Materials for organic electronic devices

Abstract

The present invention relates to specifically substituted deuterated biscarbazoles as OLED materials, to mixtures containing them, to the use thereof in organic electronic devices and to organic electronic devices containing these compounds, in particular organic electroluminescent devices or OLEDs containing these compounds as matrix materials, hole-transport materials, hole-injection materials or electron-blocking materials.

Description

[0001] Materials for organic electronic devices

[0002] Technical area

[0003] The present invention relates specifically to substituted deuterated biscarbazoles, mixtures containing them, their use in organic electronic devices and organic electronic devices containing these compounds, in particular organic electroluminescent devices or OLEDs containing these compounds, as matrix materials, hole transport materials, hole injection materials or electron blocking materials.

[0004] State of the art

[0005] Phosphorescent organometallic complexes are frequently used in organic electroluminescent devices (OLEDs). In general, there is still room for improvement in OLEDs, for example, with regard to efficiency, operating voltage, and lifetime. The properties of phosphorescent OLEDs are not only determined by the triplet emitters used. The other materials used, such as matrix materials or hole-transport materials, are also particularly important. Improvements to these materials can therefore also lead to significant improvements in OLED properties.

[0006] According to the state of the art, carbazole derivatives, dibenzofuran derivatives, indenocarbazole derivatives, indolocarbazole derivatives, benzofurocarbazole derivatives and benzothienocarbazole derivatives are used as matrix materials for phosphorescent emitters.

[0007] In WO2016102040 A1, special biscarbazoles are described as matrix materials.

[0008] In general, there is still room for improvement with these materials, particularly for use as matrix materials. The object of the present invention is to provide compounds which are particularly suitable for use as matrix materials, hole transport materials, hole injection materials or electron blocking materials in a phosphorescent OLED. In particular, the object of the present invention is to provide matrix materials which have a high temperature stability so that they can be evaporated undecomposed in a high vacuum. This property is a basic prerequisite for the reproducible production of organic electronic devices and has a particularly positive effect on the operational lifetime of these devices. The object applies in particular to the use of matrix materials in combination with a low to medium emitter concentration, i.e.Emitter concentrations in the order of 3 to 25%, in particular 3 to 15%, particularly preferably 4 to 8%, since the device lifetime is limited in particular here.

[0009] It has now been found that electroluminescent devices containing compounds of formula (1) exhibit improvements over the prior art, particularly when used as matrix material for phosphorescent dopants. By using the compounds of formula (1), the device lifetime can be significantly improved while simultaneously maintaining a low operating voltage.

[0010] It has further been found that the combination of at least one compound of formula (1) as first host material and at least one electron-transporting compound, for example in combination with one or more compounds of formulas (A), (B), (C), (D) and / or (E), as further host material(s) in a light-emitting layer of an organic electronic device, in particular an organic electroluminescent device, solves this problem and eliminates the disadvantages of the prior art.

[0011] Summary of the invention

[0012] A first object of the present invention are compounds of formula (1), Formula (1), where the symbols and indices used are:

[0013] (R) a , (R) b each independently represent a monosubstitution, a

[0014] disubstitution, a trisubstitution, the maximum allowable substitution or no substitution with the substituent R;

[0015] R is at each occurrence independently D or a non-deuterated or partially or fully deuterated aryl group having 6 to 18 C atoms;

[0016] Y is independently O or S at each occurrence; L, L1 are each independently a single bond or a non-deuterated or partially or fully deuterated arylene group having 6 to 18 C atoms;

[0017] Ar* is an aryl group with 6 to 30 C atoms or a heteroaryl group with 5 to 40 ring atoms, which can be substituted with one or more radicals R 1 can be substituted;

[0018] R 1is selected, identically or differently at each occurrence, from the group consisting of D, F, CN, Si(Aryl)3, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more non-adjacent CH2 groups may be replaced by O or S and where one or more H atoms may be replaced by D, F, or CN or a non-deuterated or partially or fully deuterated aryl group having 6 to 30 C atoms or a non-deuterated or partially or fully deuterated electron-rich heteroaryl group having 9 to 40 ring atoms;

[0019] Aryl is, at each occurrence, independently of one another, identically or differently, an aryl group having 6 to 30 C atoms or a heteroaryl group having 5 to 40 ring atoms, which may be partially or fully deuterated, where the compounds of formula (1) are partially or fully deuterated.

[0020] The invention further relates to 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 the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence).

[0021] Another object of the invention is the use of at least one compound according to formula (1) in an organic electronic device.

[0022] A further subject matter of the invention is an organic electronic, preferably electroluminescent, device comprising an anode, a cathode and at least one organic layer containing at least one compound of formula (1), as described above or preferably described later.

[0023] The invention further relates to a process for producing an organic electronic, preferably electroluminescent, device, as described above or preferably described below, characterized in that the organic layer is applied by vapor deposition or from solution. Description of the invention

[0024] In this patent application, "D" or "D atom" refers to deuterium. The degree of deuteration, expressed in mol%, represents the proportion of H atoms replaced by deuterium. Since the deuterated compounds are often a mixture of compounds that differ in the exact position and proportion of the D atoms, the degree of deuteration represents the average proportion of H atoms replaced by D. Thus, with a degree of deuteration of 50 mol%, on average 50 mol% of the H atoms in the compound are replaced by D, resulting in a medium degree of deuteration.

[0025] An aryl group within the meaning of this invention contains 6 to 40 ring atoms or preferably 6 to 30 ring atoms or preferably 6 to 18 ring atoms, where the ring atoms are C atoms. A heteroaryl group within the meaning of this invention contains 5 to 40 ring atoms, where the ring atoms comprise C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group is understood to be a simple aromatic ring, for example phenyl derived from benzene, or a condensed aryl group, for example derived from naphthalene, anthracene, phenanthrene, triphenylene, but the term aryl group within the meaning of the invention also includes biphenyl, terphenyl, quaterphenyl, fluorenyl, 9,9-dialkylfluorenyl, 9,9-diarylfluorenyl or spirobifluorenyl. A preferred 9,9-dialkylfluorenyl group is 9,9-dimethylfluorenyl.A preferred 9,9-diarylfluorenyl group is 9,9-diphenylfluorenyl. An aryl group with 6 to 18 carbon atoms is therefore preferably phenyl, naphthyl, phenanthryl, or triphenylenyl, whereby the attachment of the aryl group as a substituent is not restricted. The aryl group within the meaning of this invention can bear one or more radicals, with the suitable radical being described below. The radical is preferably deuterium. If no such radical is described, the aryl group or heteroaryl group is unsubstituted.

[0026] A heteroaryl group is understood to mean either a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a condensed heteroaryl group, for example derived from quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene or carbazole, but the term heteroaryl group in the sense of the invention also includes a heteroaryl group which is bonded to an aryl group or another heteroaryl group by a single bond, for example phenyl-bipyridyl or bipyridyl.

[0027] The heteroaryl group within the meaning of this invention can carry one or more radicals, with the suitable radical being described below. The radical is preferably deuterium. If no such radical is described, the heteroaryl group is unsubstituted.

[0028] An aromatic ring system within the meaning of this invention contains 6 to 40 carbon atoms in the ring system. The aromatic ring system includes aryl groups, as described above, and the term is used synonymously below.

[0029] An aromatic ring system with 6 to 18 carbon atoms is preferably selected from phenyl, biphenyl, naphthyl, phenanthryl, and triphenylenyl, which may carry one or more radicals, the suitable radical being described below. Preferably, the radical is deuterium. If no such radical is described, the aromatic ring system is unsubstituted.

[0030] A heteroaromatic ring system within the meaning of this invention contains 5 to 40 ring atoms and at least one heteroatom. A preferred heteroaromatic ring system has 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system comprises heteroaryl groups, as described above, and the term is used synonymously below.

[0031] An aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which can be linked to the aromatic or heteroaromatic ring via any position and which can carry one or more radicals, as described below, is preferably understood to mean the following groups, which are derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, terphenyl, quaterphenyl, fluorene, 9,9-dimehtylfluorene, 9,9-diphenylfluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, Spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine,Chinolin, Isochinolin, Acridin, Phenanthridin, Benzo-5,6-chinolin, Benzo-6,7-chinolin, Benzo-7,8-chinolin, Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1,2-Thiazol, 1,3-Thiazol, Benzothiazol, Pyridazin, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1,5-Diazaanthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1,6-Diazapyren, 1,8-Diazapyren, 4,5-Diazapyren, 4,5,9,10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenan- throlin, 1,2,3-Triazol, 1 ,2,4-Triazol, Benzotriazol, 1,2,3-Oxadiazol, 1,2,4-Oxadiazol, 1,2,5-Oxadiazol, 1,3,4-Oxadiazol, 1,2,3-Thiadiazol, 1,2,4-Thiadiazol, 1,2,5-Thiadiazol,

[0032] 1.3.4-Thiadiazol, 1 ,3,5-Triazin, 1 ,2,4-Triazin, 1 ,2,3-Triazin, Tetrazol, 1,2,4,5-Tetrazin,

[0033] 1.2.3.4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, benzothiadiazole, phenylpyridine and bipyridine.

[0034] The abbreviation Ar* stands for an aryl group with 6 to 30 C atoms or a heteroaryl group with 5 to 40 ring atoms, which can be linked to one or more radicals R 1 may be substituted, where the radical R 1 has a meaning as described above or below. The abbreviation "aryl" is, at each occurrence, independently of one another, identically or differently, an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 5 to 40 ring atoms, which may be partially or fully deuterated. The abbreviation "aryl" is preferably phenyl, which may be partially or fully deuterated.

[0035] The abbreviation Ar 5 represents, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted by one or more radicals R 7can be substituted or is synonymous with an aryl group with 6 to 40 C atoms or a heteroaryl group with 5 to 40 ring atoms, which can be substituted with one or more radicals R 7 may be substituted, where R 7 or the substituents R 7 has / have a meaning as described above or below,

[0036] A preferred meaning of Ar*, “aryl” and Ar 5 is described below.

[0037] An electron-rich heteroaromatic compound is a heterocyclic aromatic compound with a π excess, i.e., a lone pair of electrons on the heteroatom forms the cyclically delocalized electrons with the p-electrons of the carbon atoms. This definition also applies to an electron-rich heteroaromatic ring system.

[0038] A cyclic alkyl, alkoxy or thioalkyl group in the sense of this invention is understood to mean a monocyclic, a bicyclic or a polycyclic group.

[0039] In the context of the present invention, a straight-chain, branched or cyclic C1 to C 20-Alkylgruppe beispielsweise die Reste Methyl, Ethyl, n-Propyl, i-Propyl, Cyclopropyl, n-Butyl, i-Butyl, s-Butyl, t-Butyl, Cyclobutyl, 2-Methylbutyl, n-Pentyl, s-Pentyl, t-Pentyl, 2-Pentyl, neo-Pentyl, Cyclopentyl, n-Hexyl, s-Hexyl, t-Hexyl, 2-Hexyl, 3- Hexyl, neo-Hexyl, 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, Trifluormethyl, Pentafluorethyl, 2,2,2-Trifluorethyl, 1,1-Dimethyl-n-hex-1-yl-, 1,1-Dimethyl-n-hept-1-yl-, 1,1-Dimethyl-n-oct-1-yl-, 1,1-Dimethyl-n-dec-1-yl-, 1,1-Dimethyl- n-dodec-1-yl-, 1,1-Dimethyl-n-tetradec-1-yl-, 1,1-Dimethyl-n-hexadec-1-yl-, 1,1-Dimethyl- n-octadec-1-yl-, 1 , 1-Diethyl-n-hex-1-yl-, 1 , 1-Diethyl-n-hept-1 -yl-, 1 , 1-Diethyl-n-oct-1 -yl-, 1 , 1-Diethyl-n-dec-1-yl-, 1,1-Diethyl-n-dodec-1-yl-, 1,1-Diethyl-n-tetradec-1-yl-, 1,1-Diethyln-n-hexadec-1-yl-, 1,1-Diethyl-n-octadec-1-yl-, 1-(n-propyl)-cyclohex-1-yl-, 1-(n-butyl)-cyclohex-1-yl-, 1-(n-hexyl)-cyclohex-1-yl-, 1-(n-octyl)-cyclohex-1-yl- and 1-(n-decyl)-cyclohex-1-yl- understood.,

[0040] The compounds of formula (1) and their preferred embodiments are described below. The preferred embodiments also apply to the mixture according to the invention and the organic electronic or electroluminescent device according to the invention.

[0041] Preferred embodiments of the compounds of formula (1) are compounds of

[0042] Formula (1a), where Ar*, (R) a , (R) b , R, Y, L and L1 have a meaning preferably given above or below and the compounds of formula (1a) are partially or completely deuterated.

[0043] The invention accordingly further relates to compounds of formula (1a), as described above or preferably described below.

[0044] In compounds of formulas (1) or (1a), the linkers L and L1 are each independently a single bond or a non-deuterated or partially or fully deuterated arylene group having 6 to 18 C atoms corresponding to the linkers L-1 to L-17, which may be non-deuterated, partially or fully deuterated,

[0045] where the dashed lines indicate the bond to the residue of formula (1) or the residue of formula (1a) and where R 1 has a meaning previously specified or subsequently specified.

[0046] In compounds of formulas (1) and (1a), L is preferably a single bond or a linker selected from L-1 to L-7, which may be non-deuterated, partially or fully deuterated.

[0047] Particularly preferred compounds of formulas (1) or (1a) are compounds of

[0048] Formulas (1b) or (1c), Formula (1b),

[0049] Formula (1c), where Ar*, (R) a , (R) b , R, Y and L1 have a meaning preferably given above or below, c is 0, 1, 2 or 3 and the compounds of formulas (1 b) or (1c) are partially or completely deuterated.

[0050] In compounds of formulas (1), (1a), (1b) and (1c), L1 is preferably a single bond or a linker selected from L-1 to L-7, which may be non-deuterated, partially or fully deuterated.

[0051] Particularly preferred compounds of formulas (1), (1a) or (1b) are

[0052] Compounds of formula (1 d), Formula (1d), where Ar*, (R) a , (R) b, R and Y have a meaning preferably given above or below, c is 0, 1, 2 or 3 and the compounds of the formula (1d) are partially or completely deuterated.

[0053] Very particularly preferred compounds of formulas (1), (1a) or (1c) are compounds of formulas (1e) or (1f),

[0054] where Ar*, (R) a , (R) b , R and Y are a previously or subsequently preferred

[0055] meaning, c is 0, 1, 2 or 3 and the compounds of formula (1e) or (1f) are partially or completely deuterated.

[0056] A particularly preferred embodiment of the compounds of formula (1) are compounds of formulas (1d), (1e) and (1f), as described above.

[0057] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), Y preferably represents O at each occurrence.

[0058] The invention accordingly further provides compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), as described above or preferably described below, in which Y is O at each occurrence.

[0059] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) (R) a and (R) b a monosubstitution, a disubstitution, a trisubstitution, the maximum permissible substitution or no substitution with the substituent R and the substituent R, when identical or different, is preferably selected from the group D or a non-deuterated or partially or fully deuterated aryl group having 6 to 18 C atoms. The substituent R, when occurring, is preferably D or non-deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl. The substituent R, when occurring, is particularly preferably D.

[0060] In a preferred embodiment of the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), one substituent R is selected from a non-deuterated or partially or fully deuterated aryl group having 6 to 18 C atoms and the remaining substituents R are D when they occur.

[0061] In the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), Ar* is preferably selected from the group Ar-1 to Ar-42,

[0062]

[0063] Y 2 O, S or Se means

[0064] Y 3 O, S, NAr3 or C(R # )2means

[0065] R 3 H or R 1 means that the dashed bond represents the bond to the rest of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f),

[0066] Ar3 represents an aryl group having 6 to 30 ring atoms or a heteroaryl group having 5 to 40 ring atoms which is reacted with one or more radicals R 1 may be substituted, Ar' is phenylene, m is 0 or 1 and

[0067] R # at each occurrence, identically or differently, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, each of which is substituted by one or more radicals R 1 may be substituted, where one or more H atoms may be replaced by D, F or CN or an aryl group with 6 to 30 ring atoms or a heteroaryl group with 5 to 40 ring atoms, which may be substituted with one or more radicals R 1 may be substituted, and where R 1 has a previously mentioned or a previously preferred meaning.

[0068] The substituent R 1when Ar3in N-Ar3is preferably D, F or CN, particularly preferably D. In the formulas Ar-15 to Ar-18 and Ar-23 to Ar-26, Ar3when occurring in N-Ar3is Y 3 particularly preferably selected from non-deuterated, partially deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl.

[0069] The symbol Y 3 in the formulas Ar-15 to Ar-18 and Ar-23 to Ar-26 preferably means N-

[0070] Ar3, C(CH3)2, O or S, particularly preferably O or S, most preferably O.

[0071] R 1 in R# is preferably D, F or CN, particularly preferably D.

[0072] Y 2 in the formulas Ar-31 to Ar-35 is preferably S or O, particularly preferably O.

[0073] In Ar* the substituent R 1preferably on each occurrence, identically or differently selected from the group consisting of D, F, CN or a non-deuterated, partially deuterated or fully deuterated aryl group having 6 to 30 ring atoms or a non-deuterated, partially deuterated or fully deuterated electron-rich heteroaryl group having 9 to 40 ring atoms. In Ar*, the substituent R 1 particularly preferably, at each occurrence, selected identically or differently from the group consisting of D, non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl. In Ar*, the substituent R 1 especially preferred D.

[0074] In the structures Ar-1 to Ar-42 the substituent R 3preferably at each occurrence, identically or differently selected from the group consisting of H, D, F, CN or a non-deuterated, partially deuterated or fully deuterated aryl group having 6 to 30 ring atoms or a non-deuterated, partially deuterated or fully deuterated electron-rich heteroaryl group having 9 to 40 ring atoms. In the structures

[0075] Ar-1 to Ar-42 is the substituent R 3 particularly preferably selected, identically or differently at each occurrence, from the group consisting of H, D, non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-

[0076] Biphenyl. In the structures Ar-1 to Ar-42, the substituent R 3 most preferably selected, identically or differently at each occurrence, from the group consisting of H or D.

[0077] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), Ar* is particularly preferably selected from the group Ar-1 to Ar-10, Ar-15 to Ar-18, Ar-23 to Ar-26, Ar-29 and Ar-

[0078] 30 selected, where R 3 has a previously specified or preferred meaning.

[0079] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), Ar* is particularly preferably selected from the group Ar-1 to Ar-10, Ar-29 and Ar-30, where R 3 has a previously specified or preferred meaning.

[0080] Since the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) are deuterated compounds, it is possible during their preparation, provided that the preparation is chosen by reacting a non-deuterated compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e) or (1f) with a deuteration source or provided that deuterated starting compounds are chosen during the preparation which are a mixture of deuterated starting compounds, that a mixture of deuterated products of the same basic chemical structure is formed which only differ in the degree of deuteration and / or the deuteration patterns.Such mixtures of deuterated compounds of the same basic chemical structure of formula (1) or the basic structure of the preferred embodiments, which differ only in the degree of deuteration and / or the deuteration patterns, are understood by the term “at least one compound of formula (1)” in the sense of the invention.

[0081] In a preferred embodiment of the at least one compound of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), as described above or preferably described, the average degree of deuteration is from 5 mol% to 100 mol%, preferably from 30 mol% to 95 mol%, particularly preferably from 50 mol% to 90 mol%.

[0082] Corresponding deuteration methods are known to the person skilled in the art and are described, for example, in KR2016041014, WO2017 / 122988, KR202005282, KR101978651 and WO2018 / 110887 or in Bulletin of the Chemical Society of Japan, 2021, 94(2), 600-605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0083] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for diatoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more diatoms and capable of releasing them under suitable conditions.

[0084] 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. A suitable deuterium source is D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, or toluene-d8. A preferred deuterium source is D2O or a combination of D2O and a fully deuterated organic solvent. A particularly preferred deuterium source is the combination of D2O with a fully deuterated organic solvent, whereby the fully deuterated solvent is not limited here. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of D2O and toluene-d8.The reaction is preferably carried out with heating, more preferably with heating to temperatures between 100 °C and 200 °C. Furthermore, the reaction is preferably carried out under pressure.

[0085] Examples of suitable host materials of 1), (1a), (1b), (1c), (1d), (1e) and (1f) are the structures listed below in Table 1. Table 1:

[0086] Particularly suitable compounds of formulas 1), (1a), (1b), (1c), (1d), (1e) and (1f) are the compounds H1 to H21 of Table 2.

[0087] Table 2:

[0088] For the sake of simplicity, some of the compounds in Tables 1 and 2 are depicted as fully deuterated compounds. These compounds generally refer to compounds that have an average degree of deuteration of at least 50 mol%. The average degree of deuteration for these fully deuterated compounds in Tables 1 and 2 is preferably between 50 mol% and 100 mol%, or it has a preferred value as previously described. If partially deuterated compounds are described in Tables 1 and 2, a D atom means that the corresponding position in the molecule has a degree of deuteration of at least 40 mol%.

[0089] The compounds according to the invention can be prepared by synthesis steps known to the person skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc.

[0090] In the following synthesis schemes, the compounds are shown with a small number of substituents to simplify the structures. This does not exclude the presence of any additional substituents in the processes. The processes shown for the synthesis of the compounds of the invention are to be understood as examples. The skilled person can develop alternative synthesis routes within the scope of their general technical knowledge.

[0091] Scheme 1:

[0092] Scheme 2:

[0093] Detailed reaction conditions are known from the state of the art or are described in the examples section.

[0094] By these processes, optionally followed by purification, such as

[0095] Recrystallization or sublimation, the compounds of formula (1) can be obtained in high purity, preferably more than 99% (determined by 1 H-NMR and / or HPLC).

[0096] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention or mixtures of compounds of the invention with other functional materials, such as matrix materials, fluorescent emitters, phosphorescent emitters, and / or emitters exhibiting TADF, are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-Dimethylanisol, 3,5-Dimethylanisol, Acetophenon, a- Terpineol, Benzothiazol, Butylbenzoat, Cumol, Cyclohexanol, Cyclohexanon, Cyclohexylbenzol, Decalin, Dodecylbenzol, Ethylbenzoat, Indan, NMP, p-Cymol, Phenetol, 1 ,4-Diisopropylbenzol, Dibenzylether, Diethylenglycolbutylmethylether, Tri- ethylenglycolbutylmethylether, Diethylenglycoldibutylether, T riethylenglycoldimethylether, Diethylenglycolmonobutylether, Tripropyleneglycoldimethylether, Tetraethylenglycoldi- methylether, 2-lsopropylnaphthalin, Pentylbenzol, Hexylbenzol, Heptylbenzol, Octylbenzol, 1 ,1-Bis(3,4-dimethylphenyl)ethan, 2-Methylbiphenyl, 3-Methylbiphenyl, 1- Methylnaphthalin, 1-Ethylnaphthalin, Ethyloctanoat, Sebacinsäure-diethylester, Octyloctanoat, Heptylbenzol, Menthyl-isovalerat, Cyclohexylhexanoat oder Mischungen dieser Lösemittel.,

[0097] A suitable formulation is a formulation comprising at least one compound according to the invention, as described above, or a mixture according to the invention, as described below, and at least one solvent. The solvent can be one of the solvents mentioned above or a mixture of these solvents.

[0098] The compounds of formula(s) (1), (1a), (1b), (1c), (1e) and (1f) according to the invention, as described above or preferably described, are suitable for use in an organic electroluminescent device, in particular as a hole transport material, as a hole injection material, as an electron blocking material or as a matrix material.

[0099] If the compound according to the invention is used as matrix material or synonymously host material in an emitting layer, it is preferably used in combination with another compound.

[0100] The invention therefore further provides a mixture comprising at least one compound of formula (1) or at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e) or (1f), or a compound of Table 1 or one of the compounds H1 to H21 and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence). Suitable matrix materials and emitters that can be used in this mixture according to the invention are described below.

[0101] A further subject matter of the present invention is an organic electronic device comprising an anode, a cathode and at least one organic layer containing at least one compound of formula (1) or at least one preferred compound of one of the formulas (1a), (1b), (1c), (1e) or (1f), or a compound of Table 1 or one of the compounds H1 to H21.

[0102] Particularly suitable matrix materials which are advantageously combined with the compounds according to the invention in a mixed matrix system can be selected from the compounds of formulas (A), (B), (C), (D) or (E), as described below.

[0103] The organic electronic device can be selected, for example, from organic integrated circuits (OLCs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors, organic photoreceptors.

[0104] Preferably, the organic electronic device is an organic electroluminescent device.

[0105] The organic electroluminescent device according to the invention (synonymously referred to as organic electroluminescent device) is, for example, an organic light-emitting transistor (OLET), an organic field quench 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 according to the invention is, in particular, an organic light-emitting diode or an organic light-emitting electrochemical cell. The device according to the invention is particularly preferably an OLED.

[0106] The organic layer of the device according to the invention preferably contains, in addition to a light-emitting layer (EML), 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 charge-generation layers. The device according to the invention can also contain several layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. Interlayers, which, for example, have an exciton-blocking function, can also be introduced between two emitting layers.

[0107] If a plurality of emission layers are present, these preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, resulting in an overall white emission, i.e. different emitting compounds which can fluoresce or phosphoresce are used in the emitting layers. A plurality of fluorescent and / or phosphorescent compounds can also be present in one emitting layer. Systems with three emitting layers are particularly preferred, wherein the three layers exhibit blue, green and orange or red emission. As an alternative to the combination as described above, an emitting layer can also exhibit yellow emission. Such combinations are known to the person skilled in the art. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, in particular for white-emitting OLEDs.

[0108] The device may also contain inorganic materials or layers made entirely of inorganic materials.

[0109] A variety of materials known in the prior art are suitable for use in the layers of the organic electroluminescent device described above. When selecting materials, common considerations regarding the chemical and physical properties of the materials must be taken into account, as the materials in an organic electroluminescent device are interrelated. This applies, for example, to the energy positions of the orbitals (HOMO, LIIMO) or the position of triplet and singlet energies, as well as other material properties.

[0110] The compound of the formula (1) according to the invention, as described above or preferably described, can be used in different layers, depending on the precise structure. Preference is given to an organic electroluminescent device comprising a compound of the formula (1) or the preferred embodiments described above in an emitting layer as a matrix material for fluorescent emitters, phosphorescent emitters or for emitters which exhibit TADF (thermally activated delayed fluorescence), in particular for phosphorescent emitters. Furthermore, the compound of the invention can also be used in a hole-transporting layer or in a hole-injecting layer or in an electron-blocking layer. The compound of the invention is particularly preferably used as a matrix material in an emitting layer or as a hole-transporting or hole-injecting or electron-blocking material in a hole-transporting, hole-injecting orElectron blocking layer is used.

[0111] A further subject matter of the present invention is an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer which contains at least one compound of the formula (1) or the at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1e) or (1f), or a compound of Table 1 or one of the compounds H1 to H21.

[0112] In one embodiment of the invention, at least one further matrix material is selected for the device according to the invention in the light-emitting layer, which is used with compounds of the formula (1), as described above or preferably described, or with the compounds of Table 1 or the compounds H1 to H21.

[0113] A further subject matter of the present invention is accordingly an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer which contains at least one compound of the formula (1) or the at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1e) or (1f), or a compound of Table 1 or one of the compounds H1 to H21 and at least one further matrix material.

[0114] A further subject matter of the present invention is accordingly an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer which contains at least one compound of the formula (1) or the at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1e) or (1f), or a compound of Table 1 or one of the compounds H1 to H21 and at least two further matrix materials.

[0115] Suitable matrix materials that can be used in combination with the compounds according to 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, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or dibenzofuran derivatives. Likewise, another phosphorescent emitter that emits at a shorter wavelength than the actual emitter can be present in the mixture as a cohost, or a compound that does not participate, or does not participate to a significant extent, in charge transport, such as a wide-band-gap compound.

[0116] A wide-band-gap material is understood herein to mean a material within the meaning of the disclosure of US Pat. No. 7,294,849, which is characterized by a band gap of at least 3.5 eV, where the band gap is understood to be the difference between the HOMO and LUMO energy of a material. Particularly suitable matrix materials, which are advantageously combined with compounds of formula(s) (1), (1a), (1b), (1c), (1e) or (1f), as previously described or preferably described, in a mixed-matrix system, can be selected from the compounds of formulas (A), (B), (C), (D) or (E), as described below.

[0117] A further subject of the invention is therefore a mixture containing at least one compound according to the invention and at least one compound of the

[0118] Formulas (A), (B), (C), (D) and / or (E), where the symbols and indices used are:

[0119] X is the same or different at each occurrence N or CR 6 , preferably N;

[0120] L 2 is at each occurrence, identically or differently, a single bond or an aromatic or heteroaromatic ring system with 5 to 24 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted;

[0121] R## is, identically or differently at each occurrence, D, F, CN or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted with one or more radicals R 6 may be substituted and two adjacent substituents R## may together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system which may be substituted with one or more radicals R 7 can be substituted;

[0122] Y is the same or different at each occurrence N or CR 9, whereby it is excluded that two adjacent Ys simultaneously represent N;

[0123] V 2 is O or S;

[0124] R 6 is, identically or differently at each occurrence, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which may be partially or fully deuterated; two radicals R 6 also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with each other;

[0125] Ar 5 represents, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted by one or more radicals R 7 can be substituted;

[0126] R 7 is the same or different at each occurrence D, F, CI, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more non-adjacent CH2 groups are replaced by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which may be partially or fully deuterated; two or more radicals R 7 form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;

[0127] R 8 is, at each occurrence, identically or differently, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may be replaced by F;

[0128] R 9 is the same or different at each occurrence H, D, F, CI, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 6 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 6 may be substituted; two or more radicals R 9 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; b1 is 0, 1, 2, 3 or 4; b2 is 0, 1, 2 or 3.

[0129] The invention further relates to an organic electronic device, in particular an organic electroluminescent device comprising anode, cathode and at least one organic layer containing at least one light-emitting layer, wherein the at least one light-emitting layer contains at least one compound of the formula (1) as matrix material 1, as described above or described as preferred, and at least one compound of the formulas (A), (B), (C), (D) and / or (E) as matrix material 2, as described above or described below as preferred.

[0130] Preferred compounds of formula (A) are the compounds of formulas (Aa), (Ab), (Ac), (Ad), (Ae) and (Af),

[0131] where the symbols and indices for these formulas have the following meaning: W, W 1 mean, the same or different at each occurrence, O, S, C(R W )2or N- Ar 5 ;

[0132] R w is, on each occurrence, identically or differently, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more H atoms may be replaced by D, F, or CN, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more H atoms of the alkyl group on the aromatic or heteroaromatic ring system may be replaced by D, F, or CN; the two radicals R w which bind to the same carbon atom also form a ring system with each other;

[0133] A is the same or different at each occurrence CR 7or N, where a maximum of two groups A per cycle stand for N and where A stands for C, if at this position L 2 is bound; a3 is, at each occurrence, the same or different, 0, 1, 2, 3 or 4; b3 is, at each occurrence, the same or different, 0, 1, 2 or 3; is derived from an aryl group having 6 to 20 ring atoms, which may be substituted by one or more substituents R##; b means or

[0134] L 3 is an aromatic ring system with 6 to 40 ring atoms or a heteroaromatic ring system with 5 to 40 ring atoms, which are linked to one or more radicals R 7 may be substituted; and where L 2 , X, Ar , 5 R 7 and R## have the meanings given above.

[0135] Particularly preferred compounds of formulas (A) and (Aa) are the compounds of formulas (Aa-1) to (Aa-5), , where the symbols and indices used are:

[0136] Ar* is, identically or differently, an aromatic ring system with 6 to 40 ring atoms, which is substituted with one or more substituents R 7 can be substituted;

[0137] L 5 is a bond or an aromatic ring system with 6 to 40 ring atoms, which is substituted with one or more substituents R 7 can be substituted,

[0138] (R 7 ) X , (R 7 ) y , (R 7 ) X1 , (R 7 ) y1 represent a monosubstitution, a disubstitution, a trisubstitution or the maximum permissible substitution with the substituent R 7 represents,

[0139] R 18 is at each occurrence, identically or differently, a straight-chain alkyl group having 1 to 10 C atoms or an aryl group having 6 to 12 C atoms, where two substituents R 18together can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted with one or more substituents R 7 may be substituted; where L 2 , Ar 5 and R 7 have a meaning previously mentioned or a meaning previously and subsequently preferred.

[0140] In compounds of formulas (Aa-1), (Aa-2), (Aa-3), (Aa-4) and (Aa-5) the substituents R 7 in (R 7 ) x , (R 7 ) y , (R 7 ) x1 , (R 7 ) y1 when occurring preferably as indicated below, most preferably D.

[0141] Compounds of formula (Aa-4), as previously described or preferably described, are also preferred embodiments of the compound of formula (Ac).

[0142] Particularly preferred compounds of formulas (A) and (Af) are the compounds of formulas (Af-1) to (Af-3),

[0143] where the symbols and indices used are: (R 7 ) X , (R 7 ) y represent a monosubstitution, a disubstitution, a trisubstitution or the maximum permissible substitution with the substituent R 7 represents

[0144] R 18 is at each occurrence, identically or differently, a straight-chain alkyl group having 1 to 10 C atoms or an aryl group having 6 to 12 C atoms, where two substituents

[0145] R 18 together can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted with one or more substituents R 7 may be substituted; where L 2 , Ar 5 and R 7 have a meaning previously mentioned or a meaning previously and subsequently preferred.

[0146] In compounds of formulas (Af-1), (Af-2) and (Af-3) the substituents R 7 in (R 7 ) x , (R 7 ) y when occurring preferably as indicated below, most preferably D.

[0147] Preferred compounds of formula (B) are the compounds of formula (Ba), 9 9 7 Q where Y, V , L 2 , R 7 , R and a3 have a previously specified meaning, D corresponds to deuterium and a4 represents 0, 1 or 2.

[0148] Preferred compounds of formula (C) are the compounds of formula (Ca), where the symbols and indices for this formula (Ca) have the following meaning:

[0149] W 1 is the same or different at each occurrence O, S, C(R W )2or N-Ar 5 ;

[0150] #X is CR or NAr 5 , preferably NAr 5 ; R wis, on each occurrence, the same or different, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more H atoms of the alkyl group on the aromatic or heteroaromatic ring system may be replaced by D, F or CN; a3 is, on each occurrence, the same or different, 0, 1, 2, 3 or 4; is derived from an aryl group having 6 to 20 ring atoms, which may be substituted by one or more substituents R##; means or where L 2 , Ar 5and R## have the meanings given above.

[0151] In compounds of formula (Aa) W is preferably O or N-Ar 5 .

[0152] In compounds of formula (Aa), A is preferably, identically or differently at each occurrence, CH or CR 7 , where A stands for C, if at this position L 2 is bound.

[0153] In compounds of formulas (Ae) or (Ca) W 1 prefers O, C(R W )2or N-Ar 5 , particularly preferably N-Ar 5 .

[0154] In compounds of formula (Af), L 3 preferably a heteroaromatic ring system with 9 to 30 ring atoms, which is substituted by one or more radicals R 7 can be substituted.

[0155] In a preferred embodiment of the compounds of formulas (A), (Aa), (Ab), (Ac), (Ad), (Ae), (Af), (B), (Ba), (C), (Ca), (D) or (E), which can be combined according to the invention with the above-mentioned compounds of the invention, as described above, R 7 identically or differently at each occurrence selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each of which may be partially or fully deuterated. In a particularly preferred embodiment of the compounds of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E), which can be combined according to the invention with the above-listed compounds of the invention, as described above, R7 identically or differently at each occurrence selected from the group consisting of D or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, each of which may be partially or fully deuterated.

[0156] The preparation of the compounds of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E) are generally known and some of the compounds are commercially available.

[0157] If the at least one further matrix material is a deuterated compound, it is possible that this at least one matrix material is a mixture of deuterated compounds with the same basic chemical structure, differing only in the degree of deuteration and / or the deuteration pattern. The statements regarding deuterated mixtures and the preparation of deuterated materials, as previously described for compounds of formula (1), apply here accordingly.

[0158] In a preferred embodiment of the at least one further matrix material, this is a mixture of deuterated compounds of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E), as described above, wherein the average degree of deuteration of these compounds is at least 10 mol% to 100 mol%, preferably 50 mol% to 95 mol%, particularly preferably 70 mol% to 90 mol%.

[0159] Suitable compounds of formula (A) are known, for example, from the following publications: WO2007 / 077810A1, WO2008 / 056746A1, WO2010 / 136109A1 ,

[0160] WO2011 / 057706A2, WO2011 / 160757A1, WO2012 / 023947A1, WO2012 / 048781 A1, WO2013 / 077352A1, WO2013147205A1, WO2013 / 083216A1, WO2014 / 094963A1,

[0161] WO2014 / 007564A1, WO2014 / 015931 A1, WO2015 / 090504A2, WO2015 / 105251 A1, WO2015 / 169412A1, WO2016 / 015810A1, WO2016 / 013875A1, WO2016 / 010402A1, WO20 16 / 033167A1, WO2017 / 178311A1, WO2017 / 076485A1, WO2017 / 186760A1,

[0162] WO2018 / 004096A1, WO2018 / 016742A1, WO2018 / 123783A1, WO2018 / 159964A1, WO2018 / 174678A1, WO2018 / 174679A1, WO2018 / 174681 A1, WO2018 / 174682A1, WO2019 / 177407A1, WO2019 / 245164A1, WO2019 / 240473A1, WO2019 / 017730A1, WO2019 / 017731 A1, WO2019 / 017734A1, WO2019 / 145316A1, WO2019 / 121458A1,

[0163] WO2020 / 130381 A1, WO2020 / 130509A1, WO2020 / 169241 A1, WO2020 / 141949A1, WO2021 / 066623A1, WO2021 / 101220A1, WO2021 / 037401A1, WO2021 / 180614A1, WO2021 / 239772A1, WO2022 / 015084A1, WO2022 / 025714A1, WO2022 / 055169A1, EP3575296A1, EP3591728A1, US2014 / 0361254A1, U S2014 / 0361268A1, KR20210036304A, KR20210036857A, KR2021147993A, JP2011 / 160367A2 and JP2017 / 107992A2.

[0164] Suitable compounds of formula (B) are known, for example, from the following publications: WO2015 / 182872A1, WO2015 / 105316A1, WO2017 / 109637A1 ,

[0165] WO2018 / 060307A1, WO2018 / 151479A2, WO2018 / 088665A2, WO2018 / 060218A1, WO2018 / 234932A1, WO2019 / 058200A1, WO2019 / 017730A1, WO2019 / 017731 A1, WO2019 / 066282A1, WO2019 / 059577A1, WO2020 / 141949A1, WO2020 / 067657A1, WO2022063744A1, W02022 / 090108A1, WO2022 / 207678A1, WO2023061998A1, KR20170139443A, KR20190036867A, KR2019035308A, KR2021147993A,

[0166] CN110294753A, CN110437241 A, US2016 / 072078A1, US2019 / 148646A1.

[0167] Suitable compounds of formula (C) are known, for example, from the following publications: WO2017 / 160089A1, WO2019 / 017730A1, WO2019 / 017731 A1 ,

[0168] WO2020 / 032424A1.

[0169] Suitable compounds of formula (E) are known, for example, from the following publications: WO2015 / 093878A1, WO2016 / 033167A1, WO2017 / 183859A1 ,

[0170] WO2017 / 188655A1, WO2018 / 159964A1.

[0171] For combination with the compounds according to the invention, as described above or preferably described, compounds of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B) and / or (Ba) are particularly suitable, as described above or preferably described, or corresponding compounds from the tables below which fall under these formulas. The compounds of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2) and / or (Af-3) are particularly preferred.

[0172] Further examples of suitable host materials of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E), which can be combined according to the invention with the above-mentioned compounds of the invention, as described above, are the structures mentioned below in Tables 3 and 4 below.

[0173]

[0174]

[0175]

[0176]

[0177]

[0178] Particularly suitable compounds of the formulas (A), (Aa), (Ab), (Ac), (Ad), (Ae), (Af) and / or (B), which can be combined according to the invention with the above-mentioned compounds of the invention, as described above, and are used in the electroluminescent device or mixture according to the invention, are the compounds E1 to E41 of Table 4.

[0179] Table 4:

[0180] For the sake of simplicity, some of the compounds in Tables 3 and 4 are depicted as fully deuterated compounds. These compounds generally refer to compounds that have an average degree of deuteration of at least 50 mol%. The average degree of deuteration for these fully deuterated compounds in Tables 3 and 4 is preferably between 50 mol% and 100 mol%, or it has a preferred value as previously described. If partially deuterated compounds are described in Tables 3 and 4, a D atom means that the corresponding position in the molecule has a degree of deuteration of at least 40 mol%.

[0181] The above-mentioned host materials according to the invention and their preferred embodiments described can be combined as desired in the device according to the invention with the above-mentioned matrix materials / host materials, the matrix materials / host materials of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E), and their preferred embodiments described in Table 3 or the compounds E1 to E41 of Table 4.

[0182] Very particularly preferred mixtures of the compounds of the formula (1) with the host materials of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E) for the device according to the invention are obtained by combining the compounds H1 to H21 with the compounds E1 to E41. Very preferred mixtures are shown in Table 5 below. The first mixture M1, for example, is a combination of the compound E1 with H1.

[0183] Table 5:

[0184] The concentration of the host material of formula (1), as described above or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 10 wt.% to 95 wt.%, preferably in the range from 15 wt.% to 90 wt.%, more preferably in the range from 15 wt.% to 80 wt.%, even more preferably in the range from 20 wt.% to 70 wt.%, very particularly preferably in the range from 40 wt.% to 80 wt.% and most preferably in the range from 50 wt.% to 70 wt.%, based on the total mixture or based on the total composition of the light-emitting layer.

[0185] The concentration of the sum of all host materials of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E), as described above or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 5 wt.% to 90 wt.%, preferably in the range from 10 wt.% to 85 wt.%, more preferably in the range from 20 wt.% to 85 wt.%, even more preferably in the range from 30 wt.% to 80 wt.%, very particularly preferably in the range from 20 wt.% to 60 wt.% and most preferably in the range from 30 wt.% to 50 wt.%, based on the entire mixture or based on the entire composition the light-emitting layer.

[0186] The present invention also relates to a mixture which, in addition to the above-mentioned host materials according to the invention of the formula (1), hereinafter referred to as host material 1, and the host material of at least one of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E), as described above or preferably described, contains at least one phosphorescent emitter.

[0187] The present invention also relates to a mixture selected from a combination of the compounds H1 to H21 with the compounds E1 to E41 or the mixtures M1 to M630, which also contains at least one phosphorescent emitter.

[0188] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the light-emitting layer contains at least one phosphorescent emitter in addition to the above-mentioned host materials of the formula (1) and at least one of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) and (E), as described above or preferably described, in particular the material combinations M1 to M630.

[0189] The term "phosphorescent emitters" typically encompasses compounds in which light emission occurs through a spin-forbidden transition from an excited state with higher spin multiplicity, i.e., a spin state > 1, for example, through a transition from a triplet state or a state with an even higher spin quantum number, such as a quintet state. Preferably, this refers to a transition from a triplet state.

[0190] Particularly suitable phosphorescent emitters (= triplet emitters) are compounds that emit light upon suitable excitation, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds containing the above-mentioned metals are considered phosphorescent emitters.

[0191] In general, all phosphorescent complexes as used in the prior art for phosphorescent OLEDs and as known to those skilled in the art in the field of organic electroluminescent devices are suitable. Preferred phosphorescent emitters according to the present invention correspond to the formulas (I), (II), (III), (IV) or (V),

[0192] where the symbols and indices for these formulas (I), (II), (III), (IV) and (V) have the meaning:

[0193] R1is H or D, R2is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear

[0194] Alkyl group with 1 to 10 C atoms or a cycloalkyl group with 4 to 10 C atoms, which may be partially or fully substituted with deuterium.

[0195] Preferred phosphorescent emitters according to the present invention correspond to formula (VI), formula (VI), where the symbols and indices for this formula (VI) have the meaning: n+m is 3, n is 1 or 2, m is 2 or 1 ,

[0196] X is the same or different at each occurrence, N or CR,

[0197] R is, on each occurrence, identically or differently, H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 7 C atoms which may be partially or fully substituted by deuterium or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms which may be partially or fully substituted by deuterium and / or by a branched or linear alkyl group having 1 to 10 carbon atoms and / or by a partially or fully deuterated, branched or linear alkyl group having 1 to 10 carbon atoms. In emitters of the formula (VI), n is preferably 1 and m is preferably 2.

[0198] In emitters of formula (VI), one X is preferably selected from N and the other Xs are CR or all Xs, identically or differently on each occurrence, are CR. In emitters of formula (VI), at least one R is preferably different from H. In emitters of formula (VI), two Rs are preferably different from H and have one of the meanings otherwise previously given for the emitters of formula (VI).

[0199] A further subject matter of the invention is accordingly an organic electroluminescent device as described above or preferably described, characterized in that the light-emitting layer contains, in addition to the host materials 1 and 2, at least one phosphorescent emitter which corresponds to one of the formulas (I) to (VI), as described above, preferably to the formula (VI).

[0200] Preferred examples of phosphorescent emitters are described in WO2019 / 007867 on pages 120 to 126 in Table 5 and on pages 127 to 129 in Table 6. The emitters are incorporated into the description by this reference.

[0201] Particularly preferred examples of phosphorescent emitters are listed in Table 6 below.

[0202] Table 6:

[0203] In the mixtures according to the invention or in the light-emitting layer of the device according to the invention, preferably each mixture of compounds H1 to H21 with each E1 to E41, particularly preferably each mixture selected from the sum of the mixtures M1 to M630 is combined with a compound of the formulas (I) to (VI) or a compound from Table 6.

[0204] The light-emitting layer in the organic electroluminescent device according to the invention containing at least one phosphorescent emitter is preferably an infrared-emitting, yellow, orange, red, green, blue or ultraviolet-emitting layer, particularly preferably a yellow or green-emitting layer and very particularly preferably a green-emitting layer.

[0205] A yellow-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 540 to 570 nm. An orange-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 570 to 600 nm. A red-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 600 to 750 nm.

[0206] A green-emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 490 to 540 nm. A blue-emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 440 to 490 nm. The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of the layer with a layer thickness of 50 nm at room temperature, wherein the layer contains the inventive combination of the host material 1 of the formulas (1), (1a), (1b), (1c), (1d), (1e) or (1f) and the host material 2, consisting of at least one of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) and (E), and the corresponding emitter.

[0207] The photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer.

[0208] The photoluminescence spectrum of the selected emitter is usually measured in oxygen-free solution, 10 -5 molar, measured at room temperature, and any solvent in which the selected emitter dissolves at the specified concentration is suitable. Particularly suitable solvents are usually toluene or 2-methyl-THF, but also dichloromethane. The measurement is carried out using a commercially available photoluminescence spectrometer. The triplet energy T1 in eV is determined from the photoluminescence spectra of the emitters. First, the peak maximum Plmax. (in nm) of the photoluminescence spectrum is determined. The peak maximum Plmax. (in nm) is then converted to eV according to: E(T1 in eV) = 1240 / E(T1 in nm) = 1240 / PLmax. (in nm).

[0209] Preferred phosphorescent emitters are therefore yellow emitters, preferably of the formulas (I) to (VI) or from Table 6, whose triplet energy T1 is preferably between ~2.3 eV and ~2.1 eV.

[0210] Preferred phosphorescent emitters are therefore green emitters, preferably of formulas (I) to (VI) or from Table 6, whose triplet energy T1 is preferably between ~2.5 eV and ~2.3 eV.

[0211] Particularly preferred phosphorescent emitters are accordingly green emitters, preferably of the formulas (I) to (VI) or from Table 6, as previously described, whose triplet energy T1 is preferably between ~2.5 eV and ~2.3 eV.

[0212] Green emitters, preferably of the formulas (I) to (VI) or from Table 6, as described above, are very particularly preferably selected for the mixture according to the invention or the emitting layer according to the invention.

[0213] Fluorescent emitters can also be present in the light-emitting layer of the device according to the invention or in the mixture according to the invention. Preferred fluorescent emitting compounds are selected from the class of arylamines, wherein preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, particularly preferably with at least 14 ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to be a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position.An aromatic anthracenediamine is understood to be a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably being bonded in the 1-position or 1,6-position, respectively. Further preferred emitting compounds are indenofluorenamines and diamines, benzoindenofluorenamines and diamines, and dibenzoindenofluorenamines and diamines, as well as indenofluorene derivatives with fused aryl groups. Pyrene-arylamines are also preferred. Also preferred are benzoindenofluoreneamines, benzofluoreneamines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives bonded to furan units or thiophene units. In addition, the light-emitting device orthe mixture according to the invention may also contain materials that exhibit TADF (thermally activated delayed fluorescence).

[0214] In a further preferred embodiment of the invention, the at least one light-emitting layer of the organic electroluminescent device can have three or four different matrix materials, preferably three different matrix materials. These corresponding mixed-matrix systems can consist of the matrix materials described for host material 1 and host material 2, but they can also contain, as a third or fourth matrix material, for example, in addition to a host material 1 or host material 2, wide-band-gap materials, bipolar host materials, electron-transport materials (ETM), or hole-transport materials (HTM). The mixed-matrix system is preferably optimized for an emitter of the formulas (I) to (VI) or for an emitter of Table 6.

[0215] According to one embodiment of the present invention, the mixture contains no further components, i.e., functional materials, apart from the components of host material 1 and host material 2, as previously described or preferably described. These are material mixtures that are used as such to produce the light-emitting layer. These mixtures are also referred to as premix systems, which are used as the sole material source during the vapor deposition of the host materials for the light-emitting layer and which have a constant mixing ratio during vapor deposition. This allows for the simple and rapid vapor deposition of a layer with a uniform distribution of the components, without the need for precise control of a large number of material sources.

[0216] According to an alternative embodiment of the present invention, the mixture contains, in addition to the components of host material 1 and host material 2, as described above or preferably described, a phosphorescent emitter as described above. With a suitable mixing ratio during vapor deposition, this mixture can also be used as the sole material source.

[0217] Preferred are premix systems consisting of two matrix materials, namely a compound of the formulas (1), (1a), (1b), (1c), (1d), (1e) or (1f) and a compound of one of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E).

[0218] Preferred are premix systems consisting of three matrix materials, namely a compound of the formulas (1), (1a), (1b), (1c), (1d), (1e) or (1f) and two compounds of one of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E).

[0219] The components or constituents of the light-emitting layer of the device according to the invention can thus be processed by vapor deposition or from solution. The material combination of host materials 1 and 2, as described above or preferably described, optionally with the phosphorescent emitter, as described above or preferably described, is provided for this purpose in a formulation containing at least one solvent. Suitable formulations have been described previously.

[0220] The light-emitting layer in the device according to the invention according to the preferred embodiments and the emitting compound preferably contains between 99.9 and 1 vol.%, further preferably between 99 and 10 vol.%, particularly preferably between 98 and 60 vol.%, very particularly preferably between 97 and 80 vol.% of matrix material made of at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e) or (1f) and at least one compound of one of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E) according to the preferred embodiments, based on the total composition of emitter and matrix material. Accordingly, the light-emitting layer in the device according to the invention preferably contains between 0.1 and 99 vol.%, more preferably between 1 and 90 vol.%, particularly preferably between 2 and 40 vol.-%, very particularly preferably between 3 and 20 vol.% of the emitter, based on the total composition of the light-emitting layer consisting of emitter and matrix material. If the compounds are processed from solution, the corresponding amounts in wt.% are preferably used instead of the above-specified amounts in vol.%.

[0221] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the organic layer contains a hole injection layer (HIL) and / or a hole transport layer (HTL), whose hole injecting material and hole transporting material belong to the class of arylamines.

[0222] The sequence of layers in the organic electroluminescent device according to the invention is preferably as follows:

[0223] Anode / hole injection layer / hole transport layer / emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0224] This sequence of layers is a preferred sequence.

[0225] It should be noted again that not all of the layers mentioned need to be present and / or that additional layers may be present.

[0226] All materials used in the electron transport layer according to the state of the art can be used as electron transport materials. Particularly suitable are aluminum complexes, for example Alq3, zirconium complexes, for example Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives.

[0227] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the organic layer contains a hole injection layer (HIL) and / or a hole transport layer (HTL) and / or an electron blocking layer, whose hole injecting material and hole transporting material are selected from the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) or (1f), as described above or preferably described.]

[0228] Suitable cathodes for the device according to the invention include metals with low work functions, metal alloys, or multilayer structures made of different metals, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Yb, Sm, etc.). Alloys made of an alkali or alkaline earth metal and silver, for example, an alloy of magnesium and silver, are also suitable. In multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function, such as Ag or Al, can also be used. Combinations of the metals, such as Ca / Ag, Mg / Ag, or Ba / Ag, are then generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Suitable materials for this purpose include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Lithium quinolinate (LiQ) can also be used. The thickness of this layer is preferably between 0.5 and 5 nm.

[0229] Materials with a high work function are preferred as the anode. The anode preferably has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Metal / metal oxide electrodes (e.g., Al / Ni / NiOx, Al / PtOx) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Also preferred are conductive, doped organic materials, in particular conductive doped polymers.Furthermore, the anode can also consist of several layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0230] The organic electroluminescent device according to the invention is structured, contacted and finally sealed accordingly (depending on the application) during production, since the lifetime of the devices according to the invention is shortened in the presence of water and / or air.

[0231] The manufacture of the device according to the invention is not restricted in this respect. It is possible to coat one or more organic layers, including the light-emitting layer, using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6mbar. However, it is also possible that the initial pressure is even lower, for example less than 10 -7 mbar. The organic electroluminescent device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) method or by means of carrier gas sublimation. The materials are then sublimated at a pressure between 10 -5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g., BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0232] Furthermore, the organic electroluminescent device according to the invention is preferably characterized in that one or more organic layers comprising the composition according to the invention are produced from solution, for example by spin coating, or by any printing process, such as screen printing, flexographic printing, nozzle printing, or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or inkjet printing. Soluble host materials 1 and 2 and phosphorescent emitters are required for this purpose. Processing from solution has the advantage that, for example, the light-emitting layer can be applied very easily and cost-effectively. This technique is particularly suitable for the mass production of organic electroluminescent devices.

[0233] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are vapor-deposited.

[0234] These methods are generally known to the person skilled in the art and can be applied to organic electroluminescent devices.

[0235] A further subject of the invention is therefore a method for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the hole injection layer and / or hole transport layer, is applied by vapor phase deposition, in particular with a sublimation process and / or with an OVPD (Organic Vapor Phase Deposition) process and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.

[0236] When manufactured by vapor deposition, there are basically two ways in which the organic layer according to the invention, preferably the light-emitting layer, can be applied or vapor-deposited onto any substrate or the previous layer. Firstly, the materials used can each be placed in a material source and then evaporated from the various material sources ("co-evaporation"). Secondly, the various materials can be premixed ("premixed" systems) and the mixture placed in a single material source, from which it is then vaporized ("premix evaporation"). This allows for the vapor deposition of the light-emitting layer with a uniform distribution of the components in a simple and rapid manner, without the need for precise control of a large number of material sources.

[0237] The following procedures are possible:

[0238] A method for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the electron transport layer and / or hole blocking layer, is applied by vapor phase deposition, in particular with a sublimation process and / or with an OVPD (Organic Vapor Phase Deposition) process and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.

[0239] A method for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e) or (1f) together with the further materials which form the light-emitting layer are deposited successively or simultaneously from at least two material sources from the gas phase.

[0240] A method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein the at least one compound of formulas (1), (1a), (1b), (1c), (1d), (1e), or (1f) is deposited from the vapor phase together with at least one further matrix material as a premix, sequentially or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters, and / or emitters exhibiting TADF (thermally activated delayed fluorescence). The electronic devices according to the invention, in particular organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art:

[0241] The electronic devices according to the invention, in particular organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art:

[0242] 1. Electronic devices, in particular organic electroluminescent devices containing compounds according to formula (1) or the preferred embodiments described above and below, in particular as matrix material or as hole-conducting materials, exhibit a very long lifetime. These compounds, in particular, result in low roll-off, i.e., a low drop in the power efficiency of the device at high luminance levels.

[0243] 2. The compounds according to the invention according to formula (1) or the preferred embodiments described above and below show a very high stability and lifetime.

[0244] 3. Using compounds according to formula (1) or the preferred embodiments described above and below, the formation of optical loss channels can be avoided in electronic devices, particularly organic electroluminescent devices. As a result, these devices are characterized by high PL and thus high EL efficiency of emitters and excellent energy transfer from the matrices to dopants.

[0245] 4. The compounds according to formula (1) or the preferred embodiments described above and below have a deep triplet level T1, which can be in the range of 2.40 eV - 2.90 eV.

[0246] These advantages mentioned above are not accompanied by an excessive deterioration of the other electronic properties.

[0247] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Any feature disclosed in the present invention may, unless explicitly excluded, be replaced by alternative features serving the same, equivalent, or similar purpose. Thus, unless otherwise stated, any feature disclosed in the present invention is to be considered an example of a generic series or an equivalent or similar feature.

[0248] All features of the present invention may be combined with each other in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations may be used separately (and not in combination).

[0249] The teaching of technical action disclosed in the present invention can be abstracted and combined with other examples.

[0250] The invention is explained in more detail by the following examples, without intending to limit it thereby.

[0251] Examples Synthesis examples

[0252] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The compounds of the invention can be prepared using synthesis methods known to those skilled in the art.

[0253] For the sake of simplicity, the following compounds are partially depicted as fully deuterated compounds. These compounds generally refer to compounds that have an average degree of deuteration of at least 50 mol%. The average degree of deuteration for these fully deuterated compounds is preferably between 50 mol% and 100 mol%, or it has a preferred value as described above. For partially deuterated compounds, a D atom means that the corresponding position in the molecule has a degree of deuteration of at least 40 mol%. a) 3-(6-Bromo-dibenzofuran-4-yl)-9-phenyl-9H-carbazole

[0254] 10.43 g (32 mmol) of carbazole-3-boronic acid, 8.9 g (31.6 mmol) of 4,6-dibromodibenzofuran, and 31 mL (63 mmol) of Na2CO3 (2 M solution) are suspended in 120 mL of toluene and 120 mL of ethanol. 0.73 g (0.63 mmol) of Pd(PPh3)4 is added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, filtered through silica gel, washed three times with 200 mL of water, and then evaporated to dryness. The residue is recrystallized from toluene. The yield is 11.4 g (23 mmol), corresponding to 73% of theory. The following compounds can be obtained analogously: b) 3-Dibenzofuran-4-yl-9-(4-dibenzofuran-4-yl-phenyl)-9H-carbazole

[0255] Under protective gas, 23.6 g (71 mmol) of 3-(6-bromo-dibenzofuran-4-yl)-9-phenyl-9H-carbazole and 25 g (74 mmol) of 4-(4-bromo-phenyl)-dibenzofuran, 8 g (84 mmol) of sodium tert-butylate, 3.5 ml of tris-tert-butylphosphine (1M in toluene), and 0.393 mg (1.7 mmol) of palladium acetate are suspended in 300 ml of p-xylene. The reaction mixture is heated under reflux at 110 °C for 12 h. After cooling, the organic phase is separated, washed three times with 200 mL of water, and then evaporated to dryness. The product is purified by column chromatography on silica gel using toluene / heptane (1:2). The residue is extracted with hot toluene, recrystallized from toluene, and finally sublimed under high vacuum. HPLC purity is greater than 99.9%. The yield is 33.7 g (658 mmol), 80% of theory, purity according to 1 H-NMR approx. 94%.

[0256] The following connections are made analogously: c) 3-Bromo-6-(dibenzo[b,d]furan-4-yl)-9-(4-(dibenzo[b,d]furan-4-yl)phenyl)-9H-carbazole

[0257] 21.2 g (37 mmol) of 3-(dibenzo[b,d]furan-4-yl)-9-(4-(dibenzo[b,d]furan-4-yl)phenyl)-9H-carbazole are initially dissolved in 80 mL of DMF. 13.3 g (74.6 mmol) of NBS are then added in portions, and stirring is continued at this temperature for 4 h. The mixture is then treated with 15 mL of water and extracted with CH2Cl2. The organic phase is dried over MgSO4, and the solvents are removed in vacuo. The product is extracted by stirring with hot hexane and filtered off with suction. Yield: 17.4 g (27 mmol), 72% of theory, purity according to 1 H-NMR approx. 98%.

[0258] The following connections are made analogously:

[0259]

[0260]

[0261]

[0262] d) 6-(Dibenzo[b,d]furan-4-yl)-9-(4-(dibenzo[b,d]furan-4-yl)phenyl)-9'-phenyl-9H,9 , H-

[0263] 3,3'-bicarbazol

[0264] 9.1 g (32 mmol) of B-(9-phenyl-9H-carbazol-3-yl)boronic acid, 20.8 g (32 mmol) of 3-bromo-6-(dibenzo[b,d]furan-4-yl)-9-(4-(dibenzo[b,d]furan-4-yl)phenyl)-9H-carbazole, and 31 ml (63 mmol) of Na2CO3 (2 M solution) were suspended in 120 mL of toluene and 120 mL of ethanol. 0.73 g (0.63 mmol) of Pd(PPh3)4 was added to this suspension, and the reaction mixture was heated under reflux for 16 h. After cooling, the organic phase was separated, filtered through silica gel, washed three times with 200 mL of water, and then evaporated to dryness. The residue is recrystallized from toluene and after chromatographic purification under high vacuum (p = 5 x 10 -7 mbar) (purity 99.9%). The yield is 20.3 g (24 mmol), corresponding to 78% of theory.

[0265] e) 9-(dibenzo[b,d]furan-3-yl)-6-(dibenzo[b,d]furan-4-yl)-9'-phenyl-9H,9'H-3,3'- bicarbazol-d 32

[0266] 34 g (46.0 mmol; 1 ,00 eq) 9-(Dibenzo[b,d]furan-3-yl)-6-(dibenzo[b,d]furan-4-yl)-9'-phenyl- 9H,9'H-3,3'-bicarbazol wird in 640 mL (120 eq) Toluol-d8 [CAS 2037-26-5] suspendiert.

[0267] To this mixture, 16.6 mL (6.00 eq.) of trifluoromethanesulfonic acid is added while cooling. The reaction mixture is stirred at ambient temperature for 6 hours. Subsequently, 120 mL (130 eq.) of deuterium oxide [CAS 7789-20-0] is added dropwise at 0°C. After neutralization with a potassium sulfate solution, it is extracted with toluene and the combined organic phases are washed with brine and dried over sodium sulfate. After filtration, the solvent is removed under reduced pressure. 19 g (25 mmol, 55% of theory) of the product shown above, in a mixture with portions of H / D isotopomers and H / D isotopologues, are obtained after chromatographic purification and finally concentrated under high vacuum (p = 5 x 10'). 7 mbar) sublimated (purity 99.9%).

[0268] The following connection is established analogously:

[0269] Production of OLEDs

[0270] The following examples C1-1 to C4 and Ex1-1 to Ex4-3 (see Tables 7 and 8) present the data for various OLEDs. Examples Ex1-1 to Ex4-3 show data for OLEDs according to the invention, while examples C1-1 to C4 show corresponding comparative examples according to the prior art.

[0271] The substrates used for the OLEDs shown in Table 7 are glass plates coated with structured ITO (indium tin oxide) with a thickness of 50 nm. The exact structure of the OLEDs can be found in Table 7. The materials required for the fabrication of the OLEDs are shown in Table 9, unless previously described.

[0272] All materials are thermally evaporated in a vacuum chamber. The emission layer always consists of at least one matrix material (also called host material) and an emitting dopant (dopant, emitter), which is mixed into the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as E7:SdT1:TEG2 (52%:40%:8%) 40nm means that the material E7 is present in a volume fraction of 52% as host material 1, the compound SdT1 as host material 2 in a volume fraction of 40%, and TEG2 in a volume fraction of 8% in a 40nm thick layer. Analogously, the hole injection layer (HIL) and the electron transport layer (ETL), for example, can also consist of a mixture of two materials.

[0273] The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra and current-voltage-luminance characteristics (IUL characteristics) are measured, from which the EQE is calculated. The calculation assumes a Lambertian radiation pattern. The voltage required for a current density of 10 mA / cm 2 required is referred to here as U10. EQE10 denotes the external quantum efficiency at a current density of 10 mA / cm 2 .

[0274] For each example, the relative EQE and the relative voltage are calculated in comparison to the corresponding comparison example: rel. U (Ex) = 100 * (U10(Ex) / U10(V)) rel. EQE (Ex) = 100 * (EQE10(Ex) / EQE10(V)).

[0275] The lifetime LT90 is defined as the time after which the luminance when operated at a constant current density jo in mA / cm 2 from a starting luminance L0 (in cd / m 2) drops to 90% of this starting luminance. In the examples shown here, the current density used is 60mA / cm 2 .

[0276] For each example, the relative LT is calculated in comparison to the corresponding comparison example: rel. LT (Ex) = 100 * (LT90(Ex) / LT90(V))

[0277] Use of mixtures according to the invention in OLEDs

[0278] The compounds or material combinations according to the invention can be used in the emission layer in phosphorescent green OLEDs.

[0279] The examples according to the invention show, in particular, a significant advantage in the lifetime of the device and, compared to aryl-substituted biscarbazoles, a lower operating voltage. L ke Q m Q m Q m Q m Q m Q m Q m Q m Q m Q m Q m

[0280] 100100100 V2

Claims

Patent claims 1. Compounds according to formula (1), where the symbols and indices used are: (R) a , (R) b each independently represents a monosubstitution, a disubstitution, a trisubstitution, the maximum permissible substitution or no substitution with the substituent R; R is at each occurrence independently D or a non-deuterated or partially or fully deuterated aryl group having 6 to 18 C atoms; Y is independently O or S at each occurrence; L, L1 are each independently a single bond or a non-deuterated or partially or fully deuterated arylene group having 6 to 18 C atoms; Ar* is an aryl group with 6 to 30 C atoms or a heteroaryl group with 5 to 40 ring atoms, which can be substituted with one or more radicals R 1 can be substituted; R 1is selected, identically or differently at each occurrence, from the group consisting of D, F, CN, Si(Aryl)3, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more non-adjacent CH2 groups may be replaced by O or S and where one or more H atoms may be replaced by D, F, or CN or a non-deuterated or partially or fully deuterated aryl group having 6 to 30 C atoms or a non-deuterated or partially or fully deuterated electron-rich heteroaryl group having 9 to 40 ring atoms; Aryl is, at each occurrence, independently of one another, identically or differently, an aryl group having 6 to 30 C atoms or a heteroaryl group having 5 to 40 ring atoms, which may be partially or fully deuterated, where the compounds of formula (1) are partially or fully deuterated.

2. Compounds according to claim 1, wherein the compound of formula (1) corresponds to a compound of formula (1a), where Ar*, (R) a , (R) b , R, Y, L and L1 have the meaning given in claim 1 and the compounds of formula (1a) are partially or completely deuterated.

3. Compounds according to claim 1 or 2, wherein Y is each O.

4. Compounds according to one or more of claims 1 to 3, wherein the Degree of deuteration corresponds to 5 mol% to 100 mol%.

5. A compound according to one or more of claims 1 to 4, selected from the 6. A mixture comprising at least one compound of formula (1) according to one or more of claims 1 to 5 and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

7. Use of at least one compound of formula (1) according to one or more of claims 1 to 5 in an organic electronic device.

8. An organic electronic device comprising an anode, a cathode and at least one organic layer containing at least one compound of formula (1) according to one or more of claims 1 to 5.

9. The organic electronic device of claim 8, wherein the electronic device is an organic integrated circuit (OLICS), an organic field-effect transistor (OFET), an organic thin-film transistor (OTFT), an organic electroluminescent device, an organic solar cell (OSC), an organic optical detector, or an organic photoreceptor.

10. The organic electronic device according to claim 8 or 9, wherein the organic layer contains at least one light-emitting layer, a hole-transporting layer, a hole-injecting layer, or an electron-blocking layer containing at least one compound according to any one of claims 1 to 5.

11. Organic electronic device according to one or more of claims 8 to 10, characterized in that the light-emitting layer contains the at least one compound of formula (1) according to one of claims 1 to 5.

12. Organic electronic device according to one or more of claims 8 to 11, characterized in that the light-emitting layer contains at least one further matrix material in addition to the compound of formula (1) according to one of claims 1 to 5.

13. Organic electroluminescent device according to claim 12, characterized in that the further matrix material corresponds to one or more of the compounds of formulas (A), (B), (C), (D) and / or (E), , where the symbols and indices used are: X is the same or different at each occurrence N or CR 6 , preferably N; L 2 is at each occurrence, identically or differently, a single bond or an aromatic or heteroaromatic ring system with 5 to 24 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; R## is, identically or differently at each occurrence, D, F, CN or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted with one or more radicals R 6 may be substituted and two adjacent substituents R## may together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system which may be substituted with one or more radicals R 7 can be substituted; Y is the same or different at each occurrence N or CR 9 , whereby it is excluded that two adjacent Ys simultaneously mean N; V 2 is O or S; R 6is, identically or differently at each occurrence, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which may be partially or fully deuterated; two radicals R 6 also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with each other; Ar 5represents, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted by one or more radicals R 7 may be substituted; R 7 is the same or different at each occurrence D, F, CI, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more non-adjacent CH2 groups are replaced by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which may be partially or fully deuterated; two or more radicals R 7 form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Q R is, at each occurrence, identically or differently, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may be replaced by F; Q R is the same or different at each occurrence: H, D, F, CI, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 6 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 6 may be substituted; two or more radicals R 9 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; b1 is 0, 1, 2, 3 or 4; b2 is 0, 1, 2 or 3.

14. Organic electronic device according to one or more of claims 8 to 13, characterized in that the light-emitting layer contains a phosphorescent emitter.

15. Organic electronic device according to one or more of claims 8 to 14, characterized in that it is an electroluminescent device selected from the group consisting of organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic light-emitting diodes (OLEDs).

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