Materials for organic electroluminescent devices

Abstract

The present invention relates to diaza-dibenzofuran and diaza-dibenzothiophene derivatives and to electronic devices containing said compounds, in particular organic electroluminescent devices containing said compounds in the form of a triplet host material, optionally in combination with other triplet host materials and suitable phosphorescent emitters, the invention also relates to suitable mixtures and formulations.

Description

Technical Field

[0001] The present invention relates to diazadibenzofuran derivatives and diazadibenzothiophene derivatives and electronic devices containing the compounds, in particular organic electroluminescent devices containing the compounds as triplet matrix materials, optionally in combination with other triplet matrix materials and suitable phosphorescent emitters, and also to suitable mixtures and preparations. Background Art

[0002] Phosphorescent organometallic complexes are often used in organic electroluminescent devices (OLEDs). In general, OLEDs still need to be improved, for example in terms of efficiency, operating voltage and lifetime. The properties of phosphorescent OLEDs are not only determined by the triplet emitters used. More particularly, other materials used, such as matrix materials, are also of particular importance here. Therefore, improvements to these materials can also lead to significant improvements in OLED properties.

[0003] According to the prior art, matrix materials for phosphorescent emitters include carbazole derivatives, dibenzofuran derivatives, indenocarbazole derivatives, indolocarbazole derivatives, benzofuranocarbazole derivatives and benzothienocarbazole derivatives.

[0004] WO 2019 / 190239 A1, WO 2019 / 190241 A1, KR 20200136072 A and KR 20220063428 A describe specific diazadibenzofuran or diazadibenzothiophene derivatives as matrix materials.

[0005] CN 114560864 A describes specific diazadibenzofuran or diazadibenzothiophene derivatives as electron-transport materials.

[0006] In general, there is still a need to improve these materials for use as matrix materials. The problem to be solved by the present invention is to provide improved compounds which are particularly suitable for use as matrix materials in phosphorescent OLEDs. More particularly, it is an object of the present invention to provide matrix materials with an extended lifetime. This is especially true for the use of low to medium emitter concentrations, i.e. emitter concentrations in the range of 3% to 20%, in particular in the range of 3% to 15%, since the device lifetime is particularly limited here.

[0007] It has now been found that electroluminescent devices containing compounds of the following formula (1) are improved over the prior art, in particular when said compounds are used as host materials for phosphorescent dopants.

[0008] It has also been found that this problem can be solved and the disadvantages of the prior art can be eliminated by combining at least one compound of formula (1) as a first host material with at least one hole-transporting compound, for example, with one or more compounds of formula (6), (7), (8), (9), (10) or (11) as other host materials for use in the light-emitting layer of an organic electronic device, especially an organic electroluminescent device. Summary of the invention

[0009] The present invention first provides a compound of formula (1),

[0010]

[0011] Formula (1),

[0012] The symbols and notations used are as follows:

[0013] Y is independently at each occurrence N, C-[L]b-Ar2 or C-[L]b1-Ar3, wherein exactly two Y are N separated by a C-[L]b-Ar2 or C-[L]b1-Ar3 group;

[0014] V is O or S;

[0015] Het satisfies one of the equations (1-2), (1-3), (1-4) and (1-5),

[0016]

[0017] * indicates the connection with the rest of formula (1),

[0018] R 1 are, in each case identical or different and independently, H, D or phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl which is undeuterated or partially or fully deuterated;

[0019] Ar, Ar1 are identical or different in each case and are ring atoms having 5 to 40 atoms and may be replaced by one or more R 2 group-substituted aromatic or heteroaromatic ring systems;

[0020] Ar2, Ar3 are in each case identical or different and are an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, which may each be replaced by one or more R 2 group substitution;

[0021] R 2are in each case identical or different and are selected from: D, F, CN, a straight-chain alkyl radical having 1 to 20 carbon atoms or a branched or cyclic alkyl radical having 3 to 20 carbon atoms, in which one or more non-adjacent CH2 groups may be replaced by O or S and in which one or more hydrogen atoms may be replaced by D, F or CN;

[0022] R#, when present, is D or phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl which is undeuterated or partially or fully deuterated;

[0023] [L] is an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, which may be unsubstituted or partially or fully substituted by D;

[0024] b, b1, and b2 are each independently 0 or 1.

[0025] The present invention also provides a mixture comprising at least one compound of formula (1) as described above or preferably described later and at least one further compound selected from matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0026] The invention also provides a preparation comprising at least one compound of the formula (1) as described above or preferably described later or a mixture as described above and at least one solvent.

[0027] The present invention also provides an organic electronic device, preferably an electroluminescent device, comprising an anode, a cathode and at least one organic layer comprising at least one compound of the formula (1) as described above or preferably described later.

[0028] The invention further provides a method for producing an organic electronic device, preferably an electroluminescent device, as described above or preferably hereinafter, characterized in that the organic layer is applied by vapor deposition or from solution. DETAILED DESCRIPTION

[0029] In this patent application, "D" or "D atom" refers to deuterium.

[0030] The aryl groups in the context of the present invention contain 6 to 40 ring atoms, preferably carbon atoms. The heteroaryl groups in the context of the present invention contain 5 to 40 ring atoms, wherein the ring atoms include carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is up to at least 5. The heteroatoms are preferably selected from N, O and / or S. The aryl group or heteroaryl group here refers to: a simple aromatic ring derived from benzene, i.e. phenyl; or a simple heteroaromatic ring derived from pyridine, pyrimidine or thiophene, for example; or a fused aryl or heteroaryl group derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline. Therefore, the aryl group with 6 to 18 carbon atoms is preferably phenyl, naphthyl, phenanthryl or terphenylidene, and there is no restriction on the connection of the aryl group as a substituent. The aryl or heteroaryl group in the context of the present invention may carry one or more groups, wherein suitable groups are as described below. If such a group is not described, the aryl group or heteroaryl group is unsubstituted.

[0031] Aromatic ring systems in the context of the present invention contain 6 to 40 carbon atoms in the ring system.Aromatic ring systems also include aryl groups as described above.

[0032] The aromatic ring system having 6 to 18 carbon atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthrenyl and terphenylidene.

[0033] The heteroaromatic ring system in the context of the present invention contains 5 to 40 ring atoms and at least one heteroatom. Preferred heteroaromatic ring systems have 9 to 40 ring atoms and at least one heteroatom. Heteroaromatic ring systems also include heteroaryl groups as described above. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O and / or S.

[0034] Aromatic or heteroaromatic ring systems in the context of the present invention refer to systems which do not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of non-H atoms), such as carbon atoms or oxygen atoms or carbonyl groups. For example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, 9,9-dialkylfluorene, diaryl ether, stilbene, etc. should therefore also be regarded as aromatic or heteroaromatic ring systems in the context of the present invention, and similarly, systems in which two or more aryl groups are interrupted by, for example, linear or cyclic alkyl groups or by silyl groups should also be regarded as aromatic or heteroaromatic ring systems. In addition, systems in which two or more aryl or heteroaryl groups are directly bonded to each other, such as biphenyl, terphenyl, quaterphenyl or bipyridine, are also included in the definition of aromatic or heteroaromatic ring systems.

[0035] An aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may be attached to the aromatic or heteroaromatic ring system via any position is understood as meaning, for example, a radical derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, pyrene, lettuce, perylene, fluoranthene, benzofluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylylidene, terphenyl, biphenylylidene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, trimerized indene, isotrifluorene, or a combination thereof. Polyindene, spirotrimer indene, spiroisotrimer indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenazine, pyrazole, indazole, imidazole, benzimidazole, naphthymidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoximidazole, oxadiazole, benzooxadiazole, naphthooxadiazole, anthraoxadiazole, phenanthraoxadiazole, isoxadiazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenazine, phenothiazine, fluorescein ring, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3- Triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0036] The abbreviations Ar and Ar1 are in each case identical or different and refer to a ring having 5 to 40 ring atoms and which may be replaced by one or more R 2 Aromatic or heteroaromatic ring system substituted with a radical, wherein R 2 Group or substituent R 2 The definition of is as described above or below. The preferred definitions of Ar and Ar1 are as described below.

[0037] The abbreviations Ar2 and Ar3 refer, independently in each case, to an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, which may be replaced by one or more R 2 Group substitution, where R 2Group or substituent R 2 Ar2 and Ar3 are preferably defined as follows.

[0038] The abbreviation Ar5 is identical or different in each case and is a ring having 5 to 40 ring atoms and may be replaced by one or more R 7 Aromatic or heteroaromatic ring system substituted with a radical, wherein R 7 Group or substituent R 7 The definition of Ar5 is as described above or below. The preferred definition of Ar5 is as described below.

[0039] In the context of the present invention, a cyclic alkyl, alkoxy or thioalkyl group refers to a monocyclic, bicyclic or polycyclic group.

[0040] In the context of the present invention, a linear, branched or cyclic C1- to C 20 An alkyl radical is to be understood as meaning, for example, 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-hexan-1-yl, 1,1-dimethyl-n-heptan-1-yl, 1,1-dimethyl -n-octyl, 1,1-dimethyl-n-decyl, 1,1-dimethyl-n-dodecyl, 1,1-dimethyl-n-tetradecyl, 1,1-dimethyl-n-hexadecyl, 1,1-dimethyl-n-octadecyl, 1,1-diethyl-n-hexyl, 1,1-diethyl-n-heptyl, 1,1-diethyl-n-octyl, 1,1-diethyl-n-decyl, 1-(n-propyl)-cyclohexan-1-yl, 1-(n-butyl)-cyclohexan-1-yl, 1-(n-hexyl)-cyclohexan-1-yl, 1-(n-octyl)-cyclohexan-1-yl and 1-(n-decyl)-cyclohexan-1-yl.

[0041] The expression that two or more radicals can together form a ring system means that an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system is formed and, in the context of the present specification, it shall in particular mean that the two radicals are linked to one another via a chemical bond and formally eliminate two hydrogen atoms. This is illustrated by the following scheme:

[0042] .

[0043] However, in addition, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group is bound to the position where the hydrogen atom is bound, thereby forming a ring. This will be illustrated by the following scheme:

[0044] .

[0045] The compounds of the formula (1) and preferred embodiments thereof are described below. The preferred embodiments also apply to the mixtures according to the invention, the preparations according to the invention and the organic electroluminescent devices according to the invention.

[0046] In the compounds of formula (1), Y is independently N, C-[L] b -Ar2 or C-[L] b1 -Ar3, wherein exactly two Y are C-[L] b -Ar2 or C-[L] b1 -Ar3 groups separated by N.

[0047] A preferred embodiment of the compound of formula (1) is a compound of formula (1a) or (1b) wherein the positions of the two nitrogen atoms are more specifically described and the remaining Y is C-[L] b -Ar2 and C-[L] b1 -Ar3, and the symbols used are V, [L], Ar2, Ar3, b, b1, Het, R 1 , R# and b2 have the definitions given above or preferably given below:

[0048]

[0049] Formula (1a),

[0050]

[0051] Formula (1b).

[0052] The present invention therefore also provides compounds of the formulae (1a) and (1b) as described above or as preferably described hereinafter.

[0053] In the compounds of formula (1), formula (1a) and formula (1b), Het preferably represents formula (1-2). In formulas (1-2) to (1-5), R1 H or D is preferred.

[0054] In the compound of formula (1a), Het is preferably bonded to the 9-position of diazadibenzofuran or diazadibenzothiophene.

[0055] In the compound of formula (1b), Het is preferably bonded to the 5-position of diazadibenzofuran or diazadibenzothiophene.

[0056] The numbering of the positions is shown by way of example below for the diazadibenzofuran basic skeleton:

[0057] .

[0058] In the compounds of formula (1), (1a) and (1b), V is preferably O.

[0059] In the compounds of formula (1), (1a) and (1b), R 1 Preferably it is H or D, and more preferably it is H.

[0060] In the compounds of formula (1), (1a) and (1b), R#, when present, is preferably D or undeuterated or partially or fully deuterated phenyl, more preferably D.

[0061] In the compounds of formula (1), (1a) and (1b), b2 is preferably 0.

[0062] In the compounds of the formulae (1), (1a) and (1b) or in the compounds of the formulae (1), (1a) and (1b) to which preference is given, the symbol [L] is a linker for an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, which may be unsubstituted or partially or fully substituted by D.

[0063] In the compounds of formula (1), (1a) and (1b) or the compounds of formula (1), (1a) and (1b) mentioned preferably, the symbol [L], when it occurs, is independently in each case preferably a linker selected from L-1 to L-34, which may be unsubstituted or partially or fully substituted by D,

[0064]

[0065]

[0066] wherein V1 is independently O, S or N-aryl in each case, the dotted line represents the connection to Ar2 or Ar3 and the remainder of formula (1), (1a) or (1b), wherein the abbreviation "aryl" means a radical having 5 to 30 ring atoms and being substituted by one or more R 2Aromatic or heteroaromatic ring systems substituted with radicals. "Aryl" is preferably phenyl, 1,3-biphenyl, 1,4-biphenyl, dibenzofuranyl or dibenzothiophenyl, wherein these radicals may be unsubstituted or partially or completely substituted by D. V1 is preferably O or N-aryl. V1 is more preferably O.

[0067] In the compounds of formula (1), (1a) and (1b) or the preferred compounds of formula (1), (1a) and (1b), the symbol [L] when it occurs is independently more preferably a linker selected from L-2, L-3, L-4, L-5, L-21 to L-34 as described above or preferably described, which can be partially or completely substituted by D.

[0068] In the compounds of the formulae (1), (1a) and (1b) or in the compounds of the formulae (1), (1a) and (1b) mentioned as being preferred, b is preferably 0.

[0069] In the compounds of the formulae (1), (1a) and (1b) or in the compounds of the formulae (1), (1a) and (1b) mentioned as being preferred, b1 is preferably 0.

[0070] In the compounds of the formulae (1), (1a) and (1b) or in the compounds of the formulae (1), (1a) and (1b) mentioned as being preferred, Ar and Ar1 are preferably different.

[0071] Ar and Ar1 are each independently preferably selected from the following groups Ar-1 to Ar-17:

[0072]

[0073]

[0074] wherein R' is identical or different in each case and is selected from: H, D, F, Cl, Br, I, CN, NO2, N(Ar0)2, NH2, N(R 2 )2, C(=O)Ar0, C(=O)H, C(=O)R 2 , P(=O)(Ar0)2, a linear alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be replaced by one or more R 2 group, wherein one or more non-adjacent CH2 groups may be substituted by HC=CH, R 2 C=CR 2 、C≡C、Si(R 2 )2、Ge(R 2 )2、Sn(R 2)2. C=O, C=S, C=Se, C=NR 2 、P(=O)(R 2 ), SO, SO2, NH, NR 2 , O, S, CONH, or CONR 2 wherein one or more hydrogen atoms may be replaced by F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each of which may be replaced by one or more R 2 A group substituted with 5 to 40 ring atoms and may be substituted with one or more R 2 substituted aryloxy or heteroaryloxy groups, or combinations of these systems, in which two or more adjacent substituents R' may optionally form a substituted aryloxy or heteroaryloxy group which may be substituted by one or more R 2 a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system substituted with radicals;

[0075] and

[0076] Ar0 is identical or different in each case and is a ring having 5 to 40 atoms and may be replaced by one or more R 2 At the same time, one or more R' can also be directly bonded to the carbon atom of Ar0.

[0077] Dashed lines indicate the bonding sites to the remainder of formulae (1-2), (1-3), (1-4), and (1-5).

[0078] More preferably, Ar or Ar1 is each independently Ar-1, Ar-2, Ar-6, Ar-11 and Ar-17, wherein R' has the definition given above or as preferably specified below.

[0079] R′ in the substituents of the formulae Ar-1 to Ar-17 as described above is preferably selected from H, D, CN and a cyclopentane radical having 5 to 40 aromatic ring atoms and in each case being replaceable by one or more R 2 Aromatic or heteroaromatic ring systems substituted with radicals.

[0080] Ar0 in the substituents of the formulae Ar-13 to Ar-16 as described above is preferably phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl, which may optionally be partially or fully deuterated.

[0081] In the compounds of formula (1), (1a) and (1b) or the compounds of formula (1), (1a) and (1b) described preferably, Ar2 and Ar3 are each independently an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, which may be replaced by one or more R 2 Group substitution.

[0082] In the compounds of the formulae (1), (1a) and (1b) or in the compounds of the formulae (1), (1a) and (1b) mentioned as being preferred, Ar2 and Ar3 are preferably different.

[0083] Ar2 and Ar3 are each independently preferably selected from the group consisting of Ar-1 to Ar-17 as described above or as preferably described, wherein the dotted line indicates the bonding site to [L] or the remainder of formula (1), (1a) and (1b).

[0084] In the compounds of formula (1), (1a) and (1b) or the compounds of formula (1), (1a) and (1b) described preferably, Ar2 and Ar3 are each independently more preferably phenyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl, terphenylidene, fluoranthene, dibenzofuranyl, indenocarbazole-N-yl, N-arylindolecarbazole-N-yl, carbazole-N-yl or aryl-N-carbazole, which may be replaced by one or more R 2 substituted with a radical, wherein aryl has the meaning given above and R 2 has the meaning given above or below. If the substituents Ar2 or Ar3 as described above are replaced by one or more R 2 If the group is substituted, then R 2 Preferably, it is independently selected from D, F or CN at each occurrence, more preferably D.

[0085] In the compounds of formula (1), (1a) and (1b) or the compounds of formula (1), (1a) and (1b) described preferably, Ar2 and Ar3 are each independently most preferably phenyl, 1,4-biphenyl or dibenzofuranyl, which may be partially or fully deuterated.

[0086] In a preferred embodiment of the compounds of formula (1), (1a) and (1b), these compounds are partially or fully deuterated, more preferably fully deuterated.

[0087] Examples of suitable host materials of formula (1), (1a) and (1b) as described above or preferably are the structures shown in Table 1 below.

[0088] Table 1:

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] Particularly suitable compounds of the formula (1), (1a) and (1b) as described above or as preferred are compounds E1 to E27 in Table 2.

[0100] Table 2:

[0101]

[0102]

[0103]

[0104] The compounds of the present invention can be prepared by synthetic procedures known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, and the like.

[0105] Suitable compounds having a diazadibenzofuran or diazadibenzothiophene group are commercially available in many cases, and the starting compounds detailed in the examples can be obtained by known methods, so reference is made to these methods.

[0106] In the following synthetic schemes, compounds are shown as having a small amount of substituents to simplify the structure. This does not exclude the presence of any desired other substituents in the method. The methods shown for synthesizing the compounds of the present invention should be considered as exemplary. Those skilled in the art will be able to develop alternative synthetic routes within the scope of their common knowledge in this area.

[0107] Scenario 1:

[0108]

[0109] Scenario 2:

[0110]

[0111] Scheme 3: Ar and Ar' correspond to Ar2 and Ar3 in the compound of formula (1)

[0112]

[0113] Scheme 4: Ar and Ar' correspond to Ar2 and Ar3 in the compound of formula (1)

[0114]

[0115] Solution 5:

[0116]

[0117] Scheme 6: In a representative manner for all Schemes 1 to 5, Scheme 6 shows the reaction with Het-B(OH)2.

[0118]

[0119] Detailed reaction conditions are known in the art or are described in the Examples section.

[0120] By these methods, if necessary, purification such as recrystallization or sublimation can be followed to obtain high purity, preferably higher than 99% (by 1 H NMR and / or HPLC).

[0121] In order to process the compound of the present invention from liquid phase, for example, by spin coating or by printing, the preparation of the compound of the present invention or the mixture of the compound of the present invention with other functional materials such as host materials, fluorescent emitters, phosphorescent emitters and / or emitters showing TADF is required. These preparations can be, for example, solutions, dispersions or emulsions. For this reason, a mixture of two or more solvents can be preferably used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fennel, 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, α-terpineol, benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexyl Benzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate, or a mixture of these solvents.

[0122] The compounds of the formula (1) according to the invention as described above or preferably are suitable for use in organic electroluminescent devices, in particular as matrix materials.

[0123] When the compound of the present invention is used as a matrix material or, synonymously, as a host material in a light-emitting layer, it is preferably used in combination with other compounds.

[0124] Therefore, the present invention also provides a mixture comprising at least one compound of formula (1) or at least one preferred compound of one of formulas (1), (1a) and (1b) or a compound from Table 1 or one of compounds E1 to E27 and at least one other compound selected from a matrix material, a phosphorescent emitter, a fluorescent emitter and / or an emitter exhibiting TADF (thermally activated delayed fluorescence). Suitable matrix materials and emitters that can be used in such a mixture according to the present invention are described below.

[0125] The present invention further provides a preparation comprising at least one compound of the present invention as described above or a mixture of the present invention as described above and at least one solvent. The solvent may be the above solvent or a mixture of these solvents.

[0126] The present invention also provides an organic electronic device comprising an anode, a cathode and at least one organic layer, wherein the organic layer comprises at least one compound of formula (1) or at least one preferred compound of one of formulas (1), (1a) and (1b) or a compound from Table 1 or one of compounds E1 to E27.

[0127] The organic electronic device may for example be selected from organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic photodetectors, organic photoreceptors.

[0128] The organic electronic device is preferably an organic electroluminescent device.

[0129] The organic electroluminescent device of the present invention (synonymous with organic electroluminescent device) is, for example, an organic light emitting transistor (OLET), an organic field quenching device (OFQD), an organic light emitting electrochemical cell (OLEC), an organic laser diode (O-laser) or an organic light emitting diode (OLED). The organic electroluminescent device of the present invention is especially an organic light emitting diode or an organic light emitting electrochemical cell. The device of the present invention is more preferably an OLED.

[0130] The organic layer of the device of the present invention preferably comprises a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), an exciton blocking layer, an electron blocking layer and / or a charge generation layer in addition to the light-emitting layer (EML). The device of the present invention may also comprise two or more layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL and HBL. Similarly, for example, an intermediate layer having an exciton blocking function may be introduced between two light-emitting layers.

[0131] If there are multiple emitting layers, it is preferred that these emitting layers generally have several luminescence peaks between 380 nm and 750 nm, so that the overall result is white luminescence; in other words, a variety of luminescent compounds that can fluoresce or phosphoresce are used in the luminescent layer. Two or more fluorescent and / or phosphorescent compounds may also be present in the luminescent layer. Particularly preferred is a system with three luminescent layers, wherein the three layers exhibit blue, green and orange or red luminescence. As an alternative to the above combination, the luminescent layer may also exhibit yellow luminescence. Such combinations are known to those skilled in the art. The organic electroluminescent device of the present invention may also be a tandem electroluminescent device, in particular an OLED for emitting white light.

[0132] The device may also comprise inorganic materials or layers formed entirely of inorganic materials.

[0133] For a person skilled in the art, there is no difficulty in considering a variety of materials known in the prior art to select materials suitable for use in the above-mentioned layers of an organic electroluminescent device. A person skilled in the art will consider the chemical and physical properties of the materials in a conventional manner here, because he knows that the materials interact with each other in an organic electroluminescent device. This involves, for example, the energy levels of the orbitals (HOMO, LUMO) or triplet and singlet energy levels, and also other material properties.

[0134] The compounds of formula (1) of the present invention as described above or preferably described can be used in different layers according to the exact structure. Preferably, the organic electroluminescent device comprises the compound of formula (1) or the above preferred embodiment in the light-emitting layer as a matrix material of a fluorescent light emitter, a phosphorescent light emitter or a light emitter exhibiting TADF (thermally activated delayed fluorescence), especially a matrix material of a phosphorescent light emitter. In addition, the compounds of the present invention can also be used in an electron transport layer and / or a hole transport layer and / or an exciton blocking layer and / or a hole blocking layer. It is particularly preferred to use the compounds of the present invention as a matrix material in a light-emitting layer or as an electron transport material or a hole blocking material in an electron transport layer or a hole blocking layer.

[0135] The present invention also provides an organic electronic device as described above, wherein the organic layer comprises at least one light-emitting layer, the light-emitting layer comprising at least one compound of formula (1) or at least one preferred compound of one of formulas (1), (1a) and (1b) or a compound from Table 1 or one of compounds E1 to E27.

[0136] In one embodiment of the invention, for the devices according to the invention, further matrix materials are selected in the light-emitting layer and used together with the compounds of the formula (1) as described above or preferably or together with the compounds or compounds E1 to E27 from Table 1.

[0137] Therefore, the present invention also provides an organic electronic device as described above, wherein the organic layer comprises at least one emitting layer, which comprises at least one compound of formula (1) or at least one preferred compound of one of formulas (1), (1a) and (1b) or a compound from Table 1 or one of compounds E1 to E27 and other matrix materials.

[0138] Suitable matrix materials that can be used in combination with the compounds of the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, biscarbazoles, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, borazol or boric esters, triazine derivatives, zinc complexes, siladiazacyclopenta or siladiazacyclopenta derivatives, phosphadiazacyclopenta derivatives, bridged carbazole derivatives, terphenylidene derivatives or dibenzofuran derivatives. Likewise, other phosphorescent emitters having a shorter emission wavelength than the actual emitter may be present in the mixture as co-hosts, or compounds that participate in charge transport but not to a significant extent, such as wide bandgap compounds, may be present.

[0139] A wide bandgap material herein refers to a material within the disclosure of US 7,294,849, characterized by a bandgap of at least 3.5 eV, the bandgap being the gap between the energies of the HOMO and the LUMO of the material.

[0140] Particularly suitable matrix materials for advantageous combination with the compounds of the formula (1) as described above or preferably in mixed matrix systems can be selected from compounds of the formula (6), (7), (8), (9), (10) or (11) as described below.

[0141] The present invention therefore also provides an organic electronic device comprising an anode, a cathode and at least one organic layer comprising at least one emitting layer, wherein the at least one emitting layer comprises as matrix material 1 at least one compound of the formula (1) as described above or preferably described and as matrix material 2 at least one compound of the formula (6), (7), (8), (9), (10) or (11),

[0142]

[0143] Formula (6):

[0144]

[0145] Formula (7),

[0146]

[0147] Formula (8),

[0148]

[0149] Formula (9):

[0150]

[0151] The symbols and notations used are as follows:

[0152] A 1 C(R 7 )2. NR 7 , O or S;

[0153] L is a bond, O, S, C (R 7 )2 or NR 7 ;

[0154] A is independently in each case a radical of the formula (3) or (4),

[0155]

[0156] X2 is identical or different in each case and is CH, CR 6 or N, where no more than 2 symbols X2 may be N;

[0157] * represents the bonding site with formula (9);

[0158] U 1 , U 2 When present, it is a key, O, S, C (R 7 )2 or NR 7 ;

[0159] R 6 are in each case identical or different and are: D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 7 groups and one or more non-adjacent CH2 groups may be replaced by Si(R7 )2. C=O、NR 7 , O, S or CONR 7 or have 5 to 60 ring atoms and may be replaced by one or more R 7 Aromatic or heteroaromatic ring system substituted with a radical; wherein the two R 6 The groups may also together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;

[0160] Ar5 is the same or different in each occurrence and is independently a ring having 5 to 40 ring atoms and may be replaced by one or more R 7 group-substituted aromatic or heteroaromatic ring systems;

[0161] R 7 are identical or different in each case and are: D, F, Cl, Br, I, N(R 8 )2,CN,NO2,OR 8 , SR 8 ,Si(R 8 )3,B(OR 8 )2,C(=O)R 8 ,P(=O)(R 8 )2,S(=O)R 8 ,S(=O)2R 8 ,OSO2R 8 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 8 group, wherein one or more non-adjacent CH2 groups may be replaced by Si(R 8 )2. C=O, NR 8 , O, S or CONR 8 or have 5 to 40 ring atoms and may be replaced by one or more R 8 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two or more R 7 The groups may together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; preferably, R 7 The groups do not form any such ring systems;

[0162] R 8 are in each case identical or different and are: H, D, F, or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in particular a hydrocarbon radical, in which one or more hydrogen atoms may also be replaced by F;

[0163] c, c1, c2 are each independently 0 or 1, wherein the sum of the indices c+c1+c2=1 in each case;

[0164] d, d1, d2 are each independently 0 or 1, wherein the sum of the indices d+d1+d2=1 in each case;

[0165] q, q1, q2 are each independently 0 or 1;

[0166] s is the same or different in each case and is 0, 1, 2, 3 or 4;

[0167] t is the same or different in each case and is 0, 1, 2 or 3;

[0168] u is the same or different in each case and is 0, 1, or 2;

[0169] u1, u2 are each independently 0 or 1, wherein the sum u1+u2=1; and

[0170] v is 0 or 1.

[0171] In the compound of formula (6), (7), (8), (10) or (11), when R 6 When the group is not D, s is preferably 0 or 1, or more preferably 0.

[0172] In the compound of formula (6), (7) or (8), when R 6 When the group is not D, t is preferably 0 or 1, or more preferably 0.

[0173] In the compound of formula (6), (7), (8) or (10), when R 6 When the group is not D, u is preferably 0 or 1, or more preferably 0.

[0174] In the compounds of the formulae (6), (7), (8), (10) and (11), the sum of the indices s, t and u is preferably not more than 6, particularly preferably not more than 4, and even more preferably not more than 2. 6 When it is not D, it is preferred to do so.

[0175] In the compounds of the formula (9), c, c1, c2 are each independently 0 or 1, wherein the sum of the indices c+c1+c2 is 1 in each case. c2 is preferably defined as 1.

[0176] In the compound of formula (9), L is preferably a single bond or C(R 7 )2, where R 7 has the definitions given above; more preferably, L is a single bond.

[0177] In formula (4), U 1 or U 2 Where present, it is preferably a single bond or C(R 7 )2, where R 7 has the definition given above; more preferably, U 1 or U 2 When present, it is a single key.

[0178] In a preferred embodiment of the compounds of formulae (6), (7), (8), (9), (10) and (11) which can be combined with the compound of formula (1) above according to the present invention, R 6 are identical or different in each case and are selected from: D, F, CN, a straight-chain alkyl radical having 1 to 20 carbon atoms or a branched or cyclic alkyl radical having 3 to 20 carbon atoms, where the alkyl radical may be replaced by one or more R 7 or have 5 to 60 ring atoms, preferably 5 to 40 ring atoms and may in each case be substituted by one or more R 7 Aromatic or heteroaromatic ring systems substituted with radicals.

[0179] In a preferred embodiment of the compounds of formulae (6), (7), (8), (9), (10) and (11) which can be combined with the compound of formula (1) above according to the present invention, R 6 are identical or different in each case and are selected from: D or having 6 to 30 ring atoms and may be replaced by one or more R 7 Aromatic or heteroaromatic ring systems substituted with radicals.

[0180] Preferably, Ar5 in the compounds of formula (6), (7), (8), (10) and (11) is selected from: phenyl; biphenyl, in particular o-, m- or p-biphenyl; terphenyl, in particular o-, m- or p-terphenyl or branched terphenyl; quaterphenyl, in particular o-, m- or p-quaterphenyl or branched quaterphenyl; fluorenyl which may be attached via the 1, 2, 3 or 4 position; spirobifluorenyl which may be attached via the 1, 2, 3 or 4 position; naphthyl, in particular or a radical derived from indole, benzofuran, benzothiophene, carbazole that can be attached via the 1, 2, 3 or 4 position, dibenzofuran that can be attached via the 1, 2, 3 or 4 position, dibenzothiophene that can be attached via the 1, 2, 3 or 4 position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or terphenylidene, each of which can be attached via one or more R 7 Ar5 is preferably unsubstituted.

[0181] When A in formula (7) or (8) or (11) 1 NR 7When the substituent R bonded to the nitrogen atom 7 Preferably, the aromatic ring has 5 to 24 atoms and may be replaced by one or more R 8 In a particularly preferred embodiment, the substituent R 7 R is in each case identical or different and is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms. 7 Preferred embodiments are: phenyl, biphenyl, terphenyl and quaterphenyl, which are preferably unsubstituted; and groups derived from triazine, pyrimidine and quinazoline, which may be replaced by one or more R 8 Group substitution.

[0182] When A in formula (7) or (8) or (11) 1 C(R 7 )2, the substituent R bonded to the carbon atom 7 is preferably identical or different in each case and is a straight-chain alkyl radical having 1 to 10 carbon atoms or a branched or cyclic alkyl radical having 3 to 10 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be replaced by one or more R 8 Most preferably, R 7 is a methyl group or a phenyl group. In this case, R 7 The groups may also form a ring system together, thereby forming a spiro ring system.

[0183] In a preferred embodiment of the compounds of formula (6), (7), (8), (9), (10) and (11), these compounds are partially or fully deuterated, more preferably fully deuterated.

[0184] The preparation of compounds of formula (6), (7), (8), (9), (10) and (11) is generally known and some compounds are commercially available.

[0185] The compound of formula (9) is disclosed in, for example, pages 110 to 119 of WO2021 / 180614, especially in the examples on pages 120 to 127. Its preparation is disclosed in the synthesis examples on page 128 and pages 214 to 218 of WO2021 / 180614.

[0186] The preparation of triarylamines of formula (11) is known to those skilled in the art and some compounds are commercially available.

[0187] If the further matrix material is a deuterated compound, the further matrix material may be a mixture of deuterated compounds having the same chemical basic structure, differing only in the degree of deuteration.

[0188] In a preferred embodiment of other host materials, it is a mixture of deuterated compounds of formula (6), (7), (8), (9), (10) or (11) as described above, wherein the degree of deuteration of these compounds is at least 50% to 90%, preferably 70% to 100%. The corresponding deuteration method is known to those skilled in the art, and is described, for example, in KR2016041014, WO2017 / 122988, KR202005282, KR101978651 and WO2018 / 110887 or Bulletin of theChemical Society of Japan, 2021, Vol. 94 (Issue 2), pp. 600-605 or Asian Journal of Organic Chemistry, 2017, Vol. 6 (Issue 8), pp. 1063-1071.

[0189] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for deuterium atoms is to treat the compound to be deuterated in the presence of a platinum catalyst or a palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound that contains one or more deuterium atoms and is capable of releasing them under appropriate conditions.

[0190] The platinum catalyst is preferably dry platinum on carbon, preferably 5% dry platinum on carbon. The palladium catalyst is preferably dry palladium on carbon, preferably 5% dry palladium on carbon. Suitable deuterium sources are D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4 or toluene-d8. Preferred deuterium sources are D2O or a combination of D2O and a fully deuterated organic solvent. Particularly preferred deuterium sources are a combination of D2O and a fully deuterated organic solvent, wherein the fully deuterated solvent herein is not limited. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. Particularly preferred deuterium sources are a combination of D2O and toluene-d8. The reaction is preferably carried out under heating, more preferably at a temperature of 100° C. to 200° C. In addition, the reaction is preferably carried out under pressure.

[0191] Examples of suitable further matrix materials for combination with the compounds of the formula (1) as described above or preferably are the compounds described in WO 2019 / 229011, Table 3, pages 137 to 203, which may also be partially or fully deuterated.

[0192] Examples of suitable further matrix materials for combination with the compounds of the formula (1) as described above or preferably are the compounds described in Table 3 on pages 131 to 127 and Table 4 on pages 137 to 139 of WO 2021 / 180625, which may also be partially or fully deuterated.

[0193] Examples of suitable further matrix materials for combination with the compounds of the formula (1) as described above or as preferably described are the compounds described in the table on page 30 of WO 2011 / 088877, ie compounds 1 to 166, which may also be partially or fully deuterated.

[0194] Examples of suitable further matrix materials for combination with the compounds of the formula (1) as described above or as preferably described are the compounds described in the table on page 23 of WO 2011 / 128017, ie compounds 1 to 151, which may also be partially or fully deuterated.

[0195] Particularly suitable compounds of formula (6) for combination with compounds of formula (1) as described above or as preferred are compounds wherein at least one Ar5 group is a group having 5 to 40 ring atoms and which may be replaced by one or more R 7 A compound having a heteroaromatic ring system substituted with a group or a compound of formula (9) or (10).

[0196] The compounds of the formula (9) or (10) are particularly preferably suitable for combination with compounds of the formula (1) as described above or as preferably described.

[0197] The compounds of the formula (10) are particularly preferably suitable for combination with compounds of the formula (1) as described above or as preferably described.

[0198] Further examples of suitable host materials of formula (6), (7), (8), (9), (10) and (11) for combination with the compound of formula (1) as described above or preferably described are the structures in Tables 3 and 4 given below.

[0199] Table 3:

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206] Particularly suitable compounds of the formulae (6), (7), (8), (9), (10) and (11) which are selected according to the invention and are preferably used in combination with at least one compound of the formula (1) in the electroluminescent device according to the invention are the compounds in Table 4.

[0207] Table 4:

[0208]

[0209]

[0210]

[0211]

[0212] The host material of the aforementioned formula (1) and its preferred embodiments or the compounds in Table 1 as well as compounds E1 to E27 described above can be combined in the device of the present invention as required with the aforementioned matrix material / host material, i.e., the matrix material / host material of formula (6), (7), (8), (9), (10) and (11) and their preferred embodiments described in Table 3 or the compounds in Table 3 or compounds H1 to H27.

[0213] Very particularly preferred mixtures of compounds of formula (1) with host materials of formula (6), (7), (8), (9), (10) and (11) for use in the devices of the invention are obtained by combining compounds E1 to E27 with compounds H1 to H27, as shown in the following Table 5. For example, the first mixture M1 is a combination of compounds E1 and H1.

[0214] Table 5:

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223] The concentration of the host material of the formula (1) as described above or preferably in the mixture according to the invention or in the light-emitting layer of the device according to the invention is generally in the range from 5% to 90% by weight, preferably in the range from 10% to 85% by weight, more preferably in the range from 20% to 85% by weight, still more preferably in the range from 30% to 80% by weight, very particularly preferably in the range from 20% to 60% by weight, most preferably in the range from 30% to 50% by weight, based on the entire mixture or on the entire composition of the light-emitting layer.

[0224] The concentration of the host material of one of the formulae (6), (7), (8), (9), (10) and (11) as described above or preferably in the mixture according to the invention or in the light-emitting layer of the device according to the invention is typically in the range from 10% to 95% by weight, preferably in the range from 15% to 90% by weight, more preferably in the range from 15% to 80% by weight, still more preferably in the range from 20% to 70% by weight, very particularly preferably in the range from 40% to 80% by weight and most preferably in the range from 50% to 70% by weight, based on the entire mixture or on the entire composition of the light-emitting layer.

[0225] The present invention also relates to a mixture which, in addition to a host material of the above formula (1) referred to as host material 1 hereinafter as described above or preferably described above and a host material of one of the formulas (6), (7), (8), (9), (10) and (11) referred to as host material 2 hereinafter, in particular mixtures M1 to M729, also contains at least one phosphorescent emitter.

[0226] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the light-emitting layer comprises, in addition to a host material of the above formula (1) and one of the formulas (6), (7), (8), (9), (10) and (11), in particular material combinations M1 to M729, as described above or preferably described, at least one phosphorescent emitter.

[0227] The term "phosphorescent emitter" generally includes compounds in which light is emitted via a spin-forbidden transition from an excited state with a higher spin multiplicity, i.e. a spin state > 1, for example via a transition from a triplet state or a state with an even higher spin quantum number, such as a quintet state. This means that transitions from the triplet state are preferred.

[0228] Suitable phosphorescent emitters (=triplet emitters) are in particular compounds which emit light when suitably excited, preferably in the visible region, and which 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 metals with such an atomic number. Preferably used phosphorescent emitters 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 invention, all emitting compounds containing the abovementioned metals are regarded as phosphorescent emitters.

[0229] In general, all phosphorescent complexes known to the person skilled in the art for use in phosphorescent OLEDs and organic electroluminescent devices according to the prior art are suitable.

[0230] Phosphorescent emitters preferred according to the invention correspond to the formula (IIIa),

[0231]

[0232] The symbols and indices of formula (IIIa) are defined as follows:

[0233] n+m is 3, n is 1 or 2, m is 2 or 1,

[0234] X is identical or different in each case and is N or CR,

[0235] R is in each case identical or different and is: H, D, F, CN, or a branched or straight-chain alkyl radical having 1 to 10 carbon atoms, or a partially or fully deuterated branched or straight-chain alkyl radical having 1 to 10 carbon atoms, or a cycloalkyl radical having 4 to 7 carbon atoms, which may be partially or fully substituted by deuterium, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and which may be partially or fully substituted by deuterium.

[0236] The present invention therefore also provides an organic electroluminescent device as described above or preferably, characterized in that the emitting layer comprises, in addition to the host materials 1 and 2, at least one phosphorescent emitter which corresponds to the above formula (IIIa).

[0237] In the emitter of the formula (IIIa), n is preferably 1 and m is preferably 2.

[0238] In the emitter of the formula (IIIa), preferably one X is selected from N and the other X is CR, or all X are in each case identical or different and are CR.

[0239] In the emitter of the formula (IIIa), at least one R is preferably different from H. In the emitter of the formula (IIIa), preferably two R are different from H and have one of the further definitions given above for the emitter of the formula (IIIa).

[0240] Phosphorescent emitters preferred according to the invention correspond to the formula (I), (II), (III), (IV) or (V),

[0241]

[0242]

[0243]

[0244] The symbols and indices of formula (I), (II), (III), (IV) and (V) are defined as follows:

[0245] R1 is H or D, R2 is H, D, F, CN, or a branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a partially or fully deuterated branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms which may be partially or fully substituted with deuterium.

[0246] Phosphorescent emitters preferred according to the invention correspond to the formula (VI), (VII) or (VIII),

[0247]

[0248]

[0249] The symbols and indices of formulae (VI), (VII) and (VIII) are defined as follows:

[0250] R1 is H or D, R2 is H, D, F, CN, or a branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a partially or fully deuterated branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms which may be partially or fully substituted with deuterium.

[0251] Preferred examples of phosphorescent emitters are described in Table 5 on pages 120 to 126 and Table 6 on pages 127 to 129 of WO 2019 / 007867. The emitters are incorporated into the present description by this reference.

[0252] Table 6 below lists particularly preferred examples of phosphorescent emitters.

[0253] Table 6:

[0254]

[0255]

[0256]

[0257]

[0258] In the mixtures according to the invention or in the light-emitting layer of the device according to the invention, any mixture selected from the group consisting of mixtures M1 to M729 is preferably combined with a compound of the formula (IIIa) or a compound of the formulae (I) to (VIII) or a compound from Table 6.

[0259] The luminescent layer containing at least one phosphorescent emitter in the organic electroluminescent device of the present invention is preferably an infrared luminescent layer or a yellow-, orange-, red-, green-, blue- or ultraviolet-luminescent layer, more preferably a yellow- or green-luminescent layer, most preferably a green-luminescent layer.

[0260] A yellow emitting layer is a layer having a photoluminescence maximum in the range of 540 to 570 nm. An orange emitting layer is a layer having a photoluminescence maximum in the range of 570 to 600 nm. A red emitting layer is a layer having a photoluminescence maximum in the range of 600 to 750 nm. A green emitting layer is a layer having a photoluminescence maximum in the range of 490 to 540 nm. A blue emitting layer is a layer having a photoluminescence maximum in the range of 440 to 490 nm. The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of a layer having a layer thickness of 50 nm at room temperature, the layer having a combination of a host material of the formula (1) and one of the formulas (6), (7), (8), (9), (10) and (11) according to the present invention and a suitable emitter.

[0261] For example, a commercial photoluminescence spectrometer is used to record the photoluminescence spectrum of the layer.

[0262] The photoluminescence spectrum of the selected luminophore is usually within 10 -5 The measurement is carried out in a molar oxygen-free solution, a suitable solvent being any solvent in which the selected luminophore is soluble in the concentration stated. Particularly suitable solvents are usually toluene or 2-methyl-THF, but may also be dichloromethane. The measurement is carried out using a commercial photoluminescence spectrometer. The triplet energy T1 in eV is determined from the photoluminescence spectrum of the luminophore. First, the peak maximum Plmax. (in nm) of the photoluminescence spectrum is determined. The peak maximum Plmax. (in nm) is then converted to eV by the following formula: E(T1, in eV) = 1240 / E(T1, in nm) = 1240 / PLmax. (in nm).

[0263] Therefore, preferred phosphorescent emitters are yellow emitters, preferably yellow emitters of formula (IIIa), formula (I) to (VIII) or Table 6, whose triplet energy T1 is preferably ∼2.3 eV to ∼2.1 eV.

[0264] Therefore, preferred phosphorescent emitters are green emitters, preferably green emitters of formula (IIIa), formulae (I) to (VIII) or Table 6, whose triplet energy T1 is preferably ∼2.5 eV to ∼2.3 eV.

[0265] Therefore, particularly preferred phosphorescent emitters are green emitters, preferably green emitters of formula (IIIa), formula (I) to (VIII) or Table 6 as described above, whose triplet energy T1 is preferably ∼2.5 eV to ∼2.3 eV.

[0266] More preferably, for the mixture according to the invention or the light-emitting layer according to the invention, a green light emitter is selected, preferably a green light emitter of formula (IIIa), formula (I) to (VIII) or Table 6 as described above.

[0267] Fluorescent emitters may also be present in the emitting layer of the device according to the invention or in the mixture according to the invention.

[0268] Preferred fluorescent luminescent compounds are selected from arylamines, wherein at least one of the aromatic or heteroaromatic ring systems of the arylamine is preferably a fused ring system, more preferably a fused ring system having at least 14 ring atoms. Preferred examples thereof are aromatic anthraceneamine, aromatic anthracenediamine, aromatic pyreneamine, aromatic pyrenediamine, aromatic leucine or aromatic leucine diamine. Aromatic anthraceneamine refers to a compound in which one diarylamino group is directly bonded to an anthracene group, preferably bonded to the 9-position. Aromatic anthracenediamine refers to a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably bonded to the 9- and 10-positions. Aromatic pyreneamine, pyrenediamine, leucine and leucine diamine are defined in a similar manner, wherein the diarylamino group is preferably bonded to the 1-position or the 1- and 6-positions of pyrene. Also preferred luminescent compounds are indenofluoreneamine or indenofluorenediamine, benzoindenofluoreneamine or benzoindenofluorenediamine and dibenzoindenofluoreneamine or dibenzoindenofluorenediamine and indenofluorene derivatives with fused aryl groups. Also preferred are pyrene arylamines. Also preferred are benzoindenofluoreneamine, benzofluoreneamine and extended benzoindenofluorene, phenazine and fluorene derivatives connected to furan units or thiophene units. The light emitting device of the present invention or the mixture of the present invention may also additionally contain a material exhibiting TADF (thermally activated delayed fluorescence).

[0269] In other preferred embodiments of the present invention, at least one emitting layer of the organic electroluminescent device, in addition to the host materials 1 and 2 as described above or preferably described, may also include other host materials or matrix materials, referred to as a mixed matrix system. The mixed matrix system preferably comprises three or four different matrix materials, more preferably three different matrix materials (in other words, in addition to the host materials 1 and 2 as described above, it also comprises one other matrix component). The matrix material particularly suitable for use in the mixed matrix system as a matrix component combination is selected from wide bandgap materials, bipolar host materials, electron transport materials (ETM) and hole transport materials (HTM).

[0270] Preferably, the mixed-matrix system is optimized for emitters of the formula (IIIa), formulae (I) to (VIII) or Table 6.

[0271] In one embodiment of the present invention, the mixture, in addition to the composition of the main material and the main material 2 of formula (1) as described above, does not contain any other components, i.e., functional materials. These substances are therefore a material mixture for manufacturing a light-emitting layer. These mixtures are also referred to as premixed systems, which are used as the only material source in the vapor deposition of the main material of the light-emitting layer and have a constant mixing ratio in the vapor deposition. In this way, vapor deposition of a layer with a uniform component distribution can be achieved in a simple and fast manner without the need to accurately drive multiple material sources.

[0272] In an alternative embodiment of the invention, the mixture comprises, in addition to the components of the host material of formula (1) and host material 2 as described above, a phosphorescent emitter as described above. In case of suitable mixing ratios in vapor deposition, this mixture can also be used as the sole source of materials as described above.

[0273] Thus, the components or ingredients of the luminescent layer of the device according to the invention can be processed by vapor deposition or from solution. To this end, the host materials 1 and 2 as described above or preferably described are provided in a formulation containing at least one solvent, optionally in combination with the materials of the phosphorescent emitter as described above or preferably described. Suitable formulations have been described above.

[0274] Based on the overall composition of emitter and matrix material, according to preferred embodiments and the emitting compound, the emitting layer in the device according to the invention preferably contains 99.9% by volume to 1% by volume, also preferably 99% by volume to 10% by volume, particularly preferably 98% by volume to 60% by volume, very particularly preferably 97% by volume to 80% by volume of matrix material, the matrix material consisting of at least one compound of formula (1) and at least one compound of one of formulas (6), (7), (8), (9), (10) and (11) according to the preferred embodiments. Correspondingly, based on the overall composition of the emitting layer consisting of emitter and matrix material, the emitting layer in the device according to the invention preferably contains 0.1% by volume to 99% by volume, also preferably 1% by volume to 90% by volume, more preferably 2% by volume to 40% by volume, most preferably 3% by volume to 20% by volume of emitter. If the compound is processed from solution, it is preferred to use the corresponding amounts in % by weight instead of the abovementioned amounts in % by volume.

[0275] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the organic layer comprises a hole injection layer (HIL) and / or a hole transport layer (HTL), wherein the hole injection material and the hole transport material belong to the class of arylamines.

[0276] The order of the layers in the organic electroluminescent device of the present invention is preferably as follows:

[0277] Anode / hole injection layer / hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0278] This order of the layers is the preferred order.

[0279] At the same time, it should be pointed out again that not all of the layers mentioned need to be present and / or further layers may be present in addition.

[0280] The material used for the electron transport layer can be any material used as an electron transport material in the electron transport layer in the prior art. Particularly 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, phosphodiazoline derivatives and phosphine oxide derivatives.

[0281] Suitable cathodes for the device of the present invention are metals with low work functions, metal alloys or multilayer structures consisting of various metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g., Ca, Ba, Mg, Al, In, Yb, Sm, etc.). In addition, alloys consisting of alkali metals or alkaline earth metals and silver, such as alloys consisting of magnesium and silver, are suitable. In the case of multilayer structures, in addition to the metals, other metals such as Ag or Al with relatively high work functions can also be used, in which case combinations of the metals are generally used, such as Ca / Ag, Mg / Ag or Ba / Ag. It is also preferred that a thin intermediate layer of a material with a high dielectric constant be introduced between the metal cathode and the organic semiconductor. Examples of useful materials for this purpose are alkali metal fluorides or alkaline earth metal fluorides, as well as corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). In addition, lithium quinoline (LiQ) can also be used for this purpose. The layer thickness of this layer is preferably 0.5 nm to 5 nm.

[0282] Preferred anodes are materials with high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, metals with high redox potentials are suitable for this purpose, such as Ag, Pt or Au. Secondly, metal / metal oxide electrodes (such as Al / Ni / NiO x 、Al / PtO x) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to be able to illuminate the organic material (organic solar cells) or to couple out the light (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive doped organic materials, in particular conductive doped polymers. Furthermore, the anode may also consist of two or more layers, for example an inner layer of ITO and an outer layer of a metal oxide, the metal oxide being preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0283] During production, the organic electroluminescent device according to the invention is subjected to appropriate structuring (depending on the application), provision of contact connections and final sealing, since the lifetime of the device according to the invention is shortened in the presence of water and / or air.

[0284] The manufacture of the device of the invention is not restricted here. It is possible to apply one or more organic layers, including the light-emitting layer, by sublimation. In this case, the material is sublimated in a vacuum system at a temperature of less than 10 -5 mbar, preferably less than 10 -6 mbar by vapor deposition. In this case, however, it is also possible that the initial pressure is even lower, for example below 10 -7 mbar.

[0285] The organic electroluminescent device according to the invention is preferably characterized in that one or more layers are applied by the OVPD (organic vapor phase deposition) method or by means of carrier gas sublimation. -5 The material is applied at a pressure of 100 mbar to 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and thereby structured (eg MS Arnold et al., Appl. Phys. Lett., 2008, 92, 053301).

[0286] The organic electroluminescent device of the present invention is also preferably characterized in that one or more organic layers comprising the composition of the present invention are made by solution, for example, by spin coating or by any printing method such as screen printing, flexographic printing, nozzle printing or offset printing, but more preferably LITI (light induced thermal imaging, thermal transfer) or inkjet printing. For this reason, soluble host materials 1 and 2 and phosphorescent emitters are required. The advantage of processing from solution is that, for example, a luminescent layer can be applied in a very simple and inexpensive manner. This technology is particularly suitable for large-scale manufacture of organic electroluminescent devices.

[0287] Furthermore, hybrid methods are possible in which, for example, one or more layers are applied from solution and one or more other layers are applied by vapor deposition.

[0288] These methods are generally known to the person skilled in the art and can be applied to organic electroluminescent devices.

[0289] The present invention therefore also provides a method for producing an organic electroluminescent device according to the invention as described above or preferably as described, characterized in that the organic layers, preferably the emitting layers, the hole injection layers and / or the hole transport layers, are applied by vapor deposition, in particular by sublimation and / or by the OVPD (organic vapor phase deposition) method and / or by sublimation with the aid of a carrier gas, or are applied from solution, in particular by spin coating or by printing.

[0290] In the case of production by vapor deposition, there are in principle two ways in which the organic layer of the invention, preferably the luminescent layer, can be applied or vapor deposited onto any substrate or preceding layer. Firstly, each material used can first be charged into a material source and finally evaporated from different material sources ("coevaporation"). Secondly, the various materials can be premixed (premixed system), and the mixture can first be charged into a single material source and then finally evaporated from the material source ("premixed evaporation"). In this way, vapor deposition of a luminescent layer with a uniform distribution of components can be achieved in a simple and rapid manner without the need for precise driving of multiple material sources.

[0291] The present invention therefore also provides a method for producing a device according to the invention, characterized in that the emitting layer of the organic layer is applied by vapor deposition, wherein at least one compound of the formula (1) is deposited from the gas phase together with other materials forming the emitting layer, successively or simultaneously from at least two material sources.

[0292] In a preferred embodiment of the invention, the light-emitting layer is applied by vapour deposition, wherein the constituents of the composition are premixed and evaporated from a single material source.

[0293] The present invention therefore also provides a method for producing a device according to the invention, characterized in that the emitting layer of the organic layer is applied by vapor deposition, wherein at least one compound of the formula (1) is deposited from the gas phase together with at least one other matrix material as a premix, successively or simultaneously with a luminescent material selected from phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence) .

[0294] Compared with the prior art, the electronic device of the present invention, especially the organic electroluminescent device, has one or more of the following surprising advantages:

[0295] 1. Electronic devices, in particular organic electroluminescent devices, comprising the compounds of the formula (1) or the preferred embodiments described above and below, especially as matrix material or as electron-conducting material, have very good lifetimes. In this context, these compounds bring about, in particular, a low roll-off, i.e. a small drop in the power efficiency of the device at high brightness.

[0296] 2. An electronic device, in particular an organic electroluminescent device, comprising the compound of formula (1) or the preferred embodiment described above and below as an electron conducting material and / or matrix material has excellent efficiency. In this context, the compound of the present invention having the structure of formula (1) or the preferred embodiment described above and below can generate a low operating voltage when used in an electronic device.

[0297] 3. The inventive compounds of formula (1) or preferred embodiments described above and below exhibit very high stability and longevity.

[0298] 4. By using the compounds of formula (1) or the preferred embodiments described above and below, the formation of light loss channels in electronic devices, in particular organic electroluminescent devices, can be avoided. These devices are therefore characterized by high PL efficiency and thus high EL efficiency of the emitter and excellent energy transfer of the matrix to the dopant.

[0299] 5. The use of the compounds of the formula (1) or the preferred embodiments described above and below in layers of electronic devices, especially organic electroluminescent devices, leads to electron conductor structures with high mobility.

[0300] 6. The compounds of formula (1) or preferred embodiments described above and below have excellent glass film forming properties.

[0301] 7. The compounds of formula (1) or the preferred embodiments described above and below form very good films from solution.

[0302] 8. The compounds of formula (1) or preferred embodiments described above and below have a lower triplet energy level T1, which may be, for example, in the range of 2.50 eV to 2.90 eV.

[0303] These aforementioned advantages are not accompanied by excessive degradation of other electronic properties.

[0304] It should be noted that variations of the embodiments described in the present invention are included within the scope of the present invention. Unless explicitly excluded, any feature disclosed in the present invention may be replaced with an alternative feature having the same purpose or an equivalent or similar purpose. Therefore, unless otherwise specified, any feature disclosed in the present invention should be considered as an example of a general series or as an equivalent or similar feature.

[0305] Unless specific features and / or steps are mutually exclusive, all features of the present invention can be combined with each other in any way. This is particularly applicable to the preferred features of the present invention. Similarly, features of non-essential combinations can be used separately (not in combination).

[0306] The technical teachings disclosed in the present invention can be extracted and combined with other examples.

[0307] The present invention is illustrated in detail by the following examples, but is not intended to be limited thereby.

[0308] Example

[0309] General approach:

[0310] In all quantum chemical calculations, Gaussian16 (version B.01) software package was used. The neutral singlet ground state was optimized at the B3LYP / 6-31G(d) level. For the B3LYP / 6-31G(d) optimized ground state energy, HOMO and LUMO values ​​were determined at the B3LYP / 6-31G(d) level. TD-DFT singlet and triplet excitations (vertical excitations) were then calculated by the same method (B3LYP / 6-31G(d)) and the optimized ground state geometry. Standard settings for SCF and gradient convergence were used.

[0311] From the energy calculation, the HOMO is obtained as the last orbital occupied by two electrons (alpha occ. eigenvalues) and the LUMO is obtained as the first unoccupied orbital (alpha virt. eigenvalues) in Hartree units, where HEh and LEh denote the HOMO energy in Hartree units and the LUMO energy in Hartree units, respectively. This is used to determine the HOMO and LUMO values ​​in electron volts as follows, which are calibrated by cyclic voltammetry measurements:

[0312] HOMOcorr=0.90603×HOMO-0.84836,

[0313] LUMOcorr=0.99687×LUMO-0.72445.

[0314] The triplet energy level T1 of a material is defined as the relative excitation energy (in eV) of the triplet state with the lowest energy found by quantum chemical energy calculation.

[0315] The singlet energy level S1 of a material is defined as the relative excitation energy (in eV) of the singlet state with the second lowest energy found by quantum chemical energy calculation.

[0316] The singlet state with the lowest energy is called S0.

[0317] The method described herein is independent of the software package used and always gives the same results. Examples of programs frequently used for this purpose are "Gaussian09" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.). In this case, the software package "Gaussian16 (version B.01)" was used to calculate the energy.

[0318] Synthesis example

[0319] Unless otherwise stated, the following syntheses were all carried out in dry solvents under a protective gas atmosphere. The compounds of the present invention can be prepared by synthetic methods known to those skilled in the art.

[0320] a) (3-Amino-4-chloro-2-benzofuranyl)benzophenone

[0321]

[0322] To a solution of 99 g (489 mmol) of 2-bromo-6-hydroxybenzonitrile and 99.5 g (489 mmol) of bromoacetophenone in 790 ml of acetone were added portionwise 319 g (979 mmol) of cesium carbonate at room temperature under argon atmosphere.

[0323] The reaction mixture was heated to 60° C. for 2 hours. Subsequently, the mixture was cooled to room temperature, filtered, concentrated to dryness under reduced pressure, and recrystallized from heptane.

[0324] The yield was 107 g (316 mmol), corresponding to 69% of theory.

[0325] In a similar manner, the following brominated compounds were prepared:

[0326]

[0327]

[0328] b) 6-Bromo-2-cyanophenylbenzoate

[0329]

[0330] The solution of 10 g (50 mmol) 2-bromo-6-hydroxybenzonitrile, 10.4 ml (75 mmol) triethylamine and 61 mg (0.5 mmol) 4-N,N-dimethylaminopyridine in 200 ml CH2Cl2 charged first was cooled to 0°C, and then 10.5 g (75 mmol) benzoyl chloride was added. The mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into 20 ml sodium chloride solution and extracted three times with Et2O. The combined organic phases were dried with MgSO4. The organic solvent was removed under reduced pressure, and the residue was subjected to rapid column chromatography on silica gel (hexane / AcOEt=20 / 1 to 7 / 1).

[0331] Yield: 10.4 g (33 mmol), 70% of theory.

[0332] c) S-(2-cyano-3-bromophenyl)phenylthiocarboxylate

[0333]

[0334] Under argon, in a baked flask, 8 g (25 mmol) of 2-bromo-6-iodobenzonitrile, 0.47 g (10 mol%, 2.5 mmol) of CuI, 0.9 g (20 mol%, 5 mmol) of 1,10-phenanthroline and 5.1 g (37.5 mmol) of thiobenzoic acid were added to 20 ml of degassed toluene under nitrogen, and the mixture was stirred at 100°C for 24 hours. The reaction mixture was cooled to room temperature. Ether (1000 ml) and saturated sodium chloride solution (1000 ml) were added and the mixture was stirred. The organic phase was separated and the aqueous phase was extracted with ether (2×1000 ml). The combined organic phases were dried over Na2SO4 and the product was isolated by column chromatography.

[0335] Yield: 5.3 g (16.2 mmol), 65% of theory

[0336] d) (2-Amino-4-bromo-3-benzofuranyl)benzophenone

[0337]

[0338] Under argon, a solution of 0.67 g (30 mmol) Pd(OAc)2, 1.69 g (6 mmol) PCy3 (tricyclohexylphosphine), 1.96 g (30 mmol) zinc powder and 3 g 4 Å molecular sieves (MS4A) in 1200 ml DMF was first charged into a baked flask. After stirring at room temperature for 20 minutes, 9.4 g (30 mmol) bromo-2-cyanophenylbenzoate was added, and the mixture was stirred at 100°C overnight. The mixture was then mixed with a saturated NaCl solution, and the aqueous phase was extracted with Et2O (10 ml×3). The combined organic phases were dried over MgSO4 and filtered. The organic solvent was removed under reduced pressure, and the residue was purified by flash column chromatography on silica gel (hexane / AcOEt=7 / 1 to 2 / 1).

[0339] Yield: 6.2 g (20 mmol), 67% of theory.

[0340] In a similar manner, the following brominated compounds were prepared:

[0341]

[0342] e) 9-Bromo-2,4-diphenylbenzofurano[3,2-d]pyrimidine

[0343]

[0344] To an initial charge of 107 g (316 mmol) (3-amino-4-chloro-2-benzofuranyl)benzophenone and 104 g (1015 mmol) benzonitrile in 1000 ml o-xylene was added 56 g (677 mmol) sodium 2-methylpropan-2-ol under argon. The mixture was stirred at 140° C. for 5 hours. 30 ml of water were drained from the water separator, a small amount of acetone was then added, and the mixture was stirred for another hour. After cooling, the mixture was quenched with 1 liter of water. The organic phase was separated, washed three times with 300 ml of water, dried over MgSO4 and filtered, and the solvent was removed under reduced pressure. The residue was purified by column chromatography.

[0345] The yield was 64 g (160 mmol), corresponding to 48% of theory.

[0346] The following compounds were prepared in a similar manner:

[0347]

[0348]

[0349]

[0350]

[0351] f) 2,9-Dichloro-4-phenylbenzofurano[3,2-d]pyrimidine

[0352]

[0353] 13 g (110.0 mmol) of phenylboronic acid, 15.1 g (56 mmol) of 2,4,9-trichlorobenzofurano[3,2-d]pyrimidine and 21 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added to the suspension and the reaction mixture is heated under reflux for 16 hours. After cooling, the organic phase is separated off, filtered through silica gel and then concentrated to dryness. The residue is recrystallized from toluene and dichloromethane / heptane. Yield: 13.1 g (42 mmol), 75% of theory.

[0354] The following compounds were prepared in a similar manner:

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364] OLED Manufacturing

[0365] In the subsequent Examples V1 to V7 and B1 to B34 (see Tables 7 and 8), data for various OLEDs are presented.

[0366] Examples B1 to B34 show data for OLEDs according to the invention. The substrate used for the OLEDs in Table 7 was a glass plate coated with structured ITO (indium tin oxide) with a thickness of 50 nm.

[0367] The exact structure of the OLED can be found in Table 7. If not described above, the materials required to manufacture the OLED are as shown in Table 9.

[0368] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emitting layer always consists of at least one matrix material (also called host material) and a luminescent dopant (luminophore), which is added to the matrix material in a specific volume ratio by co-evaporation. The detailed information reported in the form of 7f:H2:TEG1 (33%:60%:7%) 30 nm indicates that in the 30 nm thick layer there is a volume ratio of 33% of material 7f as host material 1, a volume ratio of 60% of compound H2 as host material 2 and a volume ratio of 7% of TEG1. Similarly, the electron transport layer can also consist of a mixture of two materials.

[0369] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum and the current-voltage-luminance characteristic (IUL characteristic) were measured. From this, the EQE and the current efficiency SE (in cd / A) were calculated. The SE was calculated assuming Lambertian luminescence characteristics. The electroluminescence spectrum was calculated at a brightness of 1000 cd / m 2 The parameter U1000 in Table 8 refers to the luminance of 1000 cd / m 2 SE1000 means the voltage required when the brightness is 1000 cd / m 2 Finally, EQE1000 refers to the current efficiency achieved when the operating brightness is 1000 cd / m 2 The external quantum efficiency at .

[0370] The life span LT is defined in mA / cm 2 The lifetime is the time taken for the brightness to drop from the initial brightness L0 (in cd / m²) to a certain proportion L1 (in cd / m²) during operation at a constant current density j0. The value L1=80% in Table 8 means that the lifetime reported in the LT column corresponds to the time (in hours) for the brightness to drop to 80% of its initial value (L0).

[0371] Use of the mixtures according to the invention in OLEDs

[0372] The material combination of the invention can be used in the light-emitting layer in phosphorescent green OLEDs.

[0373] The data of various OLEDs are summarized in Table 8. Examples V1 to V7 are comparative examples of the prior art; Examples B1 to B34 show data of the OLEDs of the present invention. The examples of the present invention show a clear advantage in terms of device lifetime.

[0374] Table 7: Structure of OLED

[0375]

[0376]

[0377]

[0378] Table 8:

[0379]

[0380]

[0381] Table 9: Materials used (if not described above)

[0382]

[0383]

[0384]

Claims

1. A compound of formula (1), Formula (1), The symbols and notations used are as follows: Y is independently at each occurrence N, C-[L]b-Ar2 or C-[L]b1-Ar3, wherein exactly two Y are N separated by a C-[L]b-Ar2 or C-[L]b1-Ar3 group; V is O or S; Het satisfies one of the equations (1-2), (1-3), (1-4) and (1-5), * indicates the connection with the rest of formula (1), R 1 are, in each case identical or different and independently, H, D or phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl which is undeuterated or partially or fully deuterated; Ar, Ar1 are identical or different in each case and are ring atoms having 5 to 40 atoms and may be replaced by one or more R 2 group-substituted aromatic or heteroaromatic ring systems; Ar2, Ar3 are in each case identical or different and are an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, which may each be replaced by one or more R 2 Group substitution; R 2 are in each case identical or different and are selected from: D, F, CN, a straight-chain alkyl radical having 1 to 20 carbon atoms or a branched or cyclic alkyl radical having 3 to 20 carbon atoms, in which one or more non-adjacent CH2 groups may be replaced by O or S and in which one or more hydrogen atoms may be replaced by D, F or CN; R#, when present, is D or phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl which is undeuterated or partially or fully deuterated; [L] is an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, which may be unsubstituted or partially or fully substituted by D; b, b1, and b2 are each independently 0 or 1.

2. The compound according to claim 1, wherein Het conforms to formula (1-2).

3. The compound according to claim 1, wherein V is O.

4. A mixture comprising at least one compound according to one or more of claims 1 to 3 and at least one further compound selected from matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

5. A preparation comprising at least one compound according to one or more of claims 1 to 3 or a mixture according to claim 4 and at least one solvent. 6 . An organic electronic device comprising an anode, a cathode and at least one organic layer comprising at least one compound according to one or more of claims 1 to 3 .

7. The organic electronic device according to claim 6, wherein the electronic device is an electroluminescent device. 8 . The organic electronic device according to claim 6 , wherein the organic layer comprises at least one light-emitting layer comprising the compound according to claim 1 .

9. Organic electronic device according to one or more of claims 6 to 8, characterized in that The light-emitting layer contains other matrix materials.

10. The organic electronic device according to claim 9, characterized in that: The second host material corresponds to a compound of formula (6), (7), (8), (9), (10) or (11), Formula (6): Formula (7), Formula (8), Formula (9): Formula (10), Formula (11), The symbols and notations used are as follows: A 1 C(R 7 )2. NR 7 , O or S; L is a bond, O, S, C (R 7 )2 or NR 7 ; A is independently in each case a radical of the formula (3) or (4), X2 is in each case identical or different and is CH, CR 6 or N, where no more than 2 symbols X2 may be N; * represents the bonding site with formula (9); U 1 , U 2 When present, it is a key, O, S, C (R 7 )2 or NR 7 ; R 6 are in each case identical or different and are: D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 7 groups and one or more non-adjacent CH2 groups may be replaced by Si(R 7 )2. C=O、NR 7 , O, S or CONR 7 or have 5 to 60 ring atoms and may be replaced by one or more R 7 Aromatic or heteroaromatic ring system substituted with a radical; wherein the two R 6 The groups may also together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar5 is the same or different in each occurrence and is independently a ring having 5 to 40 ring atoms and may be replaced by one or more R 7 group-substituted aromatic or heteroaromatic ring systems; R 7 are identical or different in each case and are: D, F, Cl, Br, I, N(R 8 )2,CN,NO2,OR 8 , SR 8 ,Si(R 8 )3,B(OR 8 )2,C(=O)R 8 ,P(=O)(R 8 )2,S(=O)R 8 ,S(=O)2R 8 ,OSO2R 8 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 8 group, wherein one or more non-adjacent CH2 groups may be replaced by Si(R 8 )2. C=O, NR 8 , O, S or CONR 8 or have 5 to 40 ring atoms and may be replaced by one or more R 8 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two or more R 7 The groups may together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; preferably, R 7 The groups do not form any such ring systems; R 8 are in each case identical or different and are: H, D, F, or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in particular a hydrocarbon radical, in which one or more hydrogen atoms may also be replaced by F; c, c1, c2 are each independently 0 or 1, wherein the sum of the indices c+c1+c2=1 in each case; d, d1, d2 are each independently 0 or 1, wherein the sum of the indices d+d1+d2=1 in each case; q, q1, q2 are each independently 0 or 1; s is the same or different in each case and is 0, 1, 2, 3 or 4; t is the same or different in each case and is 0, 1, 2 or 3; u is the same or different in each case and is 0, 1, or 2; u1, u2 are each independently 0 or 1, wherein the sum u1+u2=1; and v is 0 or 1.

11. The organic electronic device according to one or more of claims 6 to 10, characterized in that The light-emitting layer contains a phosphorescent emitter.

12. Organic electronic device according to one or more of claims 6 to 11, characterized in that The organic electronic device is an electroluminescent device selected from the group consisting of an organic light emitting transistor (OLET), an organic field quenching device (OFQD), an organic light emitting electrochemical cell (OLEC, LEC, LEEC), an organic laser diode (O-laser) and an organic light emitting diode (OLED).

13. A method for producing a device according to one or more of claims 6 to 12, characterized in that The organic layers are applied by vapor deposition or from solution.

14. The method according to claim 13, characterized in that The light-emitting layer of the organic layer is applied by vapour deposition, wherein at least one compound of the formula (1) together with the other materials forming the light-emitting layer are deposited from the gas phase successively or simultaneously from at least two material sources.

15. The method according to claim 13 or 14, characterized in that The emitting layer of the organic layer is applied by vapor deposition, wherein at least one compound of the formula (1) is deposited together with at least one other matrix material as a premix from the gas phase successively or simultaneously with an emitting material selected from phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

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