / 054730, and aluminum complexes, such as those of the class of BAlQ.

[0350] In an alternative embodiment of the present invention, the composition contains no additional components, i.e., functional materials, in addition to the components of the electron transporting host and the hole transporting host. This embodiment relates to a mixture of materials used per se to form an organic layer, preferably a light-emitting layer. These systems are used as the sole material source in vapor deposition and are also referred to as premixed systems having a constant mixing ratio in vapor deposition. Then, it is possible to realize the vapor deposition of a layer in which the components are uniformly dispersed in a simple and rapid manner without requiring the precise operation of a plurality of material sources.

[0351] Accordingly, the present invention further provides a composition comprising a compound of formula (1), (1a) to (1h) or a compound selected from 1 to 36 and 67 to 81, and a compound of formula (2), (2a) to (2l) or a compound selected from 37 to 66a.

[0352] The composition of the present invention described above or as described preferably is suitable for use in an organic electronic device. Here, an organic electronic device is understood to mean a device containing at least one layer containing at least one organic compound. The device may also include inorganic materials or other layers formed entirely of inorganic materials.

[0353] Accordingly, the present invention further provides the use of a composition as described above or as described preferably, in particular a mixture selected from M1 to M1597, in an organic electronic device.

[0354] The components or constituents of the composition may be processed by vapor deposition or from a solution. When the composition is applied from a solution, a formulation of the composition of the present invention containing at least one additional solvent is required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, the use of a mixture of two or more solvents may preferably be used.

[0355] Accordingly, the present invention further provides a formulation comprising the composition of the present invention and at least one solvent.

[0356] Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fencon, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindane, or mixtures of these solvents.

[0357] The formulation may also contain at least one further organic or inorganic compound, especially a luminescent compound, especially a phosphorescent emitter and / or a further matrix material, which is likewise used in electronic devices. Suitable luminescent compounds and further matrix materials are those already detailed above.

[0358] The present invention also provides for the use of the composition of the present invention in an organic electronic device, preferably in an electron transporting layer and / or in a light emitting layer.

[0359] The organic electronic device is preferably selected from an organic integrated circuit (OIC), an organic field effect transistor (OFET), an organic thin film transistor (OTFT), an organic electroluminescent device, an organic solar cell (OSC), an organic optical detector, and an organic photoreceptor, and an organic electroluminescent device is particularly preferred.

[0360] A highly particularly preferred organic electroluminescent device containing at least one compound of formula (1) and at least one compound of formula (2) as described above or as described as preferred is an organic light emitting transistor (OLET), an organic field quenching device (OFQD), an organic light emitting electrochemical cell (OLEC, LEC, LEEC), an organic laser diode (O-laser), and an organic light emitting diode (OLED); OLEC and OLED are particularly preferred, and OLED is most preferred.

[0361] Preferably, the composition of the present invention as described above or as described as preferred is used in a layer having an electron transporting function in an electronic device. The layer is preferably an electron injection layer (EIL), an electron transport layer (ETL), a hole blocking layer (HBL) and / or a light emitting layer (EML), more preferably ETL, EIL and / or EML. Most preferably, the composition of the present invention is used in the EML, particularly as a matrix material or as a premixed system.

[0362] Therefore, the present invention further provides an organic electronic device which is particularly selected from one of the above-mentioned electronic devices and contains the composition of the present invention as described above or as described as preferred, preferably in the light emitting layer (EML), in the electron transport layer (ETL), in the electron injection layer (EIL) and / or in the hole blocking layer (HBL), very preferably in the EML, EIL and / or ETL, and most preferably in the EML.

[0363] When the layer is a light-emitting layer, particularly preferably, in addition to the composition as described above or as described as preferred, it is a phosphorescent layer characterized by containing a phosphorescent emitter together with an emitter of formula (3) or an emitter from Table 4 or 5, or a preferred emitter as described above.

[0364] Therefore, in a particularly preferred embodiment of the present invention, the electronic device is an organic electroluminescent device, most preferably an organic light-emitting diode (OLED), and contains the composition of the present invention as described above or as described later together with a phosphorescent emitter in a light-emitting layer (EML).

[0365] Therefore, in a particularly preferred embodiment of the present invention, the organic electroluminescent device includes an anode, a cathode, and at least one organic layer including at least one light-emitting layer, and at least one light-emitting layer contains at least one compound of formula (1) as host material 1 and at least one compound of formula (2) as host material 2, and the compounds of formula (1) and (2) have a structure as described above or as described as preferred or as described in combination as a specific composition or mixture.

[0366] Therefore, in a particularly preferred embodiment of the present invention, the organic electroluminescent device includes an anode, a cathode, and at least one organic layer including at least one light-emitting layer, and at least one light-emitting layer contains at least one compound of formula (1) as host material 1 and at least one compound of formula (2) as host material 2, and the compounds of formula (1) and (2) have a structure as described above or as described as preferred or as described in combination as a specific composition or mixture, and at least one light-emitting layer contains a phosphorescent emitter.

[0367] In the light-emitting layer of the device of the present invention as described above, based on the total composition of the light emitter and the matrix material, it preferably contains, by volume, from 99.9% to 1%, more preferably from 99% to 10%, particularly preferably from 98% to 60%, and most preferably from 97% to 80% of at least one compound of formula (1) and at least one compound of formula (2) as described above, which constitutes the matrix material. Correspondingly, the light-emitting layer in the device of the present invention preferably contains, by volume, from 0.1% to 99%, more preferably from 1% to 90%, still more preferably from 2% to 40%, and most preferably from 3% to 20% of the light emitter, based on the total composition of the light-emitting layer composed of the light emitter and the matrix material. When the compound is processed from a solution, it is preferable to use the corresponding amount in weight percentage instead of the amount specified above in volume percentage.

[0368] The light-emitting layer in the device of the present invention as described above preferably contains the matrix material of formula (1) and the matrix material of formula (2) in a volume ratio of from 3:1 to 1:3, preferably from 1:2.5 to 1:1, and more preferably from 1:2 to 1:1. When the compound is processed from a solution, it is preferable to use the corresponding ratio in weight percentage instead of the ratio specified above in volume percentage.

[0369] In addition to the cathode, anode, and the layer containing the composition of the present invention, the electronic device may further include additional layers. These may be, for example, in each case, one or more hole injection layers, hole transport layers, hole blocking layers, light-emitting layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, charge generation layers (IDMC2003, Taiwan; Session 21 OLED(5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and / or organic or inorganic p / n junctions. However, it should be noted that not all of these layers necessarily need to be present.

[0370] The layer arrangement in the organic electroluminescent device is preferably as follows: Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode.

[0371] This layer arrangement is a preferred arrangement.

[0372] At the same time, it should be pointed out again that not all of the layers mentioned need to be present, and / or additional layers may additionally be present.

[0373] The organic electroluminescent device of the present invention may contain two or more light emitting layers. According to the present invention, at least one of the light emitting layers contains a combination of the compound of formula (1) and the compound of formula (2) as described above. More preferably, these light emitting layers in this case have several emission maxima in the range of 380 nm to 750 nm as a whole and are adapted to produce white light as a whole; in other words, they can emit fluorescence or phosphorescence, and various light emitting compounds that emit blue or yellow or orange or red light are used in the light emitting layer. Particularly preferred is a three-layer system, i.e., a system having three light emitting layers, where the three layers exhibit blue, green and orange or red emission (see, for example, WO2005 / 011013 for the basic configuration). In the case of white light generation, individual light emitting compound that emits over a wide wavelength range may be suitable instead of a plurality of colored light emitting phosphor compounds.

[0374] Suitable charge transport materials that can be used in the hole injection or hole transport layer or electron blocking layer, or in the electron transport layer, of the organic electroluminescent device of the present invention are, for example, the compounds disclosed by Y. Shirota et al., Chem. Rev. 2007, 107(4), 953 - 1010, or other materials as used in these layers according to the prior art.

[0375] The material used for the electron transport layer may be any material that can be used as an electron transport material for the electron transport layer according to the prior art. Particularly suitable are aluminum complexes such as Alq 3 , zirconium complexes such as Zrq 4 , benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives. Further suitable materials are derivatives of the aforementioned compounds as disclosed in JP2000 / 053957, WO2003 / 060956, WO2004 / 028217, WO2004 / 080975, and WO2010 / 072300.

[0376] Preferred hole transport materials are, inter alia, materials that can be used for hole transport, hole injection, or electron blocking layers, such as indenofluorene amine derivatives (e.g., according to WO06 / 122630 or WO06 / 100896), amine derivatives disclosed in EP1661888, hexaazatriphenylene derivatives (e.g., according to WO01 / 049806), amine derivatives having a condensed aromatic system (e.g., according to US5,061,569), amine derivatives disclosed in WO95 / 09147, monobenzylindeno[1,2-b]fluorene amine (e.g., according to WO08 / 006449), dibenzylindeno[1,2-b]fluorene amine (e.g., according to WO07 / 140847), spirobifluorene amine (e.g., according to WO2012 / 034627 or unpublished EP12000929.5), fluorene amine (e.g., according to WO2014 / 015937, WO2014 / 015938, and WO2014 / 015935), spirodibenzopyran amine (e.g., according to WO2013 / 083216), and dihydroacridine derivatives (e.g., according to WO2012 / 150001).

[0377] Preferred cathodes for electronic devices are metals, metal alloys, or multilayer structures composed of various metals such as alkaline earth metals, alkali metals, main group metals, or lanthanoids (such as Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.) having a low work function. Additionally, alloys composed of an alkali metal or alkaline earth metal and silver, such as an alloy composed of magnesium and silver, are suitable. In the case of a multilayer structure, in addition to the metals mentioned, it is also possible to use a further metal having a relatively high work function, such as Ag or Al. In this case, metal combinations such as Ca / Ag, Mg / Ag, or Ba / Ag, etc. are generally used. It may also be preferable to introduce a thin intermediate layer of a material having a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials useful for this purpose are alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (such as LiF, Li 2 O, BaF 2 , MgO, NaF, CsF, Cs 2 CO 3 etc.). It is also possible to use lithium quinolate (LiQ) for this purpose. The layer thickness of this layer is preferably 0.5 to 5 nm.

[0378] Preferred anodes are materials having a high work function. Preferably, the anode has a work function exceeding 4.5 eV with respect to vacuum. First, metals having a high redox potential are suitable for this purpose, such as Ag, Pt, or Au. Second, metal / metal oxide electrodes (such as Al / Ni / NiO x , Al / PtO x) may also be preferred. Depending on the application, at least one of the electrodes must be transparent or partially transparent in order to enable irradiation of the organic material (organic solar cell) or emission of light (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Furthermore, conductive doped organic materials, especially conductive doped polymers, are preferred. In addition, the anode may also consist of two or more layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0379] Organic electronic devices are appropriately (depending on the application) structured during the manufacturing process, contacts are connected, and since the lifetime of the devices of the present invention is shortened in the presence of water and / or air, they are ultimately sealed.

[0380] In a further preferred embodiment, an organic electronic device comprising the composition of the present invention is characterized in that one or more organic layers comprising the composition of the present invention are coated by sublimation. In this case, the material is deposited by evaporation in a vacuum sublimation system at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 mbar. However, in this case, it is also possible to make the initial pressure even lower, for example less than 10 -7 mbar.

[0381] Similarly, an organic electroluminescent device characterized in that one or more layers are coated by the OVPD (organic vapor deposition) method or with the aid of carrier gas sublimation is preferred. 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 applied directly by a nozzle and thus structured (for example M.S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0382] In addition, one or more organic layers containing the composition of the present invention are formed from a solution, for example, by spin coating, or by any printing method such as screen printing, flexographic printing, nozzle printing or offset printing, but more preferably by LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. An organic electroluminescent device is preferred. For this purpose, soluble compounds of the components of the composition of the present invention are required. High solubility can be achieved by suitable substitution of the corresponding compounds. Treatment from a solution has the advantage that a layer containing the composition of the present invention can be applied in a very simple and inexpensive manner. This technique is particularly suitable for the mass production of organic electronic devices.

[0383] In addition, a hybrid method is possible, in which, for example, one or more layers are applied from a solution and one or more additional layers are applied by vapor deposition.

[0384] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

[0385] Accordingly, the present invention further provides a method for manufacturing an organic electronic device comprising the composition of the present invention as described above or as preferably described, characterized in that at least one organic layer containing the composition of the present invention is applied by vapor deposition, in particular by sublimation, and / or by OVPD (organic vapor phase deposition) method, and / or with the aid of carrier gas sublimation, or from a solution, in particular by spin coating or printing method.

[0386] In the manufacture of organic electronic devices using vapor deposition, there are, in principle, two methods by which an organic layer containing the composition of the present invention and which may contain a plurality of different components can be applied to any substrate, or can be applied by evaporation. First, the materials used can each be initially charged into a material source and ultimately evaporated from different material sources ("co-evaporation"). Second, the various materials can be premixed (premixed system) and the mixture can be initially charged into a single material source which will be its final evaporation source ("premixed evaporation"). Then, it is possible to achieve the deposition of a layer in which the components are uniformly dispersed in a simple and rapid manner without requiring the precise operation of a plurality of material sources.

[0387] Accordingly, the present invention further provides a method characterized by continuously or simultaneously depositing from the gas phase from at least two material sources at least one compound of formula (1) as described previously or as preferably described, and at least one compound of formula (2) as described previously or as preferably described, optionally together with other materials as described previously or as preferably described, to form an organic layer.

[0388] In a preferred embodiment of the present invention, at least one organic layer is applied using vapor deposition, where the components of the composition are premixed and evaporated from a single material source. For this embodiment, the following mixtures are particularly suitable: M4(1+40), M5(1+41), M24(2+37), M26(2+39), M33(2+46), M44(2+57), M48(3+38), M50(3+40), M70(4+37), M72(4+39), M81(4+48), M100(5+44), M101(5+45), M117(6+38), M130(6+51), M146(7+44), M165(8+40), M166(8+41), M238(11+44), M285(13+42), M301(13+58), M330(15+38), M332(15+40), M333(15+41), M358(16+43), M359(16+44), M379(17+41), M380(17+42), M543(24+44), M562(25+40), M592(26+44), M655(29+38), M657(29+40), M726(32+40), M727(32+41), M772(34+40) and M773(34+41) Accordingly, the present invention further provides a method characterized by using the composition of the present invention as described above or as preferably described as a material source for host-based vapor deposition and optionally forming an organic layer with additional materials.

[0389] The present invention further provides a method for manufacturing an organic electronic device comprising the composition of the present invention as described above or as preferably described, characterized by applying an organic layer using the formulation of the present invention as described above.

[0390] The composition of the present invention and the device of the present invention are characterized by the following surprising advantages over the prior art: The use of the composition of the present invention in organic electronic devices, particularly organic electroluminescent devices, particularly OLEDs or OLECs, leads to a distinct increase in power efficiency and the lifetime of the device is either equivalent or improved.

[0391] However, as is clear in Example 1 presented below, it is possible to achieve a good voltage by using a prior art compound, for example, compound SoA1. However, at a low emitter concentration of 8% in the EML in Example C1, the power efficiency is relatively low.

[0392] An improvement in power efficiency and / or lifetime at an equivalent operating voltage can be achieved by using a combination of a compound of formula (1) as described above in the present invention and a compound of formula (2) as described above.

[0393] This improvement in power efficiency at an equivalent operating voltage is preferably achievable by a combination of a compound of formula (1) as described above in the present invention and a compound of formula (2) as described above, at an emitter concentration of 2 to 25 volume percent in the light-emitting layer, preferably at an emitter concentration of 5 to 15 volume percent, more preferably at emitter concentrations of 7, 8, and 12 volume percent.

[0394] This improvement in power efficiency and lifetime at an equivalent operating voltage in the case of a specific combination is preferably achievable by a combination of a compound of formula (1) as described above in the present invention and a compound of formula (2) as described above, preferably at an emitter concentration of 2 to 25 volume percent in the light-emitting layer, preferably at an emitter concentration of 5 to 15 volume percent, more preferably at emitter concentrations of 7, 8, and 12 volume percent.

[0395] The difference between a prior art compound of a compound of formula (1) represented by Compound 4, for example, SoA1, lies in the bond to dibenzofuran at the 8-position.

[0396] It was not predictable to those skilled in the art that this change in the position of the substituent would result in an improvement of about 10% to 30% in the power efficiency of an electronic device, particularly an OLED, and the lifetime would be equivalent or improved.

[0397] The composition of the present invention has very good compatibility for use in the light-emitting layer and, as described above, exhibits improved performance data with respect to compounds from the prior art, particularly with regard to lifetime, operating voltage and / or power efficiency.

[0398] The composition of the present invention can be easily processed and thus has very good compatibility for mass production in commercial applications.

[0399] The composition of the present invention can be premixed and vapor deposited from a single material source, and thus it is possible to produce an organic layer in which the components used are uniformly dispersed in a simple and rapid manner.

[0400] These aforementioned advantages are not accompanied by further deterioration of the electronic properties of the electronic device.

[0401] It should be noted that modifications of the embodiments described in the present invention are included within the scope of the present invention. Any of the features disclosed in the present invention may be replaced with alternative features that serve the same purpose or equivalent or similar purposes, unless it is explicitly excluded. Thus, any of the features disclosed in the present invention should be regarded as an example from an inclusive series or equivalent or similar features, unless otherwise specified.

[0402] All features of the present invention may be combined with each other in any manner, provided that the specific features and / or steps are not mutually exclusive. This applies in particular to the preferred features of the present invention. Similarly, features of combinations that are not essential may be used individually (and without combination).

[0403] The technical teachings disclosed together with the present invention may be extracted and combined with other examples.

[0404] The present invention will be described in more detail by the following examples, which are not intended to limit the present invention thereby.

[0405] General method: Determination of orbital energy and electronic state The HOMO and LUMO energies of the material, as well as the triplet and singlet levels, are determined by quantum chemical calculations. For this purpose, in this case, the "Gaussian09, Revision D.01" software package (Gaussian Inc.) is used. In the case of calculations of metal-free organic substances (referred to as the "org." method), with a charge of 0 and a multiplicity of 1, structural optimization is first carried out by the semi-empirical method AM1 (Gaussian input line "#AM1 opt"). Subsequently, based on the optimized structure, (single-point) energy calculations are performed for the electronic ground state and the triplet level. This is carried out using the TDDFT (time-dependent density functional theory) method B3PW91 with a 6-31G(d) basis set (Gaussian input line "#B3PW91 / 6-31G(d)td=(50-50,nstates=4)") (charge 0, multiplicity 1). In the case of organometallic compounds (referred to as the "M-org." method), the structure is optimized by the Hartree-Fock method and the LanL2MB basis set (Gaussian input line "#HF / LanL2MB opt") (charge 0, multiplicity 1). The energy calculations are carried out as described above for organic substances, but the difference is that the "LanL2DZ" basis set is used for metal atoms and the "6-31G(d)" basis set is used for ligands (Gaussian input line "#B3PW91 / genpseudo=lanl2 td=(50-50,nstates=4)"). From the energy calculations, the HOMO is obtained in Hartree units (HEh and LEh) as the final orbital (alpha occ. eigenvalue) occupied by two electrons, and the LUMO is obtained as the first unoccupied orbital (alpha virt. eigenvalue), where Heh and LEh represent the HOMO energy in Hartree units and the LUMO energy in Hartree units, respectively. Using this, the values of the HOMO and LUMO calibrated by cyclic voltammetry measurements are determined in electron volts as follows: HOMO(eV)=(HEh*27.212)*0.8308-1.118; LUMO(eV)=(LEh*27.212)*1.0658-0.5049。

[0406] The triplet level T1 of the material is defined as the relative excitation energy (in eV) of the triplet state having the lowest energy found by quantum chemical energy calculations.

[0407] The singlet level S1 of the material is defined as the relative excitation energy (in eV) of the singlet state having the second lowest energy found by quantum chemical energy calculations.

[0408] The lowest energy singlet state is called S0.

[0409] The method described herein is independent of the software package used and always gives the same result. Examples of programs frequently used for this purpose are "Gaussian09" (Gaussian Inc.) and Q-Chem4.1 (Q-Chem, Inc.). In this case, the energy is calculated using the software package "Gaussian09, Revision D.01".

[0410] [Example 1]: Manufacture of OLED Examples I1 to I55 (see Table 6) that follow present the use of combinations of the materials of the present invention in OLEDs when compared with Examples C1 to C11.

[0411] Pretreatment for Examples C1 to I55: A glass plaque coated with structured ITO (indium tin oxide) having a thickness of 50 nm is treated first with oxygen plasma and then with argon plasma before coating. These plasma-treated glass plaques form the substrate to which the OLED is applied.

[0412] An OLED basically has the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emission layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL), and finally the cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm. The exact structure of the OLED can be found in Table 6. The materials required for the manufacture of the OLED are shown in Table 8. The device data of the OLED are listed in Table 7. Examples C1, C2, C3, C10, and C11 are comparative examples including an electron transporting host according to the prior art CN107973786. Examples C4, C5, C6, and C7 are comparative examples including a host according to the prior art WO2015 / 014435. Examples C8 and C9 are comparative examples including a host according to the prior art KR20160046077. Examples I1 - I55 show data for the OLEDs of the present invention.

[0413] All materials are applied by thermal evaporation in a vacuum chamber. In this case, the emission layer always consists of at least two matrix materials and a luminescent dopant (luminescent substance) added to the matrix materials in a specific volume ratio by co - evaporation. Details given in the form of SoA1:40:TEG3 (32%:60%:8%) mean that in the layer, material SoA1 is present in a volume ratio of 32%, compound 40 as a co - host is present in a ratio of 60%, and TEG3 is present in a ratio of 8%. Similarly, the electron transport layer may also consist of a mixture of two materials.

[0414] The OLEDs are characterized by standard methods. For this purpose, the current efficiency (SE, measured in cd / A), which is a function of luminance calculated from the current - voltage - luminance characteristics (IUL characteristics) assuming an electroluminescence spectrum and Lambertian emission characteristics, as well as the lifetime are measured. The electroluminescence spectrum is determined at a luminance of 1000 cd / m 2 and the CIE1931 x and y color coordinates are calculated therefrom. The parameter U10 in Table 7 means the voltage required for a current density of 10 mA / cm 2 PE10 is for a current density of 10 mA / cm 2It means the power efficiency achieved.

[0415] The lifetime LT is defined as the time until the luminance decreases to a certain ratio L1 during operation at the same initial luminance L0. The number L1 = 80% in Table 7 means that the lifetime in hours reported in the LT column corresponds to the time until the luminance decreases to 80% of the initial value.

[0416] In other words, for example, assuming L0 of 20000 cd / m 2 this is the time required until the sample has a luminance of only L1 = 0.8×L0 = 16000 cd / m 2 only.

[0417] Use of the mixture of the present invention in OLEDs The combination of materials of the present invention can be used in the light-emitting layer in phosphorescent green OLEDs. Combinations of Compounds 2, 3, 4, 5, 6, 9, 11, 13, 14, 17, 18, 22, 28, 30, 31, 32, 33, 34, 67, 69, 70, 72, 75, 76, 77 and 79 of the present invention with Compounds 37, 38, 40, 41, 42, 43, 44, 47, 48, 49, 52, 56, 58, 60, 61, 62, 63, 64, 65, 66 or 66a of the present invention are used as matrix materials in the light-emitting layer in Examples I1 to I55 as described in Table 6. The results shown in Table 7 indicate that when the same light emitter is used, for example, C1 and I1 or I1 and I4 or C2 and I2 are directly comparable For example, comparisons between examples of the present invention and corresponding comparative examples, such as I1 vs C1, I2 vs C2, I3 vs C3, I27 vs C4, I28 vs C5, I29 vs C6, I30 vs C7, I31 vs C8, I32 vs C9, I33 vs I10 and I34 vs C11 clearly show that the examples of the present invention each exhibit a distinct advantage in terms of lifetime.

[0418]

Table 6-1

[0419]

Table 6-2

[0420]

Table 6-3

[0421]

Table 6-4

[0422]

Table 6-5

[0423]

Table 7-1

[0424]

Table 7-2

[0425]

Table 8-1

[0426]

Table 8-2

[0427]

Table 8-3

[0428]

Table 8-4

[0429]

Table 8-5

[0430]

Table 8-6

[0431]

Table 8-7

[0432]

Table 8-8

[0433]

Table 8-9

[0434] [Example 2]: Synthesis of Compound a) 2-{12-chloro-8-oxatricyclo[7.4.0.0 2,7 trideca-1(13),2(7),3,5,9,11-hexaen-3-yl}-4-{8-oxatricyclo[7.4.0.0 2,7 trideca-1(9),2,4,6,10,12-hexaen-3-yl}-6-phenyl-1,3,5-triazine

[0435]

Chemical Structure

[0436] 58 g (210 mmol; 1.00 equivalent) of 1-boronyl-8-chlorodibenzofuran [CAS 162667-19-4], 90.2 g (252 mmol; 1.20 equivalent) of 2-chloro-4-{8-oxatricyclo[7.4.0.0 2,7{Trideca-1(9),2(7),3,5,10,12-hexaen-3-yl}-6-phenyl-1,3,5-triazine [CAS 1883265-32-4] and 44.5 g (420 mmol, 2.00 equivalents) of sodium carbonate [CAS 497-19-8] are suspended in a mixture of 1000 ml of dioxane [CAS 123-91-1], 1000 ml of toluene [CAS 108-88-3] and 400 ml of water. To this suspension is added 4.85 g (4.20 mmol / 0.02 equivalent) of tetrakis(triphenylphosphine)palladium(0) [CAS 14221-01-3], 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 concentrated to dryness. The yield is 79.1 g (151 mmol; 72% of theory).

[0437] Instead of 1-boronyl-8-chlorodibenzofuran [CAS 162667-19-4], 8-chloro-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzothiophene [CAS -2140848-96-8] can also be used.

[0438] In a similar manner, the following compounds can be obtained:

[0439]

Chemical formula

[0440]

Chemical formula

[0441]

Chemical formula

[0442] b) 3-Biphenyl-3-yl-9-[9-(4,6-diphenyl-[1,3,5]triazin-2-yl)-dibenzofuran-2-yl]-9H-carbazole

[0443]

Chem.

[0444] 21.4 g (42.7 mmol; 1.00 equivalent) of 2-{12-bromo-8-oxatricyclo[7.4.0.0 2,7 trideca-1(9),2(7),3,5,12-hexaen-3-yl}-4,6-diphenyl-1,3,5-triazine [CAS 1822310-63-3], 13.0 g (40.7 mmol; 1.10 equivalents) of 3-biphenyl-3-yl-9H-carbazole [CAS 1643526-99-1], and 7.82 g (81.4 mmol; 2.00 equivalents) of sodium tert-butoxide [CAS 865-47-4] are suspended in 500 ml of ortho-xylene [CAS 95-47-6]. To this suspension, 1.50 g (3.66 mmol; 9 mol%) of dicyclohexyl(2’,6’-dimethoxybiphenyl-2-yl)phosphine (SPhos) [CAS 657408-07-6] and 1.12 g (1.22 mmol; 3 mol%) of tris(dibenzylideneacetone)dipalladium [CAS 51364-51-3] are added, and the reaction mixture is heated under reflux for 16 hours. The reaction mixture is cooled to room temperature, and the solvent is removed under reduced pressure. The resulting solid is washed with 300 ml of ethanol and repeatedly recrystallized from a mixture of heptane and xylene. After hot filtration through Alox and subsequent sublimation under high vacuum, the purified product is obtained as a colorless solid, 21.1 g (29.5 mmol; 69%).

[0445] In a similar manner, the following compounds can be obtained:

[0446]

Chem.

[0447]

Chem.

[0448]

Chem.

[0449]

Chem.

[0450]

Chem.

[0451]

Chem.

[0452]

Chem.

[0453]

Chem.

Claims

1. At least one compound of formula (1) and at least one compound of formula (2) 【Chemistry 1】 (wherein the symbols and subscripts used are as follows: X １ are the same or different in each case, and CR ０ or N, with the proviso that at least one X １ The group is N; X is the same or different in each occurrence and is C or N, where two adjacent Xs are of the formula A 【Chemistry 2】 (wherein * in each instance is the attachment site for X, Y １ is NAr １ , C(R*) ２ , O and S. may be attached to a ring system of Y is selected from O and S; L, in each occurrence, is the same or different and is a single bond or has 6 to 30 aromatic ring atoms and is one or more R ５ an aromatic ring system optionally substituted by radicals; n and m in each occurrence are independently 0, 1, 2, or 3; o, p and q at each occurrence are independently 0, 1, 2, 3, or 4; Ar in each case １ independently has 5 to 40 aromatic ring atoms and is represented by one or more R ３ an aryl or heteroaryl group optionally substituted by a radical; R Ａ is H, -L ３ -Ar ４ Or -L １ -N(Ar) ２ and R Ｂ is Ar ３ Or -L ２ -N(Ar) ２ and L １ , L ２ are the same or different in each occurrence and are a single bond or have 5 to 30 aromatic ring atoms and one or more R ３ an aromatic or heteroaromatic ring system optionally substituted by radicals; L ３ has a single bond or 5 to 30 aromatic ring atoms and one or more R ３ an aromatic or heteroaromatic ring system optionally substituted by radicals, where one substituent R ３ is a substituent R on the carbazole ２ may form a ring together with Ar ３ is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 10 to 40 aromatic ring atoms, which may be represented by one or more R ３ may be substituted with a radical; Ar ４ are the same or different in each occurrence and are unsubstituted or substituted 9-arylcarbazolyl, or unsubstituted or substituted carbazol-9-yl, which are represented by one or more R ４ may be substituted by a radical, and in one or more cases, two R ４ Each of the radicals, or one of the R ４ The radical is one R ２ Together with the radicals, may independently form a monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring, where aryl has 5 to 30 aromatic ring atoms, R ３ an aromatic or heteroaromatic ring system optionally substituted by R* is in each occurrence the same or different and is a straight-chain alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, where two substituents R* together form one or more substituents R ５ may form an optionally substituted mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system; R ０ , R, R １ , R ２ are the same or different in each case and are H, D, F, Cl, Br, I, CN, NO ２ , N(Ar) ２ , N(R ３ ) ２ , C(=O)Ar, C(=O)R ３ , P(=O)(Ar) ２ , P(Ar) ２ , B(Ar) ２ , Si(Ar) ３ , Si(R ３ ) ３ , a straight chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of which may be represented by one or more R ３ radicals) (wherein one or more non-adjacent CH ２ The group is R ３ C=CR ３ , Si(R ３ ) ２ , C=O, C=S, C=NR ３ , P(=O)(R ３ ), SO, SO ２ , N.R. ３ , O, S or CONR ３ and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO ２ and optionally replaced by one or more R ３ an aromatic or heteroaromatic ring system, optionally substituted by a radical, having 5 to 40 aromatic ring atoms and one or more R ３ an aryloxy or heteroaryloxy group optionally substituted by a radical, or a aryloxy group having 5 to 40 aromatic ring atoms and one or more R ３ At the same time, two substituents R ０ and / or R and / or R １ and / or R ２ However, one or more R ３ Optionally capable of forming mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems, optionally substituted by radicals; R ３ are the same or different in each case, H, D, F, CN, N(Ar) ２ , an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; ３ The substituents, taken together, may form a mono- or polycyclic aliphatic ring system; R ４ are in each occurrence the same or different and are selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, a linear or branched alkyl group having 1 to 4 carbon atoms or CN; ４ The substituents, taken together, may form a monocyclic or polycyclic ring system; R ５ are the same or different in each occurrence and are selected from the group consisting of D, F, CN, and an aryl group having 6 to 18 carbon atoms; and at the same time, two or more adjacent substituents R ５ may together form a monocyclic or polycyclic aliphatic ring system; Ar, in each occurrence, is the same or different, has 5 to 30 aromatic ring atoms, and one or more non-aromatic R ３ at the same time, two Ar radicals bonded to the same nitrogen, phosphorus or boron atom are also bonded to a single bond or N(R ３ ), C(R ３ ) ２ , and may be crosslinked to each other by bridges selected from O and S; r at each occurrence is independently 0, 1, 2, or 3; s in each occurrence is independently 0, 1, 2, 3, or 4. and a composition comprising:

2. The composition according to claim 1 , wherein Y in formula (1) is O.

3. The compound of formula (2) is represented by the formulas (2a) to (2d): 【Chemistry 3】 (wherein the symbols and subscripts L １ , L ２ , L ３ , Ar, Ar ３ , Ar ４ , R ２ , r and s are as defined in claim 1.

3. The composition according to claim 1 or 2, characterized in that it meets one of the following criteria:

4. The composition according to any one of claims 1 to 3, characterized in that the composition comprises at least one further compound selected from the group consisting of hole injection materials, hole transport materials, hole blocking materials, wide band gap materials, fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron blocking materials, electron transport materials and electron injection materials, n-dopants and p-dopants.

5. The composition according to any one of claims 1 to 4, characterized in that the composition consists of a compound of formula (1) and a compound of formula (2).

6. A formulation comprising a composition according to any one of claims 1 to 5 and at least one solvent.

7. Use of a composition according to any one of claims 1 to 5 in an organic electronic device.

8. 8. The use according to claim 7, characterized in that the organic electronic device is selected from the group of organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors, and organic photoreceptors.

9. An organic electronic device comprising at least one composition according to any one of claims 1 to 5 in at least one organic layer.

10. 10. The device of claim 9, wherein the device is selected from the group of organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors, and organic photoreceptors.

11. 11. The device according to claim 9 or 10, characterized in that the device is an electroluminescent device selected from the group consisting of organic light emitting transistors (OLETs), organic field quenched devices (OFQDs), organic light emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers) and organic light emitting diodes (OLEDs).

12. The device according to any one of claims 9 to 11, characterized in that the device comprises the composition according to any one of claims 1 to 6 in an emissive layer (EML), in an electron transport layer (ETL), in an electron injection layer (EIL) and / or in a hole blocking layer (HBL).

13. 13. A device according to claim 11 or 12, comprising an anode, a cathode and at least one organic layer containing at least one light-emitting layer, characterized in that the device contains the composition according to any one of claims 1 to 5 in the at least one light-emitting layer together with a phosphorescent emitter.

14. A method for manufacturing a device according to any one of claims 9 to 13, characterized in that at least one organic layer comprising a composition according to any one of claims 1 to 5 is applied by vapor deposition or from solution.

15. 15. A method according to claim 14, characterized in that said at least one compound of formula (1) and said at least one compound of formula (2) as defined in any one of claims 1 to 4, optionally together with further materials, are deposited successively or simultaneously from the gas phase from at least two sources to form said organic layer.

16. 15. The method of claim 14, wherein the composition of claim 5 is utilized as a source of material for vapor phase deposition of a host system, optionally with additional materials, to form the organic layer.

17. 15. The method of claim 14, characterized in that the formulation according to claim 6 is used to apply the organic layer.

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