WO2024133211A1 - Nouveaux matériaux pour dispositifs électroluminescents organiques - Google Patents

Nouveaux matériaux pour dispositifs électroluminescents organiques Download PDF

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WO2024133211A1
WO2024133211A1 PCT/EP2023/086562 EP2023086562W WO2024133211A1 WO 2024133211 A1 WO2024133211 A1 WO 2024133211A1 EP 2023086562 W EP2023086562 W EP 2023086562W WO 2024133211 A1 WO2024133211 A1 WO 2024133211A1
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atoms
group
ring system
aromatic
substituted
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Amir Hossain Parham
Christian Ehrenreich
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Merck Patent Gmbh
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  • the present invention relates to new compounds and organic electroluminescent devices such as OLEDs (organic light emitting diodes) containing these compounds, for example as electron transport materials and/or matrix materials, optionally in combination with another matrix material.
  • OLEDs organic light emitting diodes
  • the present invention further relates to mixtures and formulations containing these new compounds.
  • organic electroluminescent devices e.g. OLEDs - organic light emitting diodes or OLECs - organic light emitting electrochemical cells
  • OLEDs organic light emitting diodes
  • OLECs organic light emitting electrochemical cells
  • organic semiconductors are used as organic functional materials
  • organometallic complexes that exhibit phosphorescence are increasingly being used as emitting materials (M. A. Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6).
  • organometallic compounds are used as phosphorescence emitters.
  • there is still room for improvement in both OLEDs that exhibit singlet emission and OLEDs that exhibit triplet emission particularly with regard to efficiency, operating voltage and lifetime.
  • organic electroluminescent devices are not only determined by the emitters used.
  • the other materials used such as host and matrix materials, hole blocking materials, electron transport materials, hole transport materials and electron or exciton blocking materials, are also of particular importance. Improvements to these materials can lead to significant improvements in electroluminescent devices.
  • heteroaromatic compounds in particular are used as electron transport materials and as matrix material for phosphorescent compounds.
  • matrix material is usually used when a host material for phosphorescent emitters is meant. This use of the term “matrix material” is also used for the present invention.
  • Triazinebenzimidazole derivatives are known as compounds that can be used as electron transport material and/or as matrix material in OLEDs (see KR 2018/007329, CN 106946853, CN 110922388, CN 112159361 CN202110215311 , WO 2015/000549, WO 2016/012075, WO 2015/000549, WO 2019/017734 or WO 2020/9679).
  • the object of the present invention is therefore to provide compounds which are suitable for use in an organic electroluminescent device and which, when used in this device, lead to good device properties, as well as to provide the corresponding organic electroluminescent device.
  • the object of the present invention is to provide compounds which lead to a long service life, good efficiency and low operating voltage.
  • the properties of the matrix materials in particular have a significant influence on the service life and efficiency of the organic luminescent device.
  • a further object of the present invention can be seen in providing compounds which are suitable for use in a phosphorescent or fluorescent, in particular a phosphorescent, OLED, in particular as a matrix material.
  • L 1 is selected from the group consisting of a single bond, an aromatic ring system with 6 - 40 ring atoms or a heteroaromatic ring system with 5 - 40 ring atoms, where optionally, both ring systems independently of one another are partially or fully substituted with D;
  • L 2 is a single bond or an aromatic ring system with 6 - 40 ring atoms, optionally partially or fully substituted with D;
  • L 3 is selected from the group consisting of a single bond, an aromatic ring system with 6 - 40 ring atoms or a heteroaromatic ring system with 5 - 40 ring atoms, wherein optionally, both ring systems independently of one another are partially or fully substituted with D;
  • Het is a group selected from or
  • Het 1 is selected from the group consisting of an aromatic ring system having 6 - 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms, wherein, optionally, independently of one another, both ring systems are partially or fully substituted with R 3 ;
  • R is the same or different at each occurrence and is selected from the
  • H, D, F, CN a straight-chain alkyl group with 1 to 20 C atoms or an alkenyl or alkynyl group with 2 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, where one or more non-adjacent CH2 groups can be replaced by O or S, and where at least one H atom can be replaced by D, F, or CN, or an aromatic ring system with 6 to 40 ring atoms or heteroaromatic ring system with 5 to 40 ring atoms, in which at least one H atom can be replaced by D, F, CI, Br, I or CN, and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; two or more adjacent substituents R can form an aliphatic, aromatic or heteroaromatic ring system with one another;
  • R 1 is the same or different at each occurrence and is selected from the group consisting of
  • R 2 is the same or different at each occurrence and is selected from the group consisting of
  • R 3 is the same or different at each occurrence and is selected from the group consisting of
  • R 4 is the same or different at each occurrence and is selected from the group consisting of
  • n 3 if m is 4 or m is 3 if n is 4 and wherein the following compound is excluded from the invention:
  • D or “D-atom” stands for deuterium.
  • An aryl group in the sense of this invention contains 6 to 40 ring atoms, preferably C atoms.
  • a heteroaryl group in the sense 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 or heteroaryl group is understood to be either a simple aromatic cycle, i.e.
  • phenyl derived from benzene, or a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a condensed aryl or heteroaryl group, for example derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline.
  • An aryl group with 6 to 30 C atoms is therefore preferably phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylenyl, fluoranthenyl, dibenzoanthracenyl, chrysenyl or perylenyl, whereby the attachment of the aryl group as a substituent is not restricted.
  • An aromatic ring system in the sense of this invention contains 6 to 40 C atoms in the ring system, wherein the ring system also comprises the aryl groups described above.
  • a heteroaromatic ring system in the sense 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 also includes heteroaryl groups, as described above.
  • the heteroatoms in the heteroaromatic ring system are preferably selected from N, O and/or S.
  • An aromatic or heteroaromatic ring system within the meaning of this invention is understood to mean a system which does not necessarily only contain aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be interrupted by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C or O atom or a carbonyl group.
  • a non-aromatic unit preferably less than 10% of the atoms other than H
  • systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ether, stilbene, etc.
  • aromatic or heteroaromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are interrupted, for example by a linear or cyclic alkyl group or by a silyl group.
  • systems in which two or more aryl or heteroaryl groups are directly bonded to one another such as e.g. B. biphenyl, terphenyl, quaterphenyl or bipyridine, are also included in the definition of the aromatic or heteroaromatic ring system.
  • An aromatic or heteroaromatic ring system with 5 - 40 ring atoms which can be linked to the aromatic or heteroaromatic via any position, is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxen
  • a straight-chain alkyl group with 1 to 20 C atoms includes, for example, the radicals 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
  • alkenyl group with 2 to 20 C atoms is understood to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl.
  • An alkynyl group with 2 to 20 C atoms is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.
  • a straight-chain alkyl group with 1 - 20 C atoms or a branched alkyl group with 3 to 20 C atoms, in which one or more non-adjacent CH2 groups can be replaced by O or S, and where at least one H atom can be replaced by D, F or CN, is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, thiomethyl, 1-thioethyl, 1-thio-i-propyl, 1-thio-n-propoyl, 1-thio-i-butyl, 1-thio-n-butyl or 1-thio-t-butyl.
  • this alkyl group can be selected from the above-mentioned alkyl groups.
  • Neighboring carbon atoms in the sense of the present invention are carbon atoms that are directly linked to one another. Furthermore, “neighboring radicals” in the definition of radicals means that these radicals are bonded to the same carbon atom or to neighboring carbon atoms. These definitions apply accordingly, among other things, to the terms “neighboring groups” and “neighboring substituents.”
  • the compounds according to the invention according to formula (1) can be selected from compounds of the following formula (1a) or formula (1b), preferably from compounds of formula (1a):
  • Het 1 is selected from the group consisting of an aromatic ring system with 6 - 25 ring atoms or a heteroaromatic ring system with 5 to 24 ring atoms, where, optionally, independently of one another, both ring systems can be partially or fully substituted with R 3 .
  • Het 1 is particularly preferably selected from the group consisting of an aromatic ring system with 6 - 18 ring atoms or a heteroaromatic ring system with 5 to 18 ring atoms, where, optionally, independently of one another, both ring systems can be partially or fully substituted with R 3 .
  • An aromatic ring system with 6 to 25 ring atoms is preferably selected from ortho-, meta- or para-phenyl, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl, triphenylenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, fluoranthenyl, benzofluoranthenyl or dibenzoanthracenyl and an aromatic ring system with 6 to 18 ring atoms is preferably selected from the above-mentioned phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphen
  • a heteroaromatic ring system having 5 to 24 ring atoms, if it does not represent a linker, is preferably selected from the structures of the following formulae Het (1) to Het (5):
  • Het 1 represents a heteroaromatic group having 5 to 24 ring atoms
  • this group is more preferably selected from structures according to the formulae Het (1) to Het (4) and Het (6) to Het (17); more preferably Het 1 represents a heteroaromatic group having 5 to 18 ring atoms which is selected from structures according to the formulae Het (6) to Het (17) and most preferably the heteroaromatic group having 5 to 18 ring atoms is selected from structures according to the formulae Het (10) to Het (17).
  • Het is selected from the group consisting of Het (1) to Het (3) or Het (5): where
  • Het is selected from the group consisting of Het (1), Het (2) or Het (3).
  • the linker L 1 is selected from the group consisting of a single bond, an aromatic ring system with 6 to 25 ring atoms or a heteroaromatic ring system with 5 to 18 ring atoms. It is particularly preferred that L 1 represents a single bond, an aromatic ring system with 6 to 18 ring atoms or a heteroaromatic ring system with 5 to 18 ring atoms. In the case of a heteroaromatic ring system, this ring system preferably represents a dibenzofuran or dibenzothiophene. These ring systems are optionally partially or fully substituted with D.
  • the linker L 2 is selected from the group consisting of a single bond or an aromatic ring system having 6 to 25 ring atoms. It is particularly preferred that L 2 represents a single bond or an aromatic ring system having 6 to 18 ring atoms.
  • the ring system is optionally partially or fully substituted with D.
  • the linker L 3 is preferably selected from the group consisting of a single bond, an aromatic ring system with 6 to 25 ring atoms or a heteroaromatic ring system with 5 to 18 ring atoms. It is particularly preferred that L 3 represents a single bond, an aromatic ring system with 6 to 18 ring atoms or a heteroaromatic ring system with 5 to 18 ring atoms. In the case of a heteroaromatic ring system, this ring system preferably represents a dibenzofuran or dibenzothiophene. These ring systems are optionally partially or fully substituted with D.
  • the substituent R is preferably selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where one or more non-adjacent CH 2 groups can be replaced by O or S and where at least one H atom can be replaced by D, F or CN or an aromatic ring system having 6 to 24 ring atoms or heteroaromatic ring system having 5 to 24 ring atoms, in which at least one H atom can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; more preferably, R is selected from the group consisting of H, D, F, CN, a straight-chain alkyl group with 1 to 6 C atoms or an alkenyl or alkyny
  • the substituent R 1 is preferably selected from the group consisting of H, D, F, CN, a straight-chain alkyl group with 1 to 10 C atoms or an alkenyl or alkynyl group with 2 to 10 C atoms or a branched or cyclic alkyl group with 3 to 10 C atoms, where one or more non-adjacent CH 2 groups can be replaced by O or S and where at least one H atom can be replaced by D, F or CN or an aromatic ring system with 6 to 24 ring atoms or heteroaromatic ring system with 5 to 18 ring atoms, in which at least one H atom can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; More preferably, R 1 is selected from the group consisting of H, D, F, CN, an aromatic ring system having 6 to 12 ring atoms or a heteroaromatic ring system having 5
  • the substituent R 2 is preferably selected from the group consisting of an aromatic ring system with 6 - 24 ring atoms or a heteroaromatic ring system with 5 to 18 ring atoms, where, optionally, both ring systems independently of one another are partially or fully substituted with R 4 . More preferably, R 2 is selected from the group consisting of an aromatic ring system with 6 - 18 ring atoms or a heteroaromatic ring system with 5 to 18 ring atoms. The respective ring systems can independently of one another be partially or fully substituted with R 4 .
  • the substituent R 3 is preferably selected from the group consisting of H, D, F, CN, a straight-chain alkyl group with 1 to 10 C atoms or an alkenyl or alkynyl group with 2 to 10 C atoms or a branched or cyclic alkyl group with 3 to 10 C atoms, where one or more non-adjacent CH2 groups can be replaced by O or S and where at least one H atom can be replaced by D, F or CN or an aromatic ring system with 6 to 24 C atoms or heteroaromatic ring system with 5 to 18 ring atoms, in which at least one H atom can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; two or more adjacent substituents R can form an aliphatic, aromatic or heteroaromatic ring system; more preferably R 3 is selected from the group consisting of H, D, F, CN, a
  • the substituent R 4 preferably represents H or D.
  • the present invention further provides a mixture comprising at least one compound according to formula (1) 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).
  • TADF thermalally activated delayed fluorescence
  • the present invention also further relates to a formulation comprising at least one compound according to formula (1) or a mixture as described above and at least one solvent.
  • Yet another object of the invention is an organic electroluminescent device comprising an anode, a cathode and at least one organic layer containing at least one compound of formula (1).
  • Particularly suitable compounds of formula (1) are the compounds E1 to E27 of the following Table 2:
  • the compounds of the invention can be prepared using methods known to those skilled in the art, such as Suzuki coupling.
  • the compounds according to formula (1) of the present invention can be prepared as shown in Scheme 1 below:
  • the Grignard reagent is transferred to a dropping funnel and slowly added to this solution. After stirring overnight at room temperature, the mixture is diluted with 100 ml of THF and 50 ml of 1M HCl is added. The precipitate formed is washed with water, ethanol and heptane and recrystallized from toluene.
  • the Grignard reagent is transferred to a dropping funnel and slowly added to this solution. After stirring overnight at room temperature, the mixture is diluted with 100 mL of THF and 50 mL of 1M HCl is added. The precipitate formed is washed with water, ethanol and heptane and recrystallized from toluene.
  • a suitable process for the partial or complete deuteration of a compound according to the invention according to formula (1) by exchanging one or more H atoms for D atoms is a treatment of the compound to be deuterated in the presence of a platinum catalyst or palladium catalyst and a deuterium source.
  • deuterium source means any compound which contains one or more D atoms and can release them under suitable conditions.
  • 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 ⁇ , 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, the fully deuterated solvent being 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.
  • the compounds of formula (1) can be obtained in high purity, preferably at least 98% purity (determined by 1 H-NMR and/or HPLC).
  • formulations of the compounds according to the invention or of mixtures of compounds according to the invention with further functional materials are required.
  • these formulations can be, for example, solutions, dispersions or emulsions. It may be preferable 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-methyl-naphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin
  • the above compounds according to the invention according to formula (1), preferably formula (1a) or compounds E1 to E27, are suitable for use in an organic electroluminescent device (synonymous with an organic electroluminescent device), preferably an organic light-emitting transistor ( ⁇ LET), an organic field quench device (OFQD), an organic light-emitting electrochemical cell (OLEC, LEC, LEEC), an organic laser diode (O-laser) or an organic light-emitting diode (OLED).
  • ⁇ LET organic light-emitting transistor
  • OFQD organic field quench device
  • OLED organic light-emitting electrochemical cell
  • O-laser organic laser diode
  • OLED organic light-emitting diode
  • 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.
  • 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.
  • EML light-emitting layer
  • HIL hole injection layer
  • HTL hole transport layer
  • HBL hole blocking layer
  • ETL electron transport layer
  • EIL electron injection layer
  • EIL electron injection layer
  • 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.
  • the organic electroluminescent device according to the invention can also be a tandem electroluminescent device, in particular for white-emitting OLEDs.
  • the device can also contain inorganic materials or layers that are made entirely of inorganic materials.
  • the compound of formula (1) according to the invention can be used in different layers, depending on the precise structure. Preference is given to an organic electroluminescent device comprising a compound according to formula (1) or the preferred embodiments set out above in at least one light-emitting layer as matrix material (synonym for host material) for fluorescent emitters, phosphorescent emitters or for emitters that exhibit TADF (thermally activated delayed fluorescence), in particular for phosphorescent emitters. Furthermore, the compound according to the invention can also be used in at least one electron transport layer and/or in at least one hole transport layer and/or in at least one exciton blocking layer and/or in at least one hole blocking layer. The compound according to the invention is particularly preferably used as matrix material in at least one light-emitting layer or as an electron transport or hole blocking material in an electron transport or hole blocking layer.
  • the compounds according to the invention according to formula (1) can be used as matrix material in the at least one light-emitting layer, this layer containing at least one further matrix material (so-called mixed matrix systems).
  • Suitable matrix materials which 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.
  • another phosphorescent emitter which emits at a shorter wavelength than the actual emitter, can be present in the mixture as a co-host or a compound that does not participate or does not participate to a significant extent in the charge transport, such as a wide band-gap compound.
  • a wide-band-gap material is understood here to mean a material in the sense of the disclosure of US 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 distance between the HOMO and LUMO energy of a material.
  • Particularly suitable further matrix materials which can advantageously be combined with compounds of formula (1) as previously described or preferably described in a system can be selected from the compounds of formulas (2) to (12) as described below.
  • a further subject matter of the invention is therefore an organic electroluminescent device comprising an anode, a 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 (2) to (12) as matrix material 2,
  • a 1 is C(R 7 ) 2 , NR 7 , O or S;
  • A is, at each occurrence independently, a group of the formula
  • X2 is the same or different at each occurrence and is CH, CR 6 or N, where a maximum of 2 symbols X2 N can be used;
  • Ar is, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R 7 ;
  • Ar 1 identical or different on each occurrence, represents an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R 7 ;
  • R 8 is, identically or differently on each occurrence, 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; c, c1, c2 each independently on each occurrence is 0 or
  • d, d1 , d2 each independently mean 0 or
  • s is preferably 0 or 1 when the radical R 6 is different from D, particularly preferably 0.
  • t is preferably 0 or 1 when the radical R 6 is different from D, particularly preferably 0.
  • u is preferably 0 or 1 when the radical R 6 is different from D, particularly preferably 0.
  • the sum of the indices s, t and u in compounds of the formulas (2), (3), (4) and (8) to (12) is preferably at most 6, particularly preferably at most 4 and particularly preferably at most 2. This preferably applies when R 6 is different from D.
  • c, c1, c2 each independently represent 0 or 1 at each occurrence, where the sum of the indices c+c1+c2 represents 1 at each occurrence.
  • c2 represents 1.
  • compounds of the formulas (2) to (5) and (8) to (12) can be combined with the compounds of the formula (1) according to the invention, where R 6 is the same or different on each occurrence and is 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, where the alkyl group can be substituted in each case by one or more radicals R 7 , or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably having 5 to 40 ring atoms, which can be substituted in each case by one or more radicals R 7 .
  • compounds of the formulas (2) to (5) and (8) to (12) can be combined with the compounds of the formula (1) according to the invention, where R 6 is the same or different on each occurrence and is selected from the group consisting of D or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may be substituted by one or more radicals R 7 .
  • Ar 1 in compounds of the formulae (2), (3), (4) and (8) to (12) is selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorenyl, which can be linked via the 1-, 2-, 3- or 4-position, spirobifluorenyl, which can be linked via the 1-, 2-, 3- or 4-position, naphthyl, in particular 1- or 2-linked naphthyl, or radicals derived from indole, benzofuran, benzothiophene, carbazole, which can be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which can be linked via the 1-, 2-, 3- or 4-position, dibenzo- thiophene, which can be linked via the 1-, 2-, 3-
  • the substituent R 7 which is bonded to the nitrogen atom preferably represents an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more radicals R 8 .
  • this substituent R 7 is the same or different on each occurrence and represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms.
  • R 7 Preferred embodiments for R 7 are phenyl, biphenyl, terphenyl and quaterphenyl, which are preferably unsubstituted, and radicals derived from triazine, pyrimidine and quinazoline, which may be substituted by one or more radicals R 8 .
  • a 1 in formula (3) or (4) is C(R 7 ) 2
  • the substituents R 7 which are bonded to this carbon atom are preferably identical or different on each occurrence and are a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more radicals R 8 .
  • R 7 is very particularly preferably a methyl group or a phenyl group.
  • the radicals R 7 can also form a ring system with one another, resulting in a spiro system.
  • these compounds are partially or completely deuterated, particularly preferably completely deuterated.
  • the additional matrix material is a deuterated compound
  • the additional matrix material contains a mixture of deuterated Compounds with the same basic chemical structure that differ only in the degree of deuteration.
  • this is a mixture of deuterated compounds of the formulas (2) to (5) and (8) to (12), as described above, the degree of deuteration of these compounds being at least 50% to 90%, preferably 70% to 100%.
  • 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.
  • a suitable method for deuterating a compound by replacing one or more H atoms with D atoms is to treat the compound to be deuterated in the presence of a platinum catalyst or palladium catalyst and a deuterium source.
  • deuterium source means any compound that contains one or more D atoms and can release them under suitable conditions.
  • 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, the fully deuterated solvent being 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.
  • Suitable further matrix materials for combination with compounds of formula (1) are the compounds described in WO2019/229011, Table 3, pages 137 to 203, which may also be partially or fully deuterated, or compounds described in WO2021/180625, Table 3, pages 131 to 127 and in Table 4, pages 137 to 139, or KR20230034896 A, on pages 42 to 47, compounds [2-1] to [2-110], or on pages 49 to 51, compounds [3-1] to [3-26], which may also be partially or fully deuterated.
  • Particularly suitable host materials which are selected according to the invention and are preferably used in combination with at least one compound of formula (1) or preferred compounds of formula (1a) in the electroluminescent device according to the invention are the compounds of Table 4.
  • the above-mentioned host materials of formula (1) and their preferred embodiments or the compounds of Table 1 and the compounds E1 to E27 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 formulas (2) to (5) and (8) to (12) and their preferred embodiments of Table 3 or the compounds H1 to H30.
  • Very particularly preferred mixtures of the compounds of formula (1) with the host materials of formulas (2) to (5) and (8) to (12) for the device according to the invention are obtained by combining the compounds E1 to E27 with the compounds H1 to H27 as shown below in Table 5.
  • the first mixture M1 for example, is a combination of the compound E1 with H1.
  • 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 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 total mixture or based on the total composition of the light-emitting layer.
  • the concentration of the sum of all host materials of the formulas (2) to (5) and (8) to (12) as described above or described as preferred, 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 entire mixture or based on the entire composition of the light-emitting layer.
  • the present invention also relates to a mixture which, in addition to the above-mentioned host materials of the formula (1), hereinafter referred to as host material 1, and the host material of at least one of the formulas (2) to (5) and (8) to (12), hereinafter referred to as host material 2, as previously described or preferably described, contains at least one phosphorescent emitter.
  • the present invention also relates to a mixture selected from M1 to M729, which contains at least one phosphorescent emitter.
  • a further subject matter of the invention is therefore an organic electroluminescent device comprising an anode, a 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 formula (13)
  • W is O, S, C(R 9 ) 2 , N-Ar 2 ;
  • R 9 is each independently a straight-chain or branched
  • Alkyl group having 1 to 4 C atoms which may be partially or fully deuterated, or an unsubstituted or partially or fully deuterated aromatic ring system having 6 to 18 C atoms, where two substituents R 9 can form with the C atom to which they are bonded a mono- or polycyclic, aliphatic or aromatic or heteroaromatic unsubstituted, partially deuterated or fully deuterated ring system, which can be substituted by one or more substituents R 12 ;
  • Ar 2 is, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 30 ring atoms which may be substituted by one or more R 12 radicals; two Ar 2 radicals which are bonded to the same N atom, P atom or B atom may also be bridged to one another by a single bond or a bridge selected from C(R 12 ) 2 , O or S;
  • R" is selected, identically or differently, at each occurrence from the group consisting of D, F, CN, an aliphatic hydrocarbon radical with 1 to 20 C atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, in which one or more H atoms can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each with 1 to 4 carbon atoms; two or more adjacent R 3 substituents can form a mono- or polycyclic, aliphatic ring system with each other; it came from these definitions - but I find it too broad, I will use the following definition for my foreign version - thanks for finding the error
  • R' is at each occurrence, identically or differently, an aliphatic, aromatic or heteroaromatic organic radical, in particular a Hydrocarbon residue with 1 to 20 C atoms, in which one or more H atoms can be replaced by F;
  • R 12 is, on each occurrence, the same or different, 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, where one or more non-adjacent CH 2 groups may be replaced by O or S and where one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 30 ring atoms, in which one or more H atoms may be replaced by D, F, CI, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; two or more adjacent R 12 substituents may form a mono- or polycyclic, aliphatic ring system with one another; x, x1 are, on each occurrence, independently 0, 1, 2, 3 or 4; y, z are each independently 0, 1 or 2; a1, a2 are each independently 0,
  • the compounds according to formula (1) according to the invention or the preferred embodiments are used as matrix material alone or in a mixed matrix system for an emitting compound in a light-emitting layer, they are preferably used in combination with one or more phosphorescent materials (triplet emitters).
  • phosphorescent emitters typically includes compounds in which the 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, for example a quintet state.
  • a transition from a triplet state is preferably understood here.
  • Particularly suitable phosphorescent emitters are compounds which, when suitably excited, emit light, 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.
  • 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.
  • all luminescent compounds containing the above-mentioned metals are regarded as phosphorescent emitters.
  • a further subject of the invention is therefore an organic electroluminescent device as described above or preferably described, characterized in that the light-emitting layer contains at least one phosphorescent emitter in addition to the host materials 1 and 2.
  • 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.
  • a yellow-emitting layer is understood to be a layer whose photoluminescence maximum is in the range from 540 to 570 nm.
  • An orange-emitting layer is understood to be a layer whose photoluminescence maximum is in the range from 570 to 600 nm.
  • a red-emitting layer is understood to be a layer whose photoluminescence maximum is in the range from 600 to 750 nm.
  • a green-emitting layer is understood to be a layer whose photoluminescence maximum is in the range from 490 to 540 nm.
  • a blue-emitting layer is understood to be a layer whose photoluminescence maximum is in the range from 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 comprises the inventive combination of the host material 1 of formula (1), in particular formula (1a), and the host material 2, consisting of at least one of (2) to (5) and (8) to (13) and the corresponding emitter.
  • the photoluminescence spectrum of the selected emitter is usually measured in an oxygen-free solution, 10' 5 molar, with the measurement being carried out at room temperature and any solvent in which the selected emitter dissolves in the stated concentration being 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.
  • Preferred phosphorescent emitters are therefore yellow emitters, preferably from Table 6, whose triplet energy T is preferably between ⁇ 2.3 eV and ⁇ 2.1 eV.
  • Preferred phosphorescent emitters are therefore green emitters, preferably from Table 6, whose triplet energy T 1 is preferably between ⁇ 2.5 eV and ⁇ 2.3 eV.
  • Green emitters preferably 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.
  • 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 condensed ring system, particularly preferably with at least 14 ring atoms.
  • Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines.
  • An aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group. is, preferably in the 9-position.
  • An aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are bonded directly 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 in the 1,6-position.
  • emitting compounds are indenofluorenamines or diamines, benzoindenofluorenamines or diamines, and dibenzoindenofluorenamines or diamines, as well as indenofluorene derivatives with condensed aryl groups. Pyrene-arylamines are also preferred. Also preferred are benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines and fluorene derivatives which are linked to furan units or to thiophene units.
  • the light-emitting device or the mixture according to the invention can also contain materials which exhibit TADF (thermally activated delayed fluorescence).
  • the at least one light-emitting layer of the organic electroluminescent device can comprise, in addition to the host materials (matrix materials) 1 and 2, as described above or described as preferred, further host materials or matrix materials, so-called mixed matrix systems.
  • These mixed matrix systems preferably comprise three or four different matrix materials, particularly preferably three different matrix materials (that is, a further matrix component in addition to the host materials 1 and 2, as described above).
  • Particularly suitable matrix materials which can be used in combination as a matrix component of a mixed matrix system are selected from wide-open-gap materials, bipolar host materials, electron transport materials (ETM) and hole transport materials (HTM).
  • the mixture contains no further components, i.e. functional materials, in addition to the components of the host material of formula (1) and the host material 2, as described above.
  • 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 only material source when vaporizing the host materials for the light-emitting layer and which have a constant mixing ratio when vaporizing. This makes it possible to vaporize a layer with achieve a uniform distribution of the components without the need for precise control of a large number of material sources.
  • premix systems consisting of two matrix materials, namely a compound of formula (I), in particular formula (Ia), and a compound of one of the formulae (2) to (5) and (8) to (13).
  • premix systems consisting of three matrix materials, namely a compound of formula (1), in particular formula (1a), and two compounds of formulas (2) to (5) and (8) to (13).
  • 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 the host materials 1 and 2, as described above or preferably described, optionally with the phosphorescent emitter, as described above or preferably described, are provided for this purpose in a formulation which contains at least one solvent. Suitable formulations have been described above.
  • 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. %, more preferably between 99 and 10 vol. %, particularly preferably between 98 and 60 vol. %, most preferably between 97 and 80 vol. %, of matrix material made of at least one compound of formula (1) and at least one compound of one of the formulas (2) to (5) and (8) to (13)(7), (8), (9), (10) or (11) 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.
  • the compounds are processed from solution, the corresponding amounts in wt.% are preferably used instead of the amounts in vol.% given above.
  • 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), the hole injecting material and hole transporting material of which belong to the class of arylamines.
  • HIL hole injection layer
  • HTL hole transport layer
  • the sequence of layers in the organic electroluminescent device according to the invention is preferably as follows:
  • This sequence of layers is a preferred sequence.
  • all materials that are used according to the prior art as electron transport materials in the electron transport layer can be used as materials for the electron transport layer.
  • 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.
  • Metals with a low work function 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, Mg, Yb, Sm, etc.) are suitable as the cathode of the device according to the invention. Alloys made of an alkali or alkaline earth metal and silver are also suitable, for example a Alloy of magnesium and silver. In multilayer structures, other metals with a relatively high work function can be used in addition to the metals mentioned, such as Ag or Al, in which case combinations of the metals such as Ca/Ag, Mg/Ag or Ba/Ag are generally used.
  • alkaline earth metals e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.
  • Alloys made of an alkali or alkaline earth metal and silver are also suitable, for example a Alloy of magnesium
  • a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor 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.
  • a material with a high dielectric constant between a metallic cathode and the organic semiconductor.
  • alkali metal or alkaline earth metal fluorides but also the corresponding oxides or carbonates (e.g. LiF, Ü2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.) are suitable for this purpose.
  • Lithium quinolinate (LiQ) can also be used for this purpose.
  • the layer thickness of this layer is preferably between 0.5 and 5 nm.
  • 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.
  • Metal/metal oxide electrodes e.g. Al/Ni/NiO x , Al/PtO x
  • at least one of the electrodes must be transparent or partially transparent in order 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.
  • ITO Indium tin oxide
  • IZO indium zinc oxide
  • conductive, doped organic materials in particular conductive doped polymers.
  • 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.
  • 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.
  • the manufacture of the device according to the invention is not limited here. It is possible that one or more organic layers, including the light-emitting layer, are coated 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 10'6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10' mbar.
  • the organic electroluminescent device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapour Phase Deposition) method or with the aid of carrier gas sublimation.
  • the materials are applied at a pressure between 10'5 mbar and 1 bar.
  • OVJP Organic Vapour Jet Printing
  • the materials are applied directly through a nozzle and thus structured (e.g. M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).
  • the organic electroluminescent device according to the invention is further preferably characterized in that one or more organic layers containing the composition according to the invention are produced from solution, such as by spin coating, or using any printing method, such as screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (light induced thermal imaging, thermal transfer printing) or ink-jet printing. Soluble host materials 1 and 2 and phosphorescent emitters are required for this. Processing from solution has the advantage that, for example, the light-emitting layer can be applied very easily and inexpensively. This technique is particularly suitable for the mass production of organic electroluminescent devices.
  • 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.
  • a further subject matter 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 deposited by gas phase deposition, in particular with a sublimation process and/or with an OVPD (Organic Vapour Phase Deposition) process and/or by means of a carrier gas sublimation, or from solution, in particular by spin coating or by a printing process.
  • gas phase deposition in particular with a sublimation process and/or with an OVPD (Organic Vapour Phase Deposition) process and/or by means of a carrier gas sublimation, or from solution, in particular by spin coating or by a printing process.
  • OVPD Organic Vapour Phase Deposition
  • the organic layer according to the invention preferably the light-emitting layer
  • the materials used can each be placed in a material source and then evaporated from the various material sources (“co-evaporation”).
  • the various materials can be premixed (“premix systems”) and the mixture placed in a single material source from which it is then evaporated (“premix evaporation”). This makes it possible to vaporize the light-emitting layer with a uniform distribution of the components in a simple and quick manner, without the need for precise control of a large number of material sources.
  • a further subject matter of the invention is therefore a method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (1) 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.
  • the light emitting layer is applied by vapor deposition, wherein the components of the composition are premixed and vaporized from a single material source.
  • a further subject of the invention is therefore a method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (1) together with at least one further matrix material as a premix, successively or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters and/or emitters which TADF (thermally activated delayed fluorescence) show that they can be deposited from the gas phase.
  • TADF thermalally activated delayed fluorescence
  • the electronic devices according to the invention are characterized by one or more of the following surprising advantages over the prior art:
  • Electronic devices in particular organic electroluminescent devices containing compounds according to formula (1) or the preferred embodiments set out above and below, in particular as matrix material or as electron-conducting materials, have a very good service life. In this case, these compounds in particular cause a low roll-off, i.e. a small drop in the power efficiency of the device at high luminances.
  • Electronic devices in particular organic electroluminescent devices containing compounds according to formula (1) or the preferred embodiments set out above and below as electron-conducting materials and/or matrix materials, have excellent efficiency.
  • compounds according to the invention according to formula (1) or the preferred embodiments set out above and below result in a low operating voltage when used in electronic devices.
  • optical loss channels can be avoided in electronic devices, in particular organic electroluminescent devices. As a result, these devices are characterized by a high PL and thus high EL efficiency of emitters or an excellent energy transfer from the matrices to dopants.
  • the compounds according to formula (1) or the preferred embodiments described above and below have a deep triplet level Ti, which can be, for example, in the range of 2.50 eV - 2.90 eV.
  • the Gaussian16 program package (Rev. B.01) is used in all quantum chemical calculations.
  • the neutral singlet ground state is optimized at the B3LYP/6-31G(d) level.
  • HOMO and LUMO values are determined at the B3LYP/6-31G(d) level for the ground state energy optimized with B3LYP/6-31G(d).
  • TD-DFT singlet and triplet excitations are calculated using the same method (B3LYP/6-31G(d)) and the optimized ground state geometry.
  • B3LYP/6-31G(d) the same method
  • the default settings for SCF and gradient convergence are used.
  • the HOMO is obtained as the last orbital occupied by two electrons (alpha occ. eigenvalues) and LIIMO as the first unoccupied orbital (alpha virt. eigenvalues) in Hartree units, where HEh and LEh stand for the HOMO energy in Hartree units and the LUMO energy in Hartree units, respectively. From this, the HOMO and LUMO value in electron volts, calibrated using cyclic voltammetry measurements, is determined as follows:
  • the triplet level T1 of a material is defined as the relative excitation energy (in eV) of the triplet state with the lowest energy resulting from the quantum chemical energy calculation.
  • the singlet level S1 of a material is defined as the relative excitation energy (in eV) of the singlet state with the second lowest energy resulting from the quantum chemical energy calculation.
  • the lowest energy singlet state is called SO.
  • Glass plates coated with structured ITO (indium tin oxide) with a thickness of 50 nm are coated with 20 nm PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOSTM P VP AI 4083 from Heraeus Precious Metals GmbH Germany, spun on from aqueous solution) for improved processing. These coated glass plates form the substrates onto which the OLEDs are applied.
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate
  • the OLEDs basically have the following layer structure: substrate / hole transport layer (HTL) / optional intermediate layer (IL) / electron blocking layer (EBL) / emission layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally a cathode.
  • the cathode is formed by a 100 nm thick aluminum layer.
  • Table 4 The exact structure of the OLEDs can be found in Table 4. The materials required to manufacture the OLEDs are shown in Table 5.
  • the emission layer always consists of at least one matrix material (host material) and an emitting dopant (dopant, emitter), which is mixed into the matrix material or materials by co-evaporation in a certain volume proportion.
  • a specification such as IC1:IC3:TEG1 (55%:35%:10%) means that the material IC1 is present in the layer in a volume proportion of 55%, IC3 in a proportion of 35% and TEG1 in a proportion of 10%.
  • the electron transport layer can also consist of a mixture of two materials.
  • the OLEDs are characterized as standard.
  • the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in Im/W) and the external quantum efficiency (EQE, measured in percent) are determined as a function of the luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming a Lambertian radiation characteristic, as well as the service life.
  • the electroluminescence spectra are determined at a luminance of 1000 cd/m 2 and the CIE 1931 x and y color coordinates are calculated from this.
  • the U1000 in Table 2 indicates the voltage required for a luminance of 1000 cd/m 2.
  • SE1000 and LE1000 indicate the current or power efficiency achieved at 1000 cd/m 2 .
  • EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m 2 .
  • the lifetime LD is defined as the time after which the luminance drops from the starting luminance to a certain proportion L1 when operated at a constant current.
  • LO;jO 20mA/cm 2
  • Examples V1-V5 are comparative examples according to the prior art, examples E1-E15 show data of OLEDs according to the invention.

Abstract

La présente invention concerne de nouveaux composés et des dispositifs électroluminescents organiques tels que des OLED (diodes électroluminescentes organiques) qui contiennent ces composés, par exemple en tant que matériaux de transport d'électrons et/ou matériaux de matrice, éventuellement combinés à un autre matériau de matrice. L'invention concerne également des mélanges et des formulations qui contiennent ces nouveaux composés.
PCT/EP2023/086562 2022-12-21 2023-12-19 Nouveaux matériaux pour dispositifs électroluminescents organiques WO2024133211A1 (fr)

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Application Number Priority Date Filing Date Title
EP22215598.8 2022-12-21

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WO2024133211A1 true WO2024133211A1 (fr) 2024-06-27

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