Composition for organic electronic devices

Abstract

The present invention relates to a composition comprising an electron transport host and a hole transport host, the use thereof in electronic devices and electronic devices comprising said composition. The electron transport host is more preferably selected from the class of triazine-dibenzofuran-carbazole systems or triazine-dibenzothiophene-carbazole systems. The hole transport host is preferably selected from the class of bis-carbazoles.

Description

TECHNICAL FIELD

[0001] The present application 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 systems or triazine-dibenzothiophene-carbazole systems. The hole transporting host is preferably selected from the class of bis-carbazoles. BACKGROUND

[0002] The structure of organic electroluminescent devices (e.g. OLEDs - organic light emitting diodes, or OLECs - organic light emitting electrochemical cells) in which organic semiconductors are used as functional materials has been known for a long time. In addition to fluorescent emitters, the light emitting materials used here are increasingly often organic metal complexes which exhibit phosphorescence instead of fluorescence. For quantum mechanical reasons, the use of organic metal compounds as phosphorescent emitters enables an increase in energy and power efficiency of a factor of four. However, in general, there is still a need for improvements in OLEDs, especially in OLEDs which exhibit triplet light emission (phosphorescence), for example in terms of efficiency, operating voltage and lifetime.

[0003] The properties of organic electroluminescent devices are determined not only by the emitters used. Of particular importance here are also the other materials used, such as host / matrix materials, hole blocking materials, electron transporting materials, hole transporting materials and electron or exciton blocking materials, and of particular importance among these are host or matrix materials. Improvements in these materials can lead to significant improvements in electroluminescent devices.

[0004] Host materials for use in organic electronic devices are well known to the person skilled in the art. The term "matrix material" is also frequently used in the prior art to refer to host materials for phosphorescent emitters. This use of the term also applies to the present application. At the same time, a large number of host materials have been developed for both fluorescent and phosphorescent electronic devices.

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

[0006] US 6,392,250 Bl discloses the use of a mixture of an electron transporting material, a hole transporting material and a fluorescent emitter in the light emitting layer of an OLED. By means of this mixture, the lifetime of the OLED can be improved compared to the prior art.

[0007] US 6,803,720 Bl discloses the use of a mixture comprising a phosphorescent emitter and a hole transporting material and an electron transporting material in the light emitting layer of an OLED. Both the hole transporting material and the electron transporting material are small organic molecules.

[0008] According to WO 2015 / 169412, for example, triazine-dibenzofuran-carbazole derivatives and triazine-dibenzothiophene-carbazole derivatives can likewise be used in mixtures. According to the description, the carbazole derivatives are not bonded to the dibenzofuran or dibenzothiophene basic skeleton via the nitrogen atom of the carbazole. For example, the production of an OLED designated E34 is described, which contains the host material EG1, IC6 and the phosphorescent emitter TEG1 in the emission layer. The structures of the compounds used are shown below:

[0009]

[0010] According to WO 2015 / 165563, for example, triazine-dibenzofuran-carbazole derivatives and triazine-dibenzothiophene-carbazole derivatives can likewise be used in mixtures. The carbazole derivatives are also understood to mean compounds of, for example, indolocarbazole and indenocarbazole. According to the description, the carbazole derivatives are not bonded to the dibenzofuran or dibenzothiophene basic skeleton via the nitrogen atom of the carbazole in position 8 of the dibenzofuran / dibenzothiophene. The triazine substituent is bonded in position 4 of the dibenzofuran / dibenzothiophene, directly or via a linking group. For example, the production of an OLED designated E9 is described, which contains the host material EG9, IC3 and the phosphorescent emitter TEG1 in the emission layer. The structures of the compounds EG9 and IC3 used are shown below:

[0011]

[0012] According to WO 2015 / 014435, triazine-dibenzofuran-carbazole derivatives and triazine-dibenzothiophene-carbazole derivatives can be used, for example, as host materials in the emission layer.

[0013] CN 107973786 likewise describes triazine-dibenzofuran-carbazole and triazine- dibenzothiophene-carbazole compounds. The triazine substituent is bonded in position 1 of the dibenzofuran / dibenzothiophene, directly or via a linking group. The carbazole derivative is bonded in position 6 of the dibenzofuran / dibenzothiophene, directly or via a linking group. It is further reported that these materials can be mixed with the biscarbazole H2 in a ratio of 10:90 to 90:10.

[0014] KR 20160046077 describes specific triazine-dibenzofuran-carbazole and triazine- dibenzothiophene-carbazole derivatives in the emission layer together with further host materials.

[0015] US 20160293853 describes specific dibenzofuran derivatives which can be used in combination with further host materials.

[0016] US 9771373 describes an organic light emitting device having an emission layer containing two host materials, wherein the host materials are each selected from a specific group of compounds.

[0017] WO 2016 / 015810 describes triazine-dibenzofuran-carbazole and triazine-dibenzothiophene-carbazole compounds, wherein the triazine substituent is bound in position 1 of the dibenzofuran / dibenzothiophene, either directly or via a linking group, and wherein the carbazole substituent is bound in position 8 of the dibenzofuran / dibenzothiophene via its nitrogen atom. According to the description, the mentioned compounds can be used in mixture with additional matrix materials.

[0018] KR 2018010149 describes similar compounds as those described in WO 2016 / 015810.

[0019] The publications WO 2018 / 174678 and WO 2018 / 174679 disclose devices containing mixtures of carbazole-dibenzofuran derivatives with biscarbazoles in the organic layer, wherein the linkage of the carbazole unit to the dibenzofuran backbone is possible at any position in the dibenzofuran, but is preferred in position 6 or 7.

[0020] The publication EP 3415512 describes in particular dibenzofuran derivatives of formula 1-1, wherein the phenyl, pyridine, pyrimidine or triazine substituent can be connected in position 1 of the dibenzofuran, either directly or via a linking group, and wherein at least two identical L2-Ar3 substituents can be connected in positions 6 and 8 of the dibenzofuran. Here Ar3 can be a carbazole bound via N. In the examples, such compounds are used in combination with specific biscarbazoles.

[0021] However, there is still a need for improvement in the case of using these materials or in the case of using mixtures of these materials, especially in terms of efficiency, operating voltage and / or lifetime of the organic electronic device. SUMMARY

[0022] Thus, the problem addressed by the present application is to provide materials which are suitable for use in organic electronic devices, especially in organic electroluminescent devices, and especially in phosphorescent OLEDs, and which lead to good device properties, especially in terms of improved power efficiency, improved operating voltage and / or improved lifetime, and to provide corresponding electronic devices.

[0023] It has now been found that the problems are solved and the disadvantages of the prior art are eliminated by a composition containing a compound of formula (1) and comprising a hole transport host of formula (2), and by an organic electronic device containing said composition. This composition leads to very good properties of the organic electronic device, especially an organic electroluminescent device, especially in terms of power efficiency, operating voltage and / or lifetime, and especially also in the presence of a light-emitting component in the light-emitting layer, especially in combination with a luminescent of formula (3) in a concentration of 2 to 25% by weight. The device of the present application especially shows very good power efficiency.

[0024] The present application therefore first provides a composition comprising at least one compound of formula (1) and at least one compound of formula (2),

[0025]

[0026] The symbols and indices used therein are as follows:

[0027] X1is identical or different in each case and is CR 0 or N, with the proviso that at least one X1group is N;

[0028] X is identical or different in each case and is C or N, wherein two adjacent X can be bonded to the ring system of formula A,

[0029]

[0030] wherein * is in each case a bonding site to X,

[0031] Y 1 is selected from NAr1, C(R*)2, O and S;

[0032] Y is selected from O or S;

[0033] L is identical or different in each case and is a single bond or an aromatic ring system having 6 to 30 aromatic ring atoms which can be substituted by one or more R 5 groups;

[0034] n and m are independently in each case 0, 1, 2 or 3,

[0035] o, p and q are independently in each case 0, 1, 2, 3 or 4;

[0036] Ar1is independently in each case an aryl or heteroaryl group having 5 to 40 aromatic ring atoms which can be substituted by one or more R 3 groups;

[0037] R AH, -L3-Ar4or -L1-N(Ar)2;

[0038] R B Ar3or -L2-N(Ar)2;

[0039] L1, L2are identical or different in each case and are a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which can be substituted by one or more R 3 groups;

[0040] L3is a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which can be substituted by one or more R 3 groups, where one substituent R 3 may form a ring with a substituent R 2 on the carbazole;

[0041] Ar3is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 10 to 40 aromatic ring atoms which can be substituted by one or more R 3 groups;

[0042] Ar4is identical or different in each case and is unsubstituted or substituted 9-arylcarbazolyl or unsubstituted or substituted carbazol-9-yl which can be substituted by one or more R 4 groups, and where in one or more cases each of the two R 4 groups or one R 4 group together with one R 2 group can 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 which can be substituted by R 3 ;

[0043] R * are identical or different in each case and are a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, where the two substituents R * together can form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more substituents R 5 ;

[0044] R 0 , R, R 1 , R 2 are identical or different in each case and are selected from the group consisting of H, D, F, Cl, Br, I, CN, NO2, 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(R3 ) 3, a linear alkyl, alkoxy or thioalkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 carbon atoms or an alkenyl group with 2 to 20 carbon atoms, each of which can be substituted by one or more R 3 groups, where one or more non-adjacent CH2 groups can be replaced by R 3 C=CR 3 , Si(R 3 )2, C=0, C=S, C=NR 3 , P(=0)(R 3 ), SO, S02, NR 3 , O, S or CONR 3 atoms and in each case can be substituted with one or more R 3 groups, an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms and which can be substituted by one or more R 3 groups, an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms and which can be substituted by one or more R 3 groups, or an aralkyl or heteroaralkyl group with 5 to 40 aromatic ring atoms and which can be substituted by one or more R 0 and / or R 1 and / or R 2 optionally can form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more R 3 groups;

[0045] R 3 are identical or different in each case and are selected from H, D, F, CN, N(Ar)2, an aliphatic hydrocarbon group with 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms can be replaced by D, F, Cl, Br, I or CN and which can be substituted by one or more alkyl groups each with 1 to 4 carbon atoms; while two or more adjacent R 3 substituents can together form a monocyclic or polycyclic aliphatic ring system;

[0046] R 4 are identical or different in each case and are selected from H, D, F, CN, an aliphatic hydrocarbon group with 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, a linear or branched alkyl group with 1 to 4 carbon atoms or CN; while two or more adjacent R 4The substituents can together form a monocyclic or polycyclic ring system;

[0047] R 5 are identical or different in each case and are selected from D, F, CN and aryl groups having 6 to 18 carbon atoms; while two or more adjacent substituents R 5 may together form a monocyclic or polycyclic aliphatic ring system;

[0048] Ar is identical or different in each case and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and can be substituted by one or more non-aromatic R 3 groups; while two Ar groups which are bound to the same nitrogen atom, phosphorus atom or boron atom can also be bridged to one another by a bridge selected from N(R 3 ), C(R 3 )2, O or S; and

[0049] r is independently in each case 0, 1, 2 or 3;

[0050] s is independently in each case 0, 1, 2, 3 or 4.

[0051] The present application also provides specific material combinations, formulations comprising these compositions, the use of these compositions in organic electronic devices, organic electronic devices, preferably electroluminescent devices, comprising these compositions and preferably comprising the compositions in a layer, and methods for producing these devices. The respective preferred embodiments as described below likewise form part of the subject matter of the present application. By the specific selection of known materials, especially with regard to the selection of compounds of the formula (1 ), surprising and advantageous effects are achieved.

[0052] The layer comprising a composition as described above or described below as preferred comprising at least one compound of the formula (1 ) and at least one compound of the formula (2) is especially an emission layer (EML), an electron transport layer (ETL), an electron injection layer (EIL) and / or a hole blocking layer (HBL).

[0053] When the layer is an emission layer, it is preferably a phosphorescent layer, characterized in that, in addition to the composition comprising the host materials of the formula (1 ) and of the formula (2) as described above, it also comprises a phosphorescent emitter.

[0054] In the context of the present application, adjacent carbon atoms are carbon atoms which are directly bonded to one another.

[0055] In the context of the present specification, the expression two or more groups can together form a ring is to be understood as meaning in particular that the two groups are connected to one another by a chemical bond, formally eliminating two hydrogen atoms. This is illustrated by the following scheme:

[0056]

[0057] However, additionally, the above expressions are also to be understood as meaning that if one of the two groups is hydrogen, the second group is bonded to the position where the hydrogen atom is bonded, forming a ring. This will be illustrated by the following scheme:

[0058]

[0059] Aryl groups in the context of the present application contain 6 to 40 aromatic ring atoms, preferably carbon atoms. Heteroaryl groups in the context of the present application contain 5 to 40 aromatic ring atoms; wherein the ring atoms include carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. Aryl groups or heteroaryl groups are to be understood here as meaning simple aromatic rings, i.e. phenyl groups derived from benzene, or simple heteroaromatic rings, e.g. derived from pyridine, pyrimidine or thiophene, or fused aryl or heteroaryl groups, e.g. derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline. Thus, aryl groups having 6 to 18 carbon atoms are preferably phenyl, naphthyl, phenanthryl or mesityl, without restriction on the attachment of the aryl group as substituent. Thus, arylene groups having 6 to 18 carbon atoms are preferably phenylene, naphthylene, phenanthrylene or mesitylene, without restriction on the attachment of the arylene group as linking group.

[0060] Aromatic ring systems in the context of the present application contain 6 to 40 carbon atoms in the ring system and can be substituted by one or more R 3 groups, wherein R 3 has the following definitions. Aromatic ring systems also contain aryl groups as described above.

[0061] Aromatic ring systems having 6 to 18 carbon atoms are preferably selected from phenylene, biphenylene, naphthylene, phenanthrylene and mesitylene, wherein the respective aromatic ring system can be substituted by one or more R 5 groups.

[0062] Heteroaromatic ring systems in the context of the present application contain 5 to 40 ring atoms and at least one heteroatom and can be substituted by one or more R 3 groups, wherein R 3 has the following definitions. Preferred heteroaromatic ring systems have 10 to 40 ring atoms and at least one heteroatom and can be substituted by one or more R 3 groups, wherein R 3The following definition applies. Heteroaromatic ring systems also contain heteroaryl groups as described above. The heteroatoms in a heteroaromatic ring system are preferably selected from N, O, and / or S. In the context of this invention, aromatic or heteroaromatic ring systems should be understood to mean systems that do not necessarily contain only aryl or heteroaromatic groups, but where multiple aryl or heteroaromatic groups can also be interrupted by non-aromatic units (preferably less than 10% of atoms other than H) such as carbon, nitrogen, or oxygen atoms or carbonyl groups. For example, in the context of this invention, systems such as 9,9'-spirodifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, piracene, etc., should therefore also be considered aromatic or heteroaromatic ring systems, as are systems in which two or more aryl groups are interrupted, for example, by straight-chain or cyclic alkyl groups or by silyl groups. In addition, systems in which two or more aryl or heteroaryl groups are directly bonded to each other, such as biphenyl, terphenyl, tetraphenyl, or bipyridine, are also covered by the definition of aromatic or heteroaryl ring systems.

[0063] It has 5 to 40 aromatic ring atoms and can be converted to the above R in each case. 3 Aromatic or heteroaromatic ring systems that are substituted with groups and can be attached to any desired position should be understood to refer to, for example, groups derived from: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, leucine, perylene, fluoranthene, benzo[a]fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, diphenylidene, terphenyl, diphenylidene, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indeno[a]fluorene, cis or trans monobenzo[a]indeno[a]fluorene. Fluorene, cis or trans dibenzo-indofluorene, trimer indo, isotrimer indo, spirotrimer indo, spiroisotrimer indo, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indole-carbazole, indocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenanthrene Azides, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthiazoles, phenanthreneimidazoles, pyridiniumimidazoles, pyraziniumimidazoles, quinoxalineimidazoles azole, benzo[ azole, naphtho azole, anthraquinone azole, phenanthrene azole, isotonic Azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenazine Azides, phenothiazines, fluorescent rings, naphthidine, azacarbazole, benzo[a]carbline, phenanthroline, 1,2,3-triazoles, 1,2,4-triazoles, benzo[a]triazoles, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- Diazole, 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, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indoleazine, and benzothiadiazole.

[0064] The abbreviation Ar may be the same or different in each case and is a compound with 5 to 30 aromatic ring atoms and can be converted by one or more non-aromatic R atoms. 3 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two Ar groups bonded to the same nitrogen, phosphorus, or boron atom can also be bonded via a single bond or selected from N(R) 3 ), C(R 3 2. O or S bridging bases are connected to each other. Substituent R 3 As described above or below, it is preferred.

[0065] In the context of this invention, cyclic alkyl, alkoxy, or thioalkoxy groups should be understood to mean monocyclic, bicyclic, or polycyclic groups.

[0066] In the context of this invention, where a single hydrogen atom or CH2 group may also be replaced by the C1- to C2- groups described above. 20- an alkyl group is understood to mean, for example, a methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-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 groups.

[0067] An alkenyl group is understood to mean, for example, a vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl group.

[0068] An alkynyl group is understood to mean, for example, an ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl group.

[0069] C1- to C 20 An alkoxy group is understood to mean, for example, a methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy group.

[0070] C1- to C 20 A thioalkyl group is understood to mean, for example, an S-alkyl group, for example a thiomethyl, 1 -thioethyl, 1 -thioisopropyl, 1 -thio-n-propyl, 1 -thioisobutyl, 1 -thio-n-butyl or 1 -thio-tert-butyl group.

[0071] Aryloxy or heteroaryloxy groups having 5 to 40 aromatic ring atoms mean O-aryl or O-heteroaryl and mean an aryl or heteroaryl group which is bonded via an oxygen atom.

[0072] Aryl or heteroaryl groups having 5 to 40 aromatic ring atoms mean an aromatic carbocyclic or heteroaromatic ring system which is either mono- or polycyclic, preferably 1 to 3 rings, and is either fused or non-fused.

[0073] A phosphorescent emitter in the context of the present application is a compound which exhibits luminescence from an excited state having a higher spin multiplicity, i.e. spin state > 1, in particular from an excited triplet state. In the context of the present application, all luminescent complexes with transition metals or lanthanides are considered to be phosphorescent emitters. A more precise definition is given below.

[0074] When a composition comprising at least one compound of the formula (1) as described above or as described below as preferred and at least one compound of the formula (2) as described above or as described below as preferred is used as a matrix material for a phosphorescent emitter, it is preferred that the triplet energy thereof is not significantly smaller than the triplet energy of the phosphorescent emitter. With regard to the triplet state level, it is preferred that T1(emitter) - T1(matrix) < 0.2 eV, more preferably < 0.15 eV, most preferably < 0.1 eV. Here, T1(matrix) is the triplet state level of the matrix material in the light-emitting layer, this condition applies to each of the two matrix materials, and T1(emitter) is the triplet state level of the phosphorescent emitter. If the light-emitting layer contains more than two matrix materials, the above-mentioned relationship preferably also applies to each additional matrix material.

[0075] The compounds of the formula (1) and preferred embodiments thereof are described below, which are present in the compositions and / or devices according to the application, for example as electron transport host.

[0076] The compositions according to the application contain at least one compound of the formula (1) as described above.

[0077] In the compounds of the formula (1), Y is selected from O and S.

[0078] In a preferred embodiment of the application, compounds of the formula (1) are selected in which Y is O.

[0079] In a preferred embodiment of the application, compounds of the formula (1) are selected in which Y is S.

[0080] In the compounds of the formula (1), the symbol X is N in at least one case, preferably in two cases, and CR 0 , or N in three cases.

[0081] Substituents

[0082]

[0083] Thus having the following definitions, wherein * indicates the bonding site to the dibenzofuran or dibenzothiophene and R 0 and Ar 1 having one of the definitions given above or the definitions given as preferred:

[0084]

[0085] R 0 are identical or different in each case and are preferably selected from H, D, F or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms. R 0 are more preferably H in each case.

[0086] the compounds of the formula (1), wherein X1is N in each case, are represented by the formula (1a):

[0087]

[0088] wherein Y, X, L, Ar1, R, R 1 , n, m, o and p have the definitions given above or the definitions given below.

[0089] More preferably, for the composition, at least one compound of the formula (1a) having substituents described above, described as preferred or described as preferred below is selected.

[0090] The application therefore also provides a composition as described above, wherein the compound of the formula (1) corresponds to the formula (1a), preferably the symbol Y is O.

[0091] The application therefore also provides a composition as described above, wherein the compound of the formula (1) corresponds to the formula (1a), preferably the symbol Y is S.

[0092] In the compounds of the formula (1) or (1a) or in the compounds of the formula (1) or (1a) described as preferred, when n or m is greater than 0, the substituents R are identical or different in each case and are preferably selected from 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. In the case of R, the heteroaromatic ring system having 5 to 40 aromatic ring atoms is preferably derived from dibenzofuran or dibenzothiophene. In the case of R, the aromatic ring system having 6 to 40 aromatic ring atoms is preferably phenyl, biphenyl or terphenyl, more preferably phenyl or [1,1',2',1"]-terphenyl-5'-yl. In the case of R, the alkyl group having 1 to 40 carbon atoms is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably methyl, ethyl, n-propyl or n-butyl, most preferably methyl.

[0093] In the compounds of the formula (1) or (1a), n and m are preferably 0.

[0094] In the compounds of the formula (1) or (1a) or the preferred compounds of the 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 correspond to formula A.

[0095] The preferred compounds of the formula (1) or (1a) are correspondingly the compounds of the formulae (1b), (1c), (1d), (1e), (1f), (1g) and (1h), wherein n and m are 0 and the symbols X have the definitions as described as preferred above,

[0096]

[0097]

[0098] wherein Y, Y 1 , L, Ar1and R 1 have the definitions given above or below.

[0099] In the compounds of the formula (1), (1a) to (1h) or the compounds of the formula (1), (1a) to (1h) described as preferred, the substituents R 1 are each independently selected from H, D or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms which can in each case be substituted by one or more R 3 groups, wherein R 3 has the definitions given above or below, and wherein two substituents R 1 on adjacent carbon atoms form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more R 3 groups.

[0100] In one embodiment of the application, the substituents R 1 are each independently selected from H, D or an aromatic ring system having 5 to 40 aromatic ring atoms which can in each case be substituted by one or more R 3 groups, wherein R 3 has the definitions given above or below. In said embodiment, the six or seven substituents R 1H, and the remaining substituents have the definitions as given above and are different from H. In said embodiment, the carbazole in the compounds of formula (1), (1a) and (1b) preferably carries a substituent R different from H and being an aromatic ring system having 5 to 40 aromatic ring atoms 1 .

[0101] In one embodiment of the application, the substituents R in the compounds of formula (1), (1a) and (1b) or in the compounds of formula (1), (1a) and (1b) described as preferred are 1 preferably each independently selected from H, D or a heteroaromatic ring system having 5 to 40 aromatic ring atoms and in each case can be substituted by one or more R 3 groups, wherein R 3 has the definition given above or given below. In said embodiment, preferably seven substituents R 1 are H, and the remaining substituents have the definitions as given above and are different from H. In said embodiment, the carbazole in the compounds of formula (1), (1a) and (1b) preferably carries a substituent R different from H and being a heteroaromatic ring system having 5 to 40 aromatic ring atoms 1 .

[0102] In the compounds of formula (1), (1a) to (1h) or in the compounds of formula (1), (1a) to (1h) described as preferred, the substituents R 1 are more preferably each independently selected from H or an unsubstituted or mono- or poly- R 3 substituted phenyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, triphenylenyl, 1-naphthyl, 2-naphthyl, carbazol-9-yl or 9-arylcarbazolyl, wherein aryl denotes an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and in each case can be substituted by one or more R 3 groups.

[0103] In the compounds of formula (1b), preferably six or seven substituents R 1 are defined as H, and two or one substituents R 1 have the different definitions as described above or described as preferred.

[0104] In the compounds of formula (1c) to (1h), all substituents R 1 are preferably H.

[0105] In the compounds of the formula (1), (1a) to (1h) or the compounds of the formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) described as preferred, Ar1is in each case independently preferably an aryl radical, as described above or described as preferred, which has 6 to 40 carbon atoms and can be substituted by one or more R 3 groups, or a dibenzofuranyl or dibenzothiophenyl radical, which can be substituted by one or more R 3 groups, or a carbazolyl radical, which can be bonded via C or via N and can be substituted by one or more R 3 groups. The bonding of the carbazolyl radical via a carbon atom is not limited here. Preferably, the carbazolyl radical is bonded via N and substituted by R 3 groups.

[0106] In the compounds of the formula (1), (1a) to (1h) or the compounds of the formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) described as preferred, Ar1is in each case independently preferably an aryl radical, as described above or described as preferred, which has 6 to 40 carbon atoms and can be substituted by one or more R 3 groups, or a dibenzofuranyl or dibenzothiophenyl radical, which can be substituted by one or more R 3 groups.

[0107] The bonding of the aryl radical or the dibenzofuranyl radical or the dibenzothiophenyl radical is not limited here.

[0108] Ar1may thus be preferably selected from the following Ar1-1to Ar1-12radicals, wherein R 3 have the definitions specified above or specified as preferred:

[0109]

[0110] More preferably, at least one Ar1is Ar1-1and the further aromatic substituent Ar1is an alkyl radical which has 6 to 40 carbon atoms and can be substituted by one or more R 3 groups, or a dibenzofuranyl or dibenzothiophenyl radical, preferably selected from Ar1-1to Ar1-12. More preferably, at least one Ar1is phenyl and the further aromatic substituent is a phenyl radical, which can be substituted by one or more R 3The groups Ar1are preferably phenyl, biphenyl or terphenyl, more preferably phenyl. Preferably, the aryl groups or heteroaryl groups in Ar1are each independently substituted once by R

[0111] In the compounds of the formula (1) or (1a) to (1h) or the compounds of the formula (1) or (1a) to (1h) described as preferred, as described above or described as preferred, Ar1is in each case independently an aryl or heteroaryl group which is substituted by one or more R 3 groups R 3 are in each case identical or different and are preferably selected from D, F or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms. In the case of R 3 , the heteroaromatic ring system having 5 to 40 aromatic ring atoms is preferably derived from dibenzofuran or dibenzothiophene. In the case of R 3 , the aromatic ring system having 6 to 40 aromatic ring atoms is preferably phenyl, biphenyl or terphenyl, more preferably phenyl. Preferably, the aryl groups or heteroaryl groups in Ar1are each independently substituted once by R 3 . More preferably, the aryl groups or heteroaryl groups in Ar1are substituted once by R 3 .

[0112] The substituents R 3 are preferably H. The substituents R 3 on aryl groups having 6 to 40 carbon atoms are preferably phenyl or H. Most preferably, the aryl groups or heteroaryl groups in Ar1are not substituted.

[0113] In the compounds of the formula (1), (1a), (1c), (1d), (1e), (1f), (1g) and (1h) or the compounds of the formula (1), (1a), (1c), (1d), (1e), (1f), (1g) and (1h) described as preferred, Y 1 is NAr1, C(R * )2, O or S, where Ar1has the definition given above or the definition given as preferred.

[0114] Preferably, NAr1is defined as N-phenyl. Y 1 is preferably NAr1or C(R * )2.

[0115] In one embodiment of the invention, compounds of formulas (1), (1a), and (1c) are preferred, or compounds described as preferably of formulas (1), (1a), and (1c), wherein Y 1 Having the definition given above, or where Y 1 For NAr1 and C(R) * )2, more preferably C(R) * )2.

[0116] In one embodiment of the invention, compounds of formulas (1), (1a), (1d), and (1e) are preferred, or compounds described as preferably of formulas (1), (1a), (1d), and (1e), wherein Y 1 Having the definition given above, or where Y 1 It is NAr1 and O, more preferably NAr1.

[0117] In compounds of formulas (1), (1a), (1c), (1d), (1e), (1f), (1g), and (1h), or compounds described as preferably of formulas (1), (1a), (1c), (1d), (1e), (1f), (1g), and (1h), the substituent R * In each case, they may be the same or different and are either straight-chain alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 12 carbon atoms, wherein the two substituents R * They can be formed together by one or more substituents R. 5 Substituted monocyclic or polycyclic aliphatic, aromatic, or heterocyclic ring systems. R * Preferably, the same applies in each case, or both substituents R * Together they form monocyclic or polycyclic aliphatic, aromatic, or heterocyclic ring systems. More preferably, R * Selected from methyl, ethyl, and phenyl. More preferably, the two substituents R * Together with the carbon atoms they are bonded to, they form a cyclic system selected from cyclopentyl and dibenzocyclopentyl, which can be substituted by one or more R groups. 5 Substitution. Composed of two substituents R * The formed ring system is more preferably spirodifluorene.

[0118] More preferably, Y 1 Selected from N-phenyl, C(methyl)2, O, and S. Most preferably, Y... 1 Defined as C(methyl)2.

[0119] In the compounds of the formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) or in the compounds of the formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) described as preferred, L is identical or different in each case and is a single bond or an aromatic ring system having 6 to 30 aromatic ring atoms and can be substituted by one or more R 5 groups, wherein R 5 is as defined above. R 5 is preferably selected from D and phenyl. L is preferably a single bond or an aromatic ring system having 6 to 18 carbon atoms, preferably a benzene, diphenylene, naphthylene, phenanthryl or mesityl group, wherein the attachment to the further substituent is not limited. The benzene group can be bonded here, for example, in the ortho, meta or para position to the dibenzofuran / dibenzothiophene unit.

[0120] L can thus preferably be selected from the linking groups L-1 to L-20, which can be unsubstituted or substituted by R 5 as described above:

[0121]

[0122] Preferably, the linking groups L-1 to L-20 are unsubstituted.

[0123] It is particularly preferred to use the linking groups L-1 to L-7.

[0124] Preferably, L is a single bond or a linking group selected from L-1 to L-7 or L-2 and L-3. More preferably, L is a single bond.

[0125] Particularly preferred compounds of the formula (1) comply with the formulae (1b) and (1c) as described above.

[0126] In the compounds of the formula (1), (1b) and (1c), Y is preferably O, Y 1 is preferably C(R * )2, Ar1 is independently in each case preferably phenyl, dibenzofuranyl, dibenzothiophenyl and biphenyl, as described above, and L is a single bond.

[0127] In the compounds of the formula (1), (1b) and (1c), Y is preferably O, Y 1 is preferably C(R * )2, Ar1 is independently in each case preferably phenyl, dibenzofuranyl, dibenzothiophenyl and biphenyl, as described above, and L is a single bond.

[0128] In the compounds of the formulae (1), (1 b) and (1 c), Y is preferably S, Y 1 is preferably C(R * )2, Ar1is in each case independently preferably phenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl-N- phenylidene, dibenzofuranylphenylidene, phenylcarbazolyl-N-yl, 1,3- and 1,4- biphenyl, as described above, and L is a single bond.

[0129] In the compounds of the formulae (1), (1 b) and (1 c), Y is preferably S, Y 1 is preferably C(R * )2, Ar1is in each case independently preferably phenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl-N- phenylidene, dibenzofuranylphenylidene, phenylcarbazolyl-N-yl, 1,3- and 1,4- biphenyl, as described above, and L is a single bond.

[0130] For the compositions of the present application, preference is given to selecting the compounds of the formulae (1 b) and (1 c) having the substituents Y, Y 1 , Ar1, L and R 1 as described above or as described as preferred.

[0131] Examples of suitable compounds of the formula (1), (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g) or (1 h) selected according to the present application are the structures or compounds 1 to 36 and 67 to 81 shown in Table 1 below.

[0132] Table 1:

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177] Particularly suitable compounds of formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) according to the present application are compounds 1 to 36 and 67 to 81:

[0178]

[0179]

[0180]

[0181]

[0182] The preparation of compounds of formula (1) or preferably of compounds of formula (1a) to (1h) and of compounds 1 to 36 and 67 to 81 is known to the person skilled in the art. The compounds can be prepared by synthetic steps known to the person skilled in the art, such as halogenation, preferably bromination, and subsequent organometallic coupling reactions, such as Suzuki coupling, Heck coupling or Hartwig-Buchwald coupling. The preparation of compounds of formula (1) or preferably of compounds of formula (1a) to (1h) and of compounds 1 to 36 and 67 to 81 can be derived, inter alia, from WO 2016 / 015810, in particular from the synthetic examples on page 35 and on pages 44 to 64.

[0183] Compounds of formula (1) to (1h) can be prepared according to the following Scheme 1, wherein L, X1, Y, R 1 , Ar1, n, m, o, p have one of the definitions given above.

[0184] Scheme 1:

[0185]

[0186] The following describes compounds of formula (2) and preferred embodiments thereof, which are present in the compositions and / or devices according to the application, for example as hole transport host.

[0187] The composition according to the application contains at least one compound of formula (2),

[0188]

[0189] The symbols and indices used therein are as follows:

[0190] R A is H, -L3-Ar4or -L1-N(Ar)2;

[0191] R B is Ar3or -L2-N(Ar)2;

[0192] L1, L2are identical or different in each case and are a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which can be substituted by one or more R 3 groups;

[0193] L3is a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which can be substituted by one or more R 3 groups, wherein one substituent R 3 may form a ring with a substituent R 2 on the carbazole;

[0194] Ar3is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 10 to 40 aromatic ring atoms which can be substituted by one or more R 3 groups;

[0195] Ar4is identical or different in each case and is unsubstituted or substituted 9-arylcarbazolyl or unsubstituted or substituted carbazol-9-yl which can be substituted by one or more R 4 groups, and wherein in one or more cases each of the two R 4 groups or one R 4 group together with one R 2 group can independently form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring, wherein aryl is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which can be substituted by R 3 ;

[0196] R 2 are identical or different in each case and are selected from the group consisting of H, D, F, Cl, Br, I, CN, NO2, 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 can be generated by one or more R 3 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 3 C = CR 3 Si(R) 3 2. C=O, C=S, C=NR 3 P(=O)(R) 3 SO, SO2, NR 3 O, S or CONR 3 Substitution, and one or more of the hydrogen atoms can be replaced by D, F, Cl, Br, I, CN or NO2, having 5 to 40 ring atoms and in each case can be replaced by one or more R 3 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 3 A group-substituted aryloxy or heteroaryloxy group, or a group having 5 to 40 ring atoms and being substituted with one or more R groups. 3 A group-substituted aralkyl or heteroaralkyl group; simultaneously, two substituents R bonded to the same or adjacent carbon atoms. 2 Optionally, it can be formed that can be generated by one or more R 3 Monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring systems with substituted groups;

[0197] R 3 In each case, the same or different, and selected from H, D, F, CN, N(Ar)2, an aliphatic hydrocarbon group 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 can be replaced by D, F, Cl, Br, I or CN and can be replaced by one or more alkyl groups each having 1 to 4 carbon atoms; simultaneously, two or more adjacent R 3 Substituents can work together to form monocyclic or polycyclic aliphatic ring systems;

[0198] R 4 In each case, they may be the same or different, and are selected from H, D, F, CN, aliphatic hydrocarbon groups having 1 to 20 carbon atoms or aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, straight-chain or branched alkyl groups having 1 to 4 carbon atoms or CN; and simultaneously, two or more adjacent R4 The substituents can together form a monocyclic or polycyclic ring system;

[0199] Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which can be substituted by one or more non-aromatic R 3 groups; two Ar groups which are bound to the same nitrogen, phosphorus or boron atom can also be bridged to one another by a single bond or a bridging group selected from N(R 3 ), C(R 3 )2, O or S; and

[0200] r is on each occurrence independently 0, 1, 2 or 3;

[0201] s is on each occurrence independently 0, 1, 2, 3 or 4.

[0202] In one embodiment of the application, compounds of formula (2) as described above are selected which are used in the composition together with compounds of formula (1 ), (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g) and (1 h) as described above or as described as preferred or together with the compounds in Table 1 or compounds 1 to 36 and 67 to 81.

[0203] Compounds of formula (2) can be represented by the following formulae (2a), (2b), (2c) and (2d):

[0204]

[0205] wherein L1, L2, L3, Ar, Ar3, Ar4, R 2 , r and s have the definitions given above or below.

[0206] Preferred compounds of formula (2) or (2a) are compounds of formula (2e), (2f), (2g), (2h) and (2i),

[0207]

[0208]

[0209] wherein R B , Ar3, aryl, R 2 , R 4 , r and s have the definitions given above or below, L3 in formula (2h) and (2i) is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which can be substituted by one or more R 3 groups, wherein one substituent R 2 on the carbazole can be replaced by a substituent R 3forms a ring, Z is C(R 3 )2, N-Ar, O or S, and t is 0 or 1.

[0210] Preferred compounds of formula (2) or (2c) wherein at least r is 1 are compounds of formula (2j), (2k), (2l),

[0211]

[0212] wherein Ar3, R 2 , R 3 and s have the definitions given above or below, and u, v and w are independently in each case 0 or 1.

[0213] R 3 in the compounds of formula (2j), (2k) and (2l) is preferably H or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which can be substituted by R 5 If u, v and / or w is 1, R 3 in the compounds of formula (2j), (2k) and (2l) is preferably phenyl. In preferred compounds of formula (2j), (2k) and (2l) one of the indices u, v or w is 1. More preferably, u, v and w are 0.

[0214] In the compounds of formula (2a) to (2l), when r and / or s is greater than 1, H is excluded from the definition of the substituents R 2 .

[0215] The application therefore also provides a composition as described above, wherein the compound of formula (2) corresponds to one of the compounds of formula (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l).

[0216] In the compounds of formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), one substituent R 2 and one substituent R 4 may form a ring, for example also defined by [Z] t in formula (2f), preferably the following rings Z-1 to Z-7, and wherein the dotted line in each case denotes a bond to the carbazole:

[0217]

[0218] In the compounds of formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j) and (2l), two substituents R2 In one or more cases, they can form a ring together, or two substituents R 4 (If present) they can form a ring together in one or more cases, wherein the ring is preferably selected independently from the following structures (S1) to (S9) in each case, where # and # represent the corresponding bonding sites with carbon atoms, and the structures can each be substituented by one or more substituents R. 3 replace:

[0219]

[0220] R in substructures (S1) to (S9) 3 Preferably, it is an H or aromatic or heteroaromatic ring system, wherein the aromatic or heteroaromatic ring system has 5 to 40 ring atoms and can be R 5 H or phenyl substitution is preferred.

[0221] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), and (2i), if the linking groups L1, L2, and L3 are not single bonds, they are each independently selected from linking groups L-2.1 to L-2.33:

[0222]

[0223]

[0224] Where W represents N-Ar, O, S, or C(CH3)2, Ar has the definition given above, and the linking groups L-2.1 to L-2.33 can be one or more R 3 Group substitution is indicated, and the dashed line represents the linkage with carbazole. For linking group L3, R is added to one of linking groups L-2.1 to L-2.33. 3 The group can react with the R of carbazole. 2 Groups form rings.

[0225] Preferably, the linking groups L-2.1 to L-2.33 are unsubstituted or substituted with phenyl groups.

[0226] The preferred linking group L1 is selected from structures L-2.1 to L-2.33, wherein W is defined as S or O, more preferably as O.

[0227] The preferred linker group L3 is selected from structures L-2.1 to L-2.33, wherein W is defined as O, S or N-Ar, more preferably as O or N-Ar.

[0228] In a preferred embodiment of the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), the two carbazoles are each connected to each other at the 3-position.

[0229] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), and (2i), r is preferably 0, 1, or 2, wherein R 2 It has the definition given above or the definition given below. More preferably, r is 0 or 1. Most preferably, r is 0.

[0230] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), and (2i), when r is greater than 0, the substituent R 2 In each case, they may be the same or different, and are preferably selected from D, F, alkyl groups having 1 to 40 carbon atoms, or aromatic ring groups having 5 to 40 atoms and being capable of being generated by one or more R groups. 3 The group consisting of aromatic or heteroaromatic ring systems with substituted groups. In the R... 2 Aromatic or heteroaromatic ring systems having 5 to 40 aromatic ring atoms are preferably derived from benzene, dibenzofuran, dibenzothiophene, 9-phenylcarbazole, indolo[3,2,1-jk]carbazole, biphenyl, and terphenyl, and can be generated by one or more R 3 Group substitution. Substituent [R] 2 ] r The preferred positions are 1, 2, 3, or 4 bits, or a combination of 1 and 4 bits, or 1 and 3 bits; more preferably, 1 and 3 bits, 2 or 3 bits; and most preferably, 3 bits, wherein R 2 It has one of the preferred definitions given above, and r is greater than 0. [R] 2 ] r The particularly preferred substituent R 2 It is carbazole-9-yl, biphenyl, terphenyl and dibenzofuranyl.

[0231] In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2k), and (2l), s is independently preferably 0, 1, or 2 in each case, where R 2 and R 4 It has the definition given above or the definition given below. More preferably, s is 0 or 1 independently in each case; most preferably, s is 0 in each case.

[0232] In the compounds of the formulae (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), the substituents R 4 are identical or different in each case and are preferably selected from D, F, an alkyl radical having from 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, a straight-chain or branched alkyl radical having from 1 to 4 carbon atoms or by CN. Two or more R 4 are in each case identical or different and are preferably selected from D, F, Cl, Br, I, CN, N02, N(Ar)2, NH2, N(R 4 )2, C(=0)Ar, C(=0)H, C(=0)R 4 , P(=0)(Ar)2, a straight-chain alkyl, alkoxy or thioalkyl radical having from 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having from 3 to 40 carbon atoms, or an alkenyl or alkynyl radical having from 2 to 40 carbon atoms, each of which can be substituted by one or more R s radicals, an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms which can in each case be substituted by one or more R 4 radicals, an aryloxy or heteroaryloxy radical having from 5 to 60 aromatic ring atoms which can in each case be substituted by one or more R 3 radicals. The preferred positions of the substituents R 2 are the 1, 2 or 3 positions, more preferably the 3 position, wherein R 3 has one of the preferred definitions given above and s is greater than 0. 3 Ar in N(Ar)2is preferably derived from benzene, dibenzofuran, fluorene, spirobifluorene, dibenzothiophene, 9-phenylcarbazole, biphenyl and terphenyl, which can be substituted by one or more substituents R 3 is preferably unsubstituted. 3 The substituents R 3 are identical or different in each case and are preferably selected from D, F, Cl, Br, I, CN, N02, N(Ar)2, NH2, N(R 2 )2, C(=0)Ar, C(=0)H, C(=0)R 2 , P(=0)(Ar)2, a straight-chain alkyl, alkoxy or thioalkyl radical having from 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having from 3 to 40 carbon atoms, or an alkenyl or alkynyl radical having from 2 to 40 carbon atoms, each of which can be substituted by one or more R 3 radicals, an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms which can in each case be substituted by one or more R 2 radicals, an aryloxy or heteroaryloxy radical having from 5 to 60 aromatic ring atoms which can in each case be substituted by one or more R s radicals. The preferred positions of the substituents R 2 are the 1, 2 or 3 positions, more preferably the 3 position, wherein R 2 has one of the preferred definitions given above and s is greater than 0.More preferably at its occurrence is an aromatic or heteroaromatic ring system as described above, preferably selected from and derived from benzene, carbazole, 9-phenylcarbazole, dibenzofuran, dibenzothiophene, fluorene, terphenyl or spirobifluorene, most preferably from dibenzofuran.

[0236] In the compounds of the formulae (2j), (2k) and (2l), R 2 is in each case identical or different and is preferably selected from 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 which can be substituted by one or more R 3 groups. Preferred positions of the substituents [R 2 ] s are the 1, 3 and 4 positions, more preferably the 3 position, wherein R 2 has one of the definitions given above. Preferably, s is 0 or 1. In the compounds of the formulae (2j), (2k) and (2l), R 2 in [R s ] 2 is preferably phenyl when s is 1.

[0237] In the case where one of the substituents R 2 as described above is substituted by a substituent R 3 , the definitions of R 3 as described above or as preferred apply.

[0238] In the compounds of the formulae (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2k) and (2i) as described above, Ar 3 is in each case independently an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 10 to 40 aromatic ring atoms which can be substituted by one or more R 3 groups.

[0239] In the compounds of the formulae (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i) as described above, aryl is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which can be substituted by R 3 .

[0240] Ar 3 and aryl are preferably derived from benzene, dibenzofuran, fluorene, spirobifluorene, dibenzothiophene, 9-phenylcarbazole, naphthalene, phenanthrene, triphenyl, biphenyl and terphenyl which can be substituted by one or more substituents R 3 , wherein R 3 has the definitions given above.

[0241] In the case of substituted heteroaromatic ring systems, particular preference is given to electron-rich ring systems, in which optionally R 3 In the case of substituted heteroaromatic ring systems, particular preference is given to electron-rich ring systems, in which optionally R 3 - the substituted ring system preferably contains only one nitrogen atom overall or optionally R 3 - the substituted ring system contains one or more oxygen and / or sulfur atoms overall.

[0242] In the compounds of the formulae (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l) or the compounds of the formulae (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l) described as preferred, aryl and Ar3are preferably independently selected in each case from the aromatic or heteroaromatic ring systems Ar-1 to Ar-24,

[0243]

[0244]

[0245]

[0246] where Y 3 are identical or different in each case and are O, NR # , S or C(R # )2, where the R # group bonded to N is not H, and R 3 has the above definition or the below preferred definition, and the dotted bond denotes a bond to the nitrogen atom.

[0247] R # are identical or different in each case and are H, D, F, Cl, Br, I, CN, NO2, 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 with 1 to 20 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 carbon atoms, or an alkenyl group with 2 to 20 carbon atoms, each of which can be substituted by one or more R 3 groups, where one or more non-adjacent CH2groups can be replaced by R 3 C=CR 3 , Si(R3 )2, C=0, C=S, C=NR 3 , P(=0)(R 3 ), SO, S02, NR 3 , O, S or CONR 3 may be replaced by D, F, CI, Br, I, CN or N02, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and in each case can be substituted by one or more R 3 may be replaced by D, F, CI, Br, I, CN or N02, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and in each case can be substituted by one or more R 3 may be replaced by D, F, CI, Br, I, CN or N02, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and in each case can be substituted by one or more R 3 may be replaced by D, F, CI, Br, I, CN or N02, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and in each case can be substituted by one or more R # may be replaced by D, F, CI, Br, I, CN or N02, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and in each case can be substituted by one or more R 3 may be replaced by D, F, CI, Br, I, CN or N02, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and in each case can be substituted by one or more R

[0248] Y 3 is preferably O, S or C(CH3)2. Y 3 is most preferably O.

[0249] In structures Ar-1 to Ar-24, the substituents R 3 are identical or different in each case and are selected from H, D, F, CN, an aliphatic hydrocarbon group 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 can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; while two or more adjacent substituents R 3 may together form a monocyclic or polycyclic aliphatic ring system. In structures Ar-1 to Ar-22, the substituents R 3 are identical or different in each case and are preferably selected from H, F, CN, an aliphatic hydrocarbon group 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 substituents R 3 are identical or different in each case and are preferably selected from H or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, but are preferably dibenzofuran, dibenzothiophene, 9-phenylcarbazole or spirobifluorene, as described above.

[0250] In structures Ar-1 to Ar-24, the substituents R 3 are more preferably H in each case.

[0251] Examples of suitable compounds of formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l) selected according to the application are the following structures or preferred compounds 37 to 66a from Table 2:

[0252] Table 2:

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296] Particularly suitable examples of compounds of formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i) selected according to the application are compounds 37 to 66a:

[0297]

[0298]

[0299]

[0300] The preparation of compounds of formula (2) or preferably of formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l) and of compounds from Tables 2 and 37 to 66a is known to the person skilled in the art. The compounds can be prepared by synthetic steps known to the person skilled in the art, such as halogenation, preferably bromination, and subsequent organometallic coupling reactions, such as Suzuki coupling, Heck coupling or Hartwig-Buchwald coupling. Some of the compounds of formula (2) are commercially available.

[0301] The host materials of the above formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h) and their description as preferred embodiments or the compounds from Table 1 and compounds 1 to 36 and 67 to 81 can be combined as desired according to the present application with the host materials of the above formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2l) and their description as preferred embodiments or the compounds from Table 2 or compounds 37 to 66a.

[0302] Particularly preferred mixtures of host materials of formula (1) with host materials of formula (2) for the composition according to the present application or the organic electronic device according to the present application are obtained by combining compounds 1 to 36 and 67 to 81 with the compounds from Table 2.

[0303] Very particularly preferred mixtures of host materials of formula (1) with host materials of formula (2) for the composition according to the present application or for the organic electronic device according to the present application are obtained by combining compounds 1 to 36 and 67 to 81 with compounds 37 to 66a, as shown in Table 3 below.

[0304] Table 3:

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327] The concentration of the electron transport host material of formula (1) as described above or as described as preferred, based on the overall composition / mixture or based on the overall composition of the light-emitting layer, is in the range of 5 to 90 wt.-%, preferably in the range of 10 to 85 wt.-%, more preferably in the range of 20 to 85 wt.-%, even more preferably in the range of 30 to 80 wt.-%, very particularly preferably in the range of 20 to 60 wt.-%, and most preferably in the range of 30 to 50 wt.-%, in the composition or mixture of the present application or in the light-emitting layer of the device of the present application.

[0328] The concentration of the hole transport host material of formula (2) as described above or described as preferred, based on the overall composition / mixture or based on the overall composition of the light-emitting layer, 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, in the composition or mixture of the present application or in the light-emitting layer of the device of the present application.

[0329] In another preferred embodiment, the composition of the present application can comprise, in addition to at least one compound of formula (1) as described above or described as preferred and at least one compound of formula (2) as described above or described as preferred, a further compound, especially an organic functional material. As described below, the composition according to the present application is a physical mixture of at least one compound of formula (1), at least one compound of formula (2) and optionally a further organic functional material as components of an organic layer in an electronic device.

[0330] Thus, the present application also relates to a composition comprising, in addition to the above-mentioned materials, 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, electron blocking materials, electron transport materials and electron injection materials, n-type dopants and p-type dopants. It is absolutely no difficulty for the person skilled in the art to select these materials from the multitude of materials known to the person skilled in the art.

[0331] An n-type dopant is understood here as meaning a reducing agent, i.e. an electron donor.

[0332] A p-type dopant is understood here as meaning an oxidizing agent, i.e. an electron acceptor.

[0333] A wide band gap material is understood here as meaning a material within the scope of the disclosure of US 7,294,849, characterized in that the band gap is at least 3.5 eV, the band gap being understood as meaning the gap between the HOMO energy and the LUMO energy of the material.

[0334] Preferably, the composition of the present application comprising at least one hole transport host of formula (2) and at least one electron transport host of formula (1) as described above or described as preferred additionally comprises at least one light-emitting compound or emitter, particularly preferably a phosphorescent emitter.

[0335] The application also relates to a composition / mixture which, in addition to the above-described or described as preferred host materials 1 and 2, in particular mixtures M1 to M1597, also contains at least one phosphorescent emitter.

[0336] The application also relates to an organic electroluminescent device as described above or below or described as preferred, wherein the light-emitting layer, in addition to the above-described or described as preferred host materials 1 and 2, in particular the material combinations M1 to M1597, also comprises at least one phosphorescent emitter.

[0337] The term "phosphorescent emitter" generally encompasses compounds which emit light as a result of a spin-forbidden transition from an excited state having a higher spin multiplicity, i.e. a spin state > 1, for example by transition from a triplet state or a state having an even higher spin quantum number (for example a quintet state). This is preferably to be understood as meaning a transition from a triplet state.

[0338] Suitable phosphorescent emitters (= triplet emitters) are in particular compounds which, when suitably excited, emit light, preferably in the visible region, and also 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, in particular a metal having said atomic number. Preferred phosphorescent emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum. In the context of the present application, all luminescent compounds containing the above-mentioned metals are regarded as phosphorescent emitters.

[0339] Generally, all phosphorescent complexes as used for phosphorescent OLEDs according to the prior art and as known to the person skilled in the art of organic electroluminescent devices are suitable.

[0340] Examples of the above light emitters can be found in the applications WO 2016 / 015815, WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626, WO 2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 023377, WO 2014 / 094961, WO 2014 / 094960, WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439, WO 2015 / 036074, WO 2015 / 117718 and WO 2016 / 015815.

[0341] Preferred phosphorescent emitters contain a dibenzofuran or azadibenzofuran structure in at least one ligand.

[0342] Preferred phosphorescent emitters comply with formula (3),

[0343]

[0344] wherein the symbols and indices of formula (3) are defined as follows:

[0345] n + m is 3, n is 1 or 2, m is 2 or 1,

[0346] X is N or CR,

[0347] R is H, D, a branched or straight alkyl group having 1 to 10 carbon atoms or a partially or completely deuterated branched or straight alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms which can be partially or completely substituted by deuterium.

[0348] In the emitters of formula (3), n is preferably 1 and m is preferably 2.

[0349] In the light emitter of formula (3), preferably, one X is selected from N and the other X is CR.

[0350] In the luminescent body of formula (3), at least one R is preferably different from H.

[0351] In the light emitter of formula (3), preferably two, three or four R are different from H and have one of the other definitions given above for the light emitter of formula (3).

[0352] Preferred examples of phosphorescent luminescent materials are listed in Table 4 below.

[0353] Table 4:

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367] Preferred examples of phosphorescent multipods are listed in Table 5 below.

[0368] Table 5:

[0369]

[0370]

[0371]

[0372]

[0373]

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380] In the compositions / mixtures of the present application, any mixture M1 to M1597 as described above is preferably combined with a compound of formula (3) or a compound from Table 4 or 5.

[0381] The composition of the present application preferably consists of at least one compound of formula (1), at least one compound of formula (2) and one or two luminophores selected from compounds of formula (3), Table 4 or Table 5.

[0382] The light-emitting layer in an organic electroluminescent device containing a composition as described above or described as preferred and at least one phosphorescent luminophore is preferably a layer emitting infrared light or a layer emitting yellow, orange, red, green, blue or ultraviolet light, more preferably a layer emitting yellow or green light, and most preferably a layer emitting green light. The layer containing at least one phosphorescent luminophore preferably forms a layer emitting infrared light or a layer emitting yellow, orange, red, green, blue or ultraviolet light, more preferably a layer emitting yellow or green light, and most preferably a layer emitting green light.

[0383] A layer emitting yellow light is to be understood here as meaning a layer having a photoluminescence maximum in the range from 540 nm to 570 nm. A layer emitting orange light is to be understood as meaning a layer having a photoluminescence maximum in the range from 570 nm to 600 nm. A layer emitting red light is to be understood as meaning a layer having a photoluminescence maximum in the range from 600 nm to 750 nm. A layer emitting green light is to be understood as meaning a layer having a photoluminescence maximum in the range from 490 nm to 540 nm. A layer emitting blue light is to be understood as meaning a layer having a photoluminescence maximum in the range from 440 nm to 490 nm. The photoluminescence maximum of a layer is determined here by measuring the photoluminescence spectrum of a layer having a layer thickness of 50 nm at room temperature, the layer having a composition of the application, i.e. comprising a luminophore and a matrix.

[0384] The photoluminescence spectrum of a layer is recorded, for example, with a commercial photoluminescence spectrometer.

[0385] Typically in the range from 10 -5In an oxygen-free solution of M, the photoluminescence spectrum of the selected emitter is measured, typically at room temperature, in a suitable solvent, which is any solvent in which the selected emitter is dissolved at the concentration. Particularly suitable solvents are typically toluene or 2-methyl-THF, also dichloromethane. The measurement is performed with a commercial photoluminescence spectrometer. The triplet energy T1 in eV is determined from the photoluminescence spectrum of the emitter. First, the maximum peak Plmax. (in nm) of the photoluminescence spectrum is determined. Then, the maximum peak Plmax. (in nm) is converted into eV by: E(T1, eV) = 1240 / E(T1, nm) = 1240 / Plmax. (nm).

[0386] Preferred phosphorescent emitters are thus infrared emitters, preferably of formula (3) or from Table 4 or 5, which have a triplet energy T1 of preferably from about 1.9 eV to about 1.0 eV.

[0387] Preferred phosphorescent emitters are thus red emitters, preferably of formula (3) or from Table 4 or 5, which have a triplet energy T1 of preferably from about 2.1 eV to about 1.9 eV.

[0388] Preferred phosphorescent emitters are thus yellow emitters, preferably of formula (3) or from Table 4 or 5, which have a triplet energy T1 of preferably from about 2.3 eV to about 2.1 eV.

[0389] Preferred phosphorescent emitters are thus green emitters, preferably of formula (3) or from Table 4 or 5, which have a triplet energy T1 of preferably from about 2.5 eV to about 2.3 eV.

[0390] Preferred phosphorescent emitters are thus blue emitters, preferably of formula (3) or from Table 4 or 5, which have a triplet energy T1 of preferably from about 3.1 eV to about 2.5 eV.

[0391] Preferred phosphorescent emitters are thus ultraviolet emitters of formula (3) or from Table 4 or 5, which have a triplet energy T1 of preferably from about 4.0 eV to about 3.1 eV.

[0392] Particularly preferred phosphorescent emitters are thus green or yellow emitters, preferably of formula (3) or from Table 4 or 5 as described above.

[0393] Very particularly preferred phosphorescent emitters are thus green emitters, preferably of formula (3) or from Table 4 or 5, which have a triplet energy T1 of preferably from about 2.5 eV to about 2.3 eV.

[0394] Most preferably, a green emitter as described above, preferably of formula (3) or from Table 4 or 5, is selected for the composition of the application or the light-emitting layer of the application.

[0395] Preferred fluorescent emitters are selected from the class of aryl amines. Aryl amines or aromatic amines in the context of the present application are understood to mean compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bound to a nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a condensed ring system, more preferably a condensed ring system having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthracene amines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysamine or aromatic chrysamine diamines. Aromatic anthracene amines are understood to mean compounds in which one diaryl amino group is directly bound to an anthracene radical, preferably in the 9-position. Aromatic anthracene diamines are understood to mean compounds in which two diaryl amino groups are directly bound to an anthracene radical, preferably in the 9,10-positions. Aromatic pyrene amines, pyrene diamines, chrysamine and chrysamine diamines are defined in an analogous manner to this, in which the diaryl amino groups are bound to the pyrene, preferably in the 1 -position or in the 1,6-positions. Further preferred fluorescent emitters are indenofluorene amines or indenofluorene diamines, such as according to WO 2006 / 108497 or WO 2006 / 122630; benzoindenofluorene amines or benzoindenofluorene diamines, such as according to WO 2008 / 006449; and dibenzoindenofluorene amines or dibenzoindenofluorene diamines, such as according to WO 2007 / 140847; as well as indenofluorene derivatives having condensed aryl radicals, which are disclosed in WO 2010 / 012328.

[0396] In another preferred embodiment of the present application, the composition of the present application is used as a component of a hybrid matrix system. The hybrid matrix system preferably comprises three or four different matrix materials, more preferably three different matrix materials (in other words, one further matrix component in addition to the composition of the present application). Examples of suitable matrix materials which can be combined with the composition of the present application as a matrix component in a hybrid matrix system are selected from the group consisting of wide bandgap materials, electron transport materials (ETM) and hole transport materials (HTM).

[0397] It is preferred that the hybrid matrix system is used in a phosphorescent organic electroluminescent device. One source of more detailed information on hybrid matrix systems is the application WO 2010 / 108579. Particularly suitable matrix materials which can be combined with the composition of the present application as a matrix component of a hybrid matrix system in a phosphorescent or fluorescent organic electroluminescent device are selected from the preferred matrix materials specified below for phosphorescent emitters or from the preferred matrix materials specified for fluorescent emitters, depending on the type of emitter used. Preferably, the hybrid matrix system is optimized for emitters of formula (3) or from Tables 4 or 5.

[0398] In addition to the compositions of the application as described above, which more preferably comprise a mixture of materials selected from M1 to M1597, various substance classes can be used as additional host material, preferably for fluorescent emitters. Preferred additional host materials are selected from the following classes: oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), in particular oligoarylenes containing fused aromatic groups, oligoarylenevinylene (e.g. DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (e.g. according to WO 2004 / 081017), hole-conducting compounds (e.g. according to WO 2004 / 058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides etc. (e.g. according to WO 2005 / 084081 and WO 2005 / 084082), atropisomers (e.g. according to WO 2006 / 048268), boronic acid derivatives (e.g. according to WO 2006 / 117052) or benzanthracenes (e.g. according to WO 2008 / 145239). Particularly preferred host materials are selected from the following classes: oligoarylenes comprising naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds; oligoarylenevinylene, ketones, phosphine oxides and sulfoxides. Very particularly preferred matrix materials are selected from the following classes: oligoarylenes comprising anthracene, benzanthracene, benzophenanthrene and / or pyrene or atropisomers of these compounds. Oligoarylenes in the context of the present application are understood to mean compounds in which at least three aryl or arylene groups are bonded to one another.

[0399] In addition to the compositions of the invention as described above, which more preferably contain a mixture of materials selected from M1 to M1597, various material classes can be used as useful additional matrix materials, preferably additional matrix materials for phosphorescent emitters. Preferred additional matrix materials are selected from the following categories: aromatic amines, especially triarylamines, such as those according to US 2005 / 0069729; carbazole derivatives (e.g., CBP, N,N-biscarbazole biphenyl), or compounds according to WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851; bridged carbazole derivatives, such as those according to WO 2011 / 088877 and WO 2011 / 128017; indobenzocarbazole derivatives, such as those according to WO 2010 / 136109 and WO2011 / 000455; azacarbazole derivatives, such as those according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 0069729; car ... 2005 / 347160; Indolocarbazole derivatives, e.g., according to WO 2007 / 063754 or WO 2008 / 056746; Ketones, e.g., according to WO2004 / 093207 or WO 2010 / 006680; Phosphine oxides, sulfoxides and sulfones, e.g., according to WO 2005 / 003253; Oligophenylene oxides, bipolar matrix materials, e.g., according to WO 2007 / 137725; Silanes, e.g., according to WO 2005 / 111172; Borazines or borate esters, e.g., according to WO 2006 / 117052; Triazine derivatives, e.g., according to WO 2010 / 015306, WO2007 / 063754 or WO 2008 / 056746; Zinc complexes, e.g., according to EP 652273 or WO 2009 / 062578; aluminum complexes, such as BAlq; silicon diazacyclopentane derivatives and silicon tetraazacyclopentane derivatives, such as according to WO 2010 / 054729; phosphorus diazacyclopentane derivatives, such as according to WO 2010 / 054730; and aluminum complexes, such as BAlQ.

[0400] In an alternative embodiment of the invention, the composition contains no other components besides the electron transport host and hole transport host components, i.e., no functional materials. This embodiment relates to the use of such material mixtures to fabricate organic layers, preferably luminescent layers. These systems are also called premixed systems, which serve as the sole material source in vapor deposition and have a constant mixing ratio during vapor deposition. Thus, vapor deposition of layers with uniformly distributed components can be achieved simply and quickly without the need for precisely exciting multiple material sources.

[0401] The application therefore also provides a composition consisting of 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.

[0402] The composition of the application as described above or described as preferred is suitable for use in an organic electronic device. An organic electronic device is understood here to mean a device which comprises at least one layer which contains at least one organic compound. The device can also comprise further layers which are formed of inorganic materials or are formed completely of inorganic materials.

[0403] The application therefore also provides the use of a composition as described above or described as preferred, in particular a mixture selected from M1 to M1597, in an organic electronic device.

[0404] The components or constituents of the composition can be processed by vapour deposition or from solution. If the composition is applied from solution, a formulation of the composition of the application comprising at least one further solvent is required. These formulations can be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents can preferably be used.

[0405] The application therefore also provides a formulation comprising a composition of the application and at least one solvent.

[0406] Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetraline, veratrol, THF, methyl-THF, THP, chlorobenzene, di alkyl, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-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-isopropyl naphthalene, amylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindane or mixtures of these solvents.

[0407] The formulations can also comprise at least one further organic or inorganic compound which is likewise used in electronic devices, in particular a luminescent compound, in particular a phosphorescent emitter, and / or a further matrix material. Suitable luminescent compounds and further matrix materials have already been described in detail above.

[0408] The present application also provides the use of the compositions of the present application in organic electronic devices, preferably in the electron transport layer and / or in the light-emitting layer.

[0409] The organic electronic device is preferably selected from the group consisting 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, particularly preferred is an organic electroluminescent device.

[0410] Very particularly preferred organic electroluminescent devices containing at least one compound of the formula (1 ) and at least one compound of the formula (2) as described above or described as preferred are organic light-emitting transistors (OLETs), organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers) and organic light-emitting diodes (OLEDs); particularly preferred are OLECs and OLEDs, and most preferred are OLEDs.

[0411] Preferably, the compositions of the present application as described above or described as preferred are used in layers having an electron transport function in electronic devices. The layers are preferably electron injection layers (EILs), electron transport layers (ETLs), hole blocking layers (HBLs) and / or light-emitting layers (EMLs), more preferably ETLs, EILs and / or EMLs. Most preferably, the compositions of the present application are used in EMLs, especially as matrix material or as a premix system.

[0412] The present application therefore also provides an organic electronic device, especially selected from one of the above-mentioned electronic devices, and preferably comprising a composition of the present application as described above or described as preferred 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.

[0413] In the case where the layer is a light-emitting layer, it is particularly preferred to be a phosphorescent layer, which is characterized in that, in addition to the composition as described above or described as preferred, it also comprises a phosphorescent emitter, especially together with an emitter of the formula (3) or from Tables 4 or 5 or a preferred emitter as described above.

[0414] Thus, in a particularly preferred embodiment of the present application, the electronic device is an organic electroluminescent device, most preferably an organic light emitting diode (OLED), which contains the inventive composition as described above or below and a phosphorescent emitter in the light emitting layer (EML).

[0415] In a particularly preferred embodiment of the present application, the organic electroluminescent device is thus a device comprising an anode, a cathode and at least one organic layer, which comprises at least one light emitting layer, wherein the 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, wherein the compounds of formula (1) and (2) have the structure as described above or described as preferred or as a specific composition or combination of mixtures.

[0416] In a particularly preferred embodiment of the present application, the organic electroluminescent device is thus a device comprising an anode, a cathode and at least one organic layer, which comprises at least one light emitting layer, wherein the 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, wherein the compounds of formula (1) and (2) have the structure as described above or described as preferred or as a specific composition or combination of mixtures, and wherein the at least one light emitting layer contains a phosphorescent emitter.

[0417] The light emitting layer in the inventive device as described above contains preferably 99.9 vol.% to 1 vol.%, further preferably 99 vol.% to 10 vol.%, especially preferably 98 vol.% to 60 vol.%, very especially preferably 97 vol.% to 80 vol.% of the host material consisting of at least one compound of formula (1) and at least one compound of formula (2) as described above, based on the total composition of the emitter and the host material. Accordingly, the light emitting layer in the inventive device contains preferably 0.1 vol.% to 99 vol.%, further preferably 1 vol.% to 90 vol.%, more preferably 2 vol.% to 40 vol.%, most preferably 3 vol.% to 20 vol.% of the emitter, based on the total composition of the light emitting layer consisting of the emitter and the host material. If the compounds are processed from solution, it is preferred to use the corresponding amounts in wt.% instead of the above specified amounts in vol.%.

[0418] The light emitting layer in the inventive device as described above contains preferably the host material of formula (1) and the host material of formula (2) in a volume ratio percentage of 3:1 to 1:3, preferably 1:2.5 to 1:1, more preferably 1:2 to 1:1. If the compounds are processed from solution, it is preferred to use the corresponding ratio in wt.% instead of the above specified ratio in vol.%.

[0419] In addition to the cathode, the anode and the layer comprising the composition according to the application, the electronic device can comprise further layers. These layers are in each case selected from, for example, 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, interlayers, charge generation layers (IDMC 2003, Taiwan; Section 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. It should be noted, however, that not necessarily every one of these layers is present.

[0420] The sequence of layers in the organic electroluminescent device is preferably as follows:

[0421] Anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode.

[0422] The sequence of layers is a preferred sequence.

[0423] At the same time, it should again be noted that not necessarily all of the layers are present and / or further layers can additionally be present.

[0424] The organic electroluminescent device according to the application can comprise two or more light-emitting layers. According to the application, at least one light-emitting layer contains a combination of a compound of the formula (1) as described above and a compound of the formula (2). More preferably, these light-emitting layers in this case have several emission maxima between 380 nm and 750 nm in total in this case, so that the overall result is white emission; in other words, various emitter compounds which can emit fluorescent or phosphorescent and emit blue or yellow or orange or red light are used in the light-emitting layers. A three-layer system, i.e. a system with three light-emitting layers, in which the three layers show blue, green and orange or red emission, is particularly preferred (for the basic structure, see, for example, WO 2005 / 011013). It should be noted that, in order to produce white light, it can also be suitable to use an emitter compound which emits light in a broad wavelength range alone, instead of a plurality of emitter compounds of different emission colours.

[0425] Suitable charge transport materials which can be used in the hole injection or hole transport layers or electron blocking or electron transport layers of the organic electroluminescent device according to the application are, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials as used in these layers according to the prior art.

[0426] The material used for the electron transport layer can be any material as used for electron transport materials in electron transport layers according to the prior art. Especially suitable are aluminum complexes, such as Alq3; zirconium complexes, such as Zrq4; benzimidazole derivatives; triazine derivatives; pyrimidine derivatives; pyridine derivatives; pyrazine derivatives; quinoxaline derivatives; quinoline derivatives; oxadiazole derivatives; aromatic ketones; lactams; boranes; phosphinazolides and phosphine oxide derivatives. Further suitable materials are derivatives of the above compounds disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975 and WO 2010 / 072300.

[0427] Preferred hole transport materials are especially materials which can be used in hole transport, hole injection or electron blocking layers, such as indenofluorene amine derivatives (e.g. according to WO 06 / 122630 or WO 06 / 100896), amine derivatives disclosed in EP 1661888, hexaazatriphenylalanmine derivatives (e.g. according to WO 01 / 049806), amine derivatives with fused aromatic systems (e.g. according to US 5,061,569), amine derivatives disclosed in WO 95 / 09147, mono-benzoindenofluorene amine (e.g. according to WO 08 / 006449), di-benzoindenofluorene amine (e.g. according to WO 07 / 140847), spirobifluorene amine (e.g. according to WO 2012 / 034627 or still unpublished EP 12000929.5), fluorene amine (e.g. according to WO 2014 / 015937, WO 2014 / 015938 and WO 2014 / 015935), spiro-bis-benzopyran amine (e.g. according to WO 2013 / 083216) and dihydroacridine derivatives (e.g. according to WO 2012 / 150001).

[0428] Preferred cathodes for electronic devices are metals having a low work function, metal alloys or multilayered structures composed of various metals, such as alkali earth metals, alkali metals, main group metals or lanthanides (for example, Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys composed of alkali or alkali earth metals and silver, for example alloys composed of magnesium and silver. In the case of multilayered structures, in addition to the metals mentioned, further metals having a relatively high work function, for example Ag or Al, can also be used, in which case combinations of metals are generally used, for example Ca / Ag, Mg / Ag or Ba / Ag. It can also be preferred to introduce a thin intermediate layer of a material having a high dielectric constant between the metal cathode and the organic semiconductor. Examples of useful materials for this purpose are alkali or alkali earth metal fluorides, and also the corresponding oxides or carbonates (for example, LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Lithium quinolate (LiQ) can also be used for this purpose. The layer thickness of the layer is preferably between 0.5 nm and 5 nm.

[0429] Preferred anodes are materials having a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, metals having a high redox potential are suitable for this purpose, for example Ag, Pt or Au. Secondly, metal / metal oxide electrodes (for example, Al / Ni / NiOx x , Al / PtO x ) can also be preferred. For some applications, at least one electrode must be transparent or partially transparent in order to be able to irradiate the organic material (organic solar cell) or to emit light (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is also given to conductive doped organic materials, in particular conductive doped polymers. Furthermore, the anode can 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.

[0430] The organic electronic devices are suitably constructed (depending on the application) during manufacture, contact-connected and finally sealed, since the lifetime of the devices according to the application is shortened in the presence of water and / or air.

[0431] In a further preferred embodiment, the organic electronic device comprising the composition according to the application is characterized in that one or more organic layers comprising the composition according to the application are applied by a sublimation process. In this case, the material is applied by vapour deposition in a vacuum sublimation system at an initial pressure of less than 10 -5 millibar, preferably less than 10 -6 millibar. However, in this case, the initial pressure can also be even lower, for example less than 10-7 millibar.

[0432] Also preferred is an organic electroluminescence device, characterized in that one or more layers are applied by means of OVPD (organic vapor phase deposition) or by means of carrier gas sublimation. In this case, the material is applied at a pressure of 10 -5 millibar and 1 bar. A special case of the method is the OVJP (organic vapor jet printing) method, in which the material is applied directly through a nozzle and is thus structured (e.g. M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0433] Further preferred is an organic electroluminescence device, characterized in that one or more layers comprising the composition according to the application are produced from a solution, for example by spin coating, or by any printing method, such as screen printing, flexographic printing or offset printing, but more preferably LITI (light induced thermal imaging, thermal transfer printing) or inkjet printing. To this end, soluble compounds of the components of the composition according to the application are required. High solubility can be achieved by suitable substitution of the respective compounds. The advantage of processing from a solution is that the layer comprising the composition according to the application can be applied in a very simple and inexpensive manner. The said techniques are particularly suitable for mass production of organic electronic devices.

[0434] In addition, hybrid methods are possible, in which for example one or more layers are applied from a solution and one or more further layers are applied by vapor deposition.

[0435] These methods are known to the person skilled in the art and can be applied to organic electroluminescence devices.

[0436] The application therefore also provides a method for producing an organic electronic device comprising the composition according to the application as described above or described as preferred, characterized in that at least one organic layer comprising the composition according to the application is applied by vapor deposition, in particular by a sublimation method and / or by an OVPD (organic vapor phase deposition) method and / or by means of carrier gas sublimation, or from a solution, in particular by spin coating or by a printing method.

[0437] In the process of manufacturing organic electronic devices by vapor deposition, in principle, there are two methods by which an organic layer comprising the composition of the present application and which can comprise a plurality of different components can be applied or deposited by vapor deposition to any substrate. First, the materials used can be initially charged into material sources each and finally evaporated from the different material sources ("co-evaporation"). Second, the various materials can be pre-mixed (pre-mix system) and the mixture can be initially charged into a single material source, from which it is finally evaporated ("pre-mix evaporation"). In this way, vapor deposition of a layer with a homogeneous distribution of components can be achieved in a simple and fast manner without the need for precise activation of a plurality of material sources.

[0438] The present application therefore also provides a process, characterized in that at least one compound of the formula (1) as described above or as described as preferred and at least one compound of the formula (2) as described above or as described as preferred are deposited from at least two material sources, optionally together with further materials as described above or as described as preferred, and form an organic layer.

[0439] In a preferred embodiment of the present application, the at least one organic layer is applied by vapor deposition, wherein the components of the composition are pre-mixed 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).

[0440] The present application therefore also provides a process, characterized in that a composition of the present application as described above or as described as preferred is used as a material source for the vapor deposition of a host system and, optionally together with further materials, forms an organic layer.

[0441] The present application also provides a method of manufacturing an organic electronic device comprising a composition of the present application as described above or described as preferred, characterized in that a formulation of the present application as described above is used for applying the organic layer.

[0442] The composition of the present application and the device of the present application are characterized by the following surprising advantages over the prior art:

[0443] The use of the composition of the present application in an organic electronic device, especially in an organic electroluminescent device, and especially in an OLED or OLEC leads to a significant increase in power efficiency and comparable or improved lifetime of the device.

[0444] However, as clearly shown in Example 1 introduced below, by using a compound of the prior art, such as compound SoA1, a good voltage but a relatively low power efficiency can be achieved at a low emitter concentration of 8% in the EML in Example VI.

[0445] The improvement in power efficiency and / or lifetime at comparable operating voltage can be achieved by a combination of a compound of formula (1) as described above with a compound of formula (2) as described above.

[0446] This improvement in power efficiency at comparable operating voltage can preferably be achieved by the inventive combination of a compound of formula (1) as described above with a compound of formula (2) as described above at an emitter concentration of 2 to 25 vol.%, preferably at an emitter concentration of 5 to 15 vol.%, more preferably at an emitter concentration of 7, 8 and 12 vol.% in the emitting layer.

[0447] For the specific combination, this improvement in power efficiency and lifetime at comparable operating voltage can preferably be achieved by the inventive combination of a compound of formula (1) as described above with a compound of formula (2) as described above at an emitter concentration of 2 to 25 vol.%, preferably at an emitter concentration of 5 to 15 vol.%, more preferably at an emitter concentration of 7, 8 and 12 vol.% in the emitting layer.

[0448] The compound of formula (1) represented by compound 4 differs from the prior art compound such as SoA1 in that a dibenzofuran is attached in position 8.

[0449] What could not be anticipated by the person skilled in the art is that this change in the position of the substituent leads to an improvement in the power efficiency of the electronic device, especially the power efficiency of the OLED, of about 10 to 30%, while having comparable or improved lifetime.

[0450] The compositions of the present application are very suitable for use in light-emitting layers and exhibit improved performance data compared to the compounds from the prior art as described above, especially in terms of lifetime, operating voltage and / or power efficiency.

[0451] The compositions of the present application can be easily processed and are thus very suitable for mass production in commercial use.

[0452] The compositions of the present application can be pre-mixed and vapor-deposited from a single material source, thus organic layers with a homogeneous distribution of the used components can be manufactured in a simple and fast way.

[0453] These above-mentioned advantages do not go along with a deterioration of further electronic properties of the electronic device.

[0454] It should be noted that variations of the embodiments described in the present application are encompassed by the scope of the present application. Unless explicitly excluded, each feature disclosed in the present application can be replaced by an alternative feature serving the same, or a similar, or an equivalent purpose. Thus, unless otherwise stated, each feature disclosed in the present application is to be considered an example of a generic series or equivalent or similar features.

[0455] All features of the present application can be combined with each other in any way, unless specific features and / or steps are mutually exclusive. This applies in particular to the preferred features of the present application. Likewise, features of non-essential combinations can be used individually (rather than in combination).

[0456] The technical teaching disclosed in relation to the present application can be refined and combined with other embodiments.

[0457] The present application is illustrated in more detail by the following examples, but is not intended to be limited thereby.

[0458] General methods:

[0459] Determination of the orbital energies and electronic states

[0460] The HOMO energy and LUMO energy and the triplet energy level and the singlet energy level of a material are determined via quantum chemical calculations. For this purpose, in the present case, the software package “Gaussian 09, Revision D.01” (Gaussian Inc.) is used. For the calculation of organic substances without metals (referred to as “org. method”), first a geometry optimization is carried out by means of the semi-empirical method AM1 (Gaussian input line “#AM1 opt”) with a charge of 0 and multiplicity of 1. Subsequently, based on the optimized geometry, an (single-point) energy calculation is carried out for the electronic ground state and the triplet energy 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, nstate=4)”)(charge 0, multiplicity 1). For organometallic compounds (referred to as “M-org.” method), the geometry is optimized by means of the Hartree-Fock method and the LanL2MB basis set (Gaussian input line “#HF / LanL2MB opt”)(charge 0, multiplicity 1). Analogous to for organic substances, the energy calculation is carried out as described above, with the exception that for the metal atom the “LanL2DZ” basis set is used and for the ligands the “6-31G(d)” basis set (Gaussian input line “#B3PW91 / gen pseudo=lanl2 td=(50-50, nstate=4)”). From the energy calculation, the HOMO is obtained as the last orbital occupied by two electrons (aocc. eigenvalue) and the LUMO as the first unoccupied orbital (avirt. eigenvalue) in Hartree, wherein HEhand LEhdenote the HOMO energy in Hartree and the LUMO energy in Hartree, respectively. This is used to determine the HOMO value and the LUMO value in electron volts calibrated by cyclic voltammetry measurements as follows:

[0461] HOMO(eV) = (HEh*27.212)*0.8308 - 1.118;

[0462] LUMO(eV) = (LEh*27.212)*1.0658 - 0.5049.

[0463] The triplet energy level T1 of a material is defined as the relative excitation energy (eV) of the triplet state having the lowest energy resulting from the quantum chemical energy calculation.

[0464] The singlet energy level S1 of a material is defined as the relative excitation energy (eV) of the singlet state having the second lowest energy resulting from the quantum chemical energy calculation.

[0465] The energetically lowest singlet state is referred to as S0.

[0466] The methods described herein are independent of the software package used and always give the same results. Examples of programs that are commonly used for this purpose are "Gaussian09" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem Inc.). In the present case, the energies were calculated using the software package "Gaussian09, revision D.01". DETAILED DESCRIPTION

[0467] Example 1 : Manufacture of OLEDs

[0468] The following examples E1 to E55 (see Table 6) provide the use of the inventive material combinations in OLEDs by comparison with examples V1 to V11.

[0469] Pre-treatment of examples V1 to E55: The glass plates coated with structured ITO (indium tin oxide) with a thickness of 50 nm were treated before coating, first with an oxygen plasma and then with an argon plasma. These plasma-treated glass plates formed the substrate to which the OLEDs were applied.

[0470] The OLEDs essentially had the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emitting layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally a cathode. The cathode was formed by an aluminum layer with a thickness of 100 nm. The precise structure of the OLEDs can be found in Table 6. The materials required for the manufacture of the OLEDs are shown in Table 8. The device data of the OLEDs are listed in Table 7. Examples V1, V2, V3, V10 and V11 are comparative examples with electron transport hosts according to prior art CN107973786. Examples V4, V5, V6 and V7 are comparative examples with hosts according to prior art WO 2015 / 014435. Examples V8 and V9 are comparative examples with hosts according to prior art KR20160046077. Examples E1 to E55 show the data of the inventive OLEDs.

[0471] All materials were applied by thermal vapor deposition in a vacuum chamber. In this case, the emitting layer always consisted of at least two matrix materials and an emitting dopant (emitter), which was added to one or more matrix materials in a specific volume ratio by co-evaporation. Details given in the form of e.g. SoA1 :40:TEG3 (32%:60%:8%) here mean that the material SoA1 is present in the layer in a proportion of 32% by volume, the compound 40 as co-host in a proportion of 60% by volume and TEG3 in a proportion of 8% by volume. Similarly, the electron transport layer can also consist of a mixture of two materials.

[0472] OLEDs were characterized in a standard way. For this purpose, electroluminescence spectra and current efficiency (SE, measured in cd / A) were measured as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) which exhibit Lambertian emission characteristics, and lifetime was measured. The electroluminescence spectra were determined at a luminance of 1000 cd / m 2 and the CIE 1931 x and y color coordinates were calculated therefrom. The parameter U10 in Table 7 refers to the voltage required at a current density of 10 mA / cm 2 . SE10 refers to the power efficiency obtained at 10 mA / cm 2 .

[0473] Lifetime LT is defined as the time after which the luminance has dropped to a certain fraction LI of the same initial luminance L0 during operation. The number LI = 80% in Table 7 means that the lifetime (in hours (h)) reported in the column LT corresponds to the time after which the luminance has dropped to 80% of its initial value.

[0474] In other words, for example, given L0 = 20 000 cd / m 2 , this would be the time at which the sample is sampled at a luminance of only LI = 0.8 x L0 = 16000 cd / m 2 .

[0475] Use of the mixtures of the application in OLEDs

[0476] The material combinations of the application can be used in the light-emitting layer in phosphorescent green OLEDs. As described in Table 6, the combinations of the application 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 with compounds 37, 38, 40, 41, 42, 43, 44, 47, 48, 49, 52, 56, 58, 60, 61, 62, 63, 64, 65, 66 or 66a are used as matrix materials in the light-emitting layer in Examples E1 to E55. When using the same emitter, the results from Table 7, for example VI with E1 or E1 with E4 or V2 with E2, are directly comparable.

[0477] For example, in comparing the examples of the application with the corresponding comparative examples, for example E1 with VI, E2 with V2, E3 with V3, E27 with V4, E28 with V5, E29 with V6, E30 with V7, E31 with V8, E32 with V9, E33 with E10 and E34 with V11, it is clear that the examples of the application each show a clear advantage in terms of lifetime.

[0478] Table 6: Structure of the OLED

[0479]

[0480]

[0481]

[0482]

[0483]

[0484]

[0485]

[0486]

[0487] Table 7: Data for OLEDs

[0488]

[0489]

[0490]

[0491] Table 8: Structural Formulas for Materials in OLEDs

[0492]

[0493]

[0494]

[0495]

[0496]

[0497]

[0498]

[0499]

[0500]

[0501] Example 2: Synthesis of Compounds

[0502] a) 2-{12-chloro-8-oxatricyclo[7.4.0.0 2,7 ]trideca-l(13),2(7),3,5,9,11-hexaen-3-yl}-4-{8-oxatricyclo[7.4.0.02,7 ]trideca-1 (9), 2, 4, 6, 10, 12-hexaen-3-yl}-6-phenyl-1, 3, 5-triazine

[0503]

[0504] trideca-1 (9), 2, 4, 6, 10, 12-hexaen-3-yl}-6-phenyl-1, 3, 5-triazine 2,7 ]trideca-1 (9), 2, 4, 6, 10, 12-hexaen-3-yl}-6-phenyl-1, 3, 5-triazine [CAS 1883265-32-4] and 44.5 g (420 mmol, 2.00 eq) sodium carbonate [CAS 497-19-8] were suspended in a mixture of 1000 ml dichloroethane [CAS 123-91-1], 1000 ml toluene [CAS 108-88-3] and 400 ml water. To the suspension 4.85 g (4.20 mmol / 0.02 eq) tetrakis(triphenylphosphine)palladium(0) [CAS 14221-01-3] were added and the reaction mixture was heated to reflux for 16 hours. After cooling the organic phase was removed, filtered over silica gel, washed with 200 ml water three times and concentrated to dryness. The yield was 79.1 g (151 mmol; 72% of theory). trideca-1 (9), 2, 4, 6, 10, 12-hexaen-3-yl}-6-phenyl-1, 3, 5-triazine [CAS 1883265-32-4] and 44.5 g (420 mmol, 2.00 eq) sodium carbonate [CAS 497-19-8] were suspended in a mixture of 1000 ml dichloroethane [CAS 123-91-1], 1000 ml toluene [CAS 108-88-3] and 400 ml water. To the suspension 4.85 g (4.20 mmol / 0.02 eq) tetrakis(triphenylphosphine)palladium(0) [CAS 14221-01-3] were added and the reaction mixture was heated to reflux for 16 hours. After cooling the organic phase was removed, filtered over silica gel, washed with 200 ml water three times and concentrated to dryness. The yield was 79.1 g (151 mmol; 72% of theory).

[0505] Instead of 1-boronyl-8-chlorodibenzofuran [CAS 162667-19-4] it is also possible to use 8-chloro-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzothiophene [CAS-2140848-96-8].

[0506] In a similar manner the following compounds can be obtained:

[0507]

[0508]

[0509]

[0510] b) 3-biphenyl-3-yl-9-[9-(4,6-diphenyl-[1,3,5]triazin-2-yl)-dibenzofuran-2-yl]-9H-carbazole

[0511]

[0512] To a solution of 21.4 g (42.7 mmol; 1.00 equiv) 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 equiv) 3-biphenyl-3-yl-9H-carbazole [CAS 1643526-99-1] and 7.82 g (81.4 mmol; 2.00 equiv) sodium tert-butoxide [CAS 865-47-4] in 500 ml o-xylene [CAS 95-47-6] 1.50 g (3.66 mmol; 9 mol%) bis(cyclohexyl)(2',6'-dimethoxybiphenyl-2-yl)phosphine (SPhos) [CAS 657408-07-6] and 1.12 g (1.22 mmol; 3 mol%) tris(dibenzylideneacetone)dipalladium [CAS 51364-51-3] were added and the reaction mixture was heated to reflux for 16 h. The reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. The obtained solid was washed with 300 ml ethanol and recrystallized repeatedly from a mixture of heptane and xylene. By Alox hot filtration followed by sublimation under high vacuum 21.1 g (29.5 mmol; 69%) of the purified product was obtained as a colorless solid.

[0513] In a similar manner the following compounds can be obtained:

[0514]

[0515]

[0516]

[0517]

[0518]

[0519]

[0520]

Claims

1. A composition comprising at least one compound of formula (1) and at least one compound of formula (2f), (2j), (2k) or (2l), wherein the symbols and indices used are as follows: X1is N; X is C and o is 4 and p is 4; or X is C and both adjacent X are bound to the ring system of formula A and o is 2, q is 4 and p is 4 or o is 4, q is 4 and p is 2, wherein * is in each case the point of attachment to X, aryl is Ar-1 to Ar-24: Y is selected from O or S; n and m are independently in each case 0, 1, 2 or 3, Y 1 is selected from NAr1, C(R*)2, O and S; Y 3 is O, S or C(CH3)2; r is independently in each case 0, 1, 2 or 3; L is identical or different at each occurrence and is a single bond or an aromatic ring system having 6 to 30 aromatic ring atoms, which can be substituted by one or more R 5 groups; n is 0, 1, 2, 3, 4, 5 or 6; and R1is H, F, Cl, Br, I, CN, NCO, NCS, NO2, CF3, O s is independently in each case 0, 1, 2, 3 or 4; Ar1is independently at each occurrence a substituted or unsubstituted aryl or heteroaryl group having 5 to 40 aromatic ring atoms, which can be substituted with one or more R 3 groups; and n is 1, 2, 3, 4, 5, or 6. R B is Ar3; Ar3is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 10 to 40 aromatic ring atoms, which aromatic ring system or heteroaromatic ring system can be substituted by one or more R 3 groups; R * in each case identical or different and are linear alkyl radicals having 1 to 10 carbon atoms or aryl radicals having 6 to 12 carbon atoms, where two substituents R * together can form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, which can be substituted by one or more substituents R 5 ; R, R 1 , R 2 in each case are identical or different and are selected from the group consisting of H, D, F, Cl, Br, I, CN, NO2, 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 with 1 to 20 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 carbon atoms or alkenyl group with 2 to 20 carbon atoms, each of which can be substituted by one or more R 3 groups, where one or more non-adjacent CH2 groups can be replaced by R 3 C=CR 3 , Si(R 3 )2, C=O, C=S, C=NR 3 , P(=O)(R 3 ), SO, SO2, NR 3 , O, S or CONR 3 , and where one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms which can in each case be substituted by one or more R 3 groups, an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms which can be substituted by one or more R 3 groups, or an aralkyl or heteroaralkyl group with 5 to 40 aromatic ring atoms which can be substituted by one or more R 3 groups; and two substituents R and / or R 1 and / or R 2 bonded to adjacent carbon atoms optionally can form a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more R 3 groups. R 3 in each case identical or different and are selected from the group consisting of H, D, F, CN, N(Ar)2, an aliphatic hydrocarbon group having from 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms can be replaced by D, F, Cl, Br, I or CN and which aromatic or heteroaromatic ring system can be substituted by one or more alkyl groups each having from 1 to 4 carbon atoms; and two or more adjacent R 3 The substituents can together form a mono- or polycyclic aliphatic ring system; R 4 are identical or different in each occurrence and are selected from H, D, F, CN, an aliphatic hydro- gen group 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 can be replaced by D, F, Cl, Br, I, a linear or branched alkyl group having 1 to 4 carbon atoms, or CN; while two or more adjacent R 4 substituents can together form a mono- or polycyclic ring system; R 5 are identical or different in each case and are selected from D, F, CN and aryl groups having 6 to 18 carbon atoms; while two or more adjacent substituents R 5 may together form a mono- or polycyclic aliphatic ring system; Ar is identical or different at each occurrence and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which can be substituted by one or more non-aromatic R 3 groups; also two Ar groups which are bound to the same nitrogen atom, phosphorus atom or boron atom can be bridged to one another by a single bond or a bridging group selected from N(R 3 ), C(R 3 )2, O or S; and and u, v and w are independently in each case 0 or 1. Y in formula (1) is O. Z is C(R 3 )2, N-Ar, O or S, and t is 1, the compound of formula (2f), (2j), (2k) or (2l) is selected from the group consisting of the following compounds:

2. The composition of claim 1, wherein 4. The composition according to claim 1 or 2, wherein the compound of formula (1) is selected from the group consisting of compounds of formula (1b) to (1h), 3. The composition according to claim 1 or 2, characterized in that 5. The composition according to claim 1 or 2, wherein the compound of formula (1) is selected from the group consisting of the following compounds: 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-type dopants and p-type dopants. wherein Y, Y 1 , L, Ar1and R 1 have the definitions given in claim 1 or 2. the composition consists of the compound of formula (1) and the compound of formula (2f), (2j), (2k) or (2l).

6. The composition according to claim 1 or 2, characterized in that 8. A formulation comprising the composition according to any one of claims 1 to 7 and at least one solvent.

7. The composition according to claim 1 or 2, characterized in that 9. Use of the composition according to any one of claims 1 to 7 in an organic electronic device. the organic electronic device is selected from the group consisting 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. An organic electronic device comprising at least one composition according to any one of claims 1 to 7 in at least one organic layer.

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

12. The device of claim 11, wherein ​ 13. The device of claim 11 or 12, wherein ​ 14. The device of claim 11 or 12, wherein The device comprises the composition according to any one of claims 1 to 5 in the light-emitting layer (EML), in the electron-transporting layer (ETL), in the electron-injection layer (EIL) and / or in the hole-blocking layer (HBL).

15. A device according to claim 13 comprising an anode, a cathode and at least one organic layer comprising at least one light-emitting layer, characterised in that The device contains the composition according to any one of claims 1 to 7 in the at least one light-emitting layer and a phosphorescent emitter.

16. A method for manufacturing a device according to claim 11 or 12, characterized by At least one organic layer comprising the composition according to any one of claims 1 to 7 is applied by vapor deposition or from solution.

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