EP4416155A1 - Matériaux pour dispositifs électroluminescents organiques - Google Patents

Matériaux pour dispositifs électroluminescents organiques

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Publication number
EP4416155A1
EP4416155A1 EP22802544.1A EP22802544A EP4416155A1 EP 4416155 A1 EP4416155 A1 EP 4416155A1 EP 22802544 A EP22802544 A EP 22802544A EP 4416155 A1 EP4416155 A1 EP 4416155A1
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European Patent Office
Prior art keywords
atoms
substituted
occurrence
pct
carbon atoms
Prior art date
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EP22802544.1A
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German (de)
English (en)
Inventor
Amir Hossain Parham
Christian Ehrenreich
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Merck Patent GmbH
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Merck Patent GmbH
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Publication of EP4416155A1 publication Critical patent/EP4416155A1/fr
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/14—Ortho-condensed systems
    • C07D491/147—Ortho-condensed systems the condensed system containing one ring with oxygen as ring hetero atom and two rings with nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/90—Multiple hosts in the emissive layer
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene

Definitions

  • the present invention relates to diazabenzofurocarbazole derivatives
  • OLEDs organic electroluminescent devices
  • carbazole derivatives dibenzofuran derivatives, indenocarbazole derivatives, indolocarbazole derivatives, benzofurocarbazole derivatives and benzothienocarbazole derivatives are used as matrix materials for phosphorescent emitters.
  • Benzofurocarbazole derivatives and benzothienocarbazole derivatives are described, for example, in WO10107244, WO10083872, KR20130109837, US20150021556, US20160308142 and KR20170086329.
  • Azabenzofurocarbazole derivatives and azabenzothienocarbazole derivatives are described, for example, in KR20170139443, WO18050583, US2019148646 and WO19179497.
  • US2015236262 describes a light-emitting device whose
  • 35 light-emitting layer contains at least one carbazole-based compound and at least one heterocyclic compound.
  • the heterocyclic compound can also be a benzofurocarbazole derivative or a benzothienocarbazole derivative.
  • organic layer which may be unsubstituted or partially deuterated, contained in particular in an emitting auxiliary layer.
  • the object of the present invention is to provide
  • electroluminescent devices containing compounds of the following formula (1) have improvements over the prior art, in particular when using the compounds as matrix material for
  • a first object of the present invention is a compound according to formula (1), P21177 SC
  • Each occurrence of Y is, independently of one another, N, [L]b-Ar2 or [L]t>i -Ars, where exactly two Ys stand for N, which are linked by at least one group [L]b-Ar2 and/or [L] bi-ars are separated;
  • V is O or S
  • Li is a single bond or an aromatic or heteroaromatic ring system containing 5 to 30 ring atoms which is unsubstituted or partially or fully substituted with D
  • Rx, R# are identical or different on each occurrence and are aromatic
  • Ring system with 6 to 30 ring atoms which can be substituted with one or more groups R or a heteroaromatic ring system with 5 to 30 ring atoms, which can be substituted with one or more groups R;
  • L is, identically or differently, on each occurrence an aromatic ring system having 5 to 30 ring atoms, which may be unsubstituted or partially or fully substituted by D;
  • Ar2 Ars are identical or different on each occurrence with an aryl group
  • R is selected on each occurrence, identically or differently, from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, one or more non- adjacent CH2 groups may be replaced by O or S and one or more H atoms may be replaced by D, F, or CN
  • carbon atoms may be substituted; two or more adjacent substituents R can form a mono- or polycyclic, aliphatic ring system with one another;
  • R is selected identically or differently on each occurrence from the group
  • D, F, CN a straight-chain alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, where one or more non-adjacent CH2 groups can be replaced by O or S and where one or more H atoms can be replaced by D, F or CN or an aromatic ring system having 6 to 30 ring atoms in which one or more H atoms can be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms or a heteroaryl group having 9 to 30 atoms, the atoms comprising carbon atoms and at least one heteroatom, 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 having 1 to 4 carbon atoms; two or more adjacent substituents R can form a mono- or polycyclic, aliphatic ring system with one another; b, b1 are each independently 0 or 1;
  • 20 b2 is 0 or 1 ; n is 0, 1, 2, 3 or 4 and n1 is 0, 1 or 2.
  • Another object of the invention is a mixture containing at least one
  • a further subject matter of the invention is a formulation containing at least one compound of the formula (1), as described above or as preferably described later, or a mixture as described above, and at least one solvent.
  • Another object of the invention is an organic electroluminescent
  • 35 Device comprising an anode, a cathode and at least one organic layer containing at least one compound according to formula (1), as described above or preferably described later.
  • a further subject matter of the invention is a method for producing an organic electroluminescent device, as described above or as preferably described below, characterized in that the organic layer is applied by gas phase deposition or from solution.
  • An aryl group within the meaning of this invention contains 6 to 40 ring atoms, preferably C atoms.
  • a heteroaryl group in the context of this invention contains 5 to 40 ring atoms, the ring atoms comprising carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5.
  • the heteroatoms are preferably selected from N, O and/or S.
  • An aryl group or heteroaryl group is either a simple aromatic ring, ie
  • An aryl group having 6 to 18 carbon atoms is therefore preferably phenyl, naphthyl, phenanthryl or triphenylenyl, where
  • the attachment of the aryl group as a substituent is not restricted.
  • the aryl or heteroaryl group within the meaning of this invention can carry one or more radicals, with the suitable radical being described below. If no such radical is described, the aryl group or heteroaryl group is unsubstituted.
  • An aromatic ring system within the meaning of this invention contains 6 to 40 carbon atoms in the ring system.
  • the aromatic ring system also includes aryl groups as previously described.
  • An aromatic ring system having 6 to 18 carbon atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthryl and triphenylenyl.
  • 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.
  • heteroaryl groups as previously described.
  • the heteroatoms in the heteroaromatic ring system are preferably selected from N, O and/or S. P21177 SC
  • aromatic or heteroaromatic ring system in the context of this invention is understood to mean a system that does not necessarily only contain aryl or heteroaryl groups, but also in which several aryl or heteroaryl groups are replaced by a non-aromatic unit (preferably less than 10% of those other than H
  • a C or O atom or a carbonyl group can be interrupted.
  • systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diarylether, stilbene, etc. should also be understood as aromatic or heteroaromatic ring systems within the meaning of this invention, and also systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group.
  • aromatic or heteroaromatic ring system with 5-40 ring atoms which can be linked via any position on the aromatic or heteroaromatic, is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene,
  • Triazine 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.
  • Ar2 and Ars mean the same or different on each occurrence, an aryl group having 6 to 30 carbon atoms, which may be substituted by one or more radicals R, or a heteroaryl group having 9 to 30 atoms, the atoms being carbon atoms and at least one heteroatom, which are terminated with one or more radicals R
  • radical R or the substituents R has/have a meaning as described above or below.
  • Ar2 and Ars is described below.
  • Ars stands, identically or differently on each occurrence, for an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which can be substituted by one or more radicals R 7 , where the radical R 7 or the substituents R 7 has/have a meaning, as described above or below.
  • a cyclic alkyl, alkoxy or thioalkyl group is understood to mean a monocyclic, a bicyclic or a polycyclic group.
  • cyclic C 1 to C 20 alkyl group 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, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-oc
  • a straight-chain or branched C 1 -C 20 alkoxy group is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy.
  • a straight-chain Ci to C2o-thioalkyl group for example, S-
  • alkyl groups for example thiomethyl, 1-thioethyl, 1-thio-i-propyl, 1-thio-n-propoyl, 1-thio-i-butyl, 1-thio-n-butyl or 1-thio-t-butyl .
  • An aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms means O-aryl or O-heteroaryl and means that the aryl or heteroaryl group is bonded via an oxygen atom, the aryl or heteroaryl group having a meaning as described above.
  • the above formulation should also be understood to mean that if one of the two radicals is hydrogen, the second radical binds to the position to which the hydrogen atom was bonded, forming a ring. This should be illustrated by the following scheme:
  • Y is independently N, [L]b-Ar2 or [L]bi-Ars on each occurrence, where exactly two Ys stand for N, which are connected by at least one group [L]b-Ar2 or [L]bi-Ars are separated.
  • Preferred embodiments of the compounds of the formula (1) are compounds of the formulas (1a), (1b) or (1c) in which the position of the two N atoms is described in more detail, the remaining Y are [L]b-Ar2 and [L ]bi-Ars mean, and the used
  • a further subject matter of the invention is accordingly compounds of the formulas (1a), (1b) or (1c), as described above or as preferably described below.
  • Preferred embodiments of the compounds of formula (1) are also compounds of formulas (1d), (1e), (1f), (1g), (1h) or (1i),
  • a further subject of the invention are therefore compounds of the formulas (1d), (1e), (1f), (1g), (1h) or (1i), as described above or as preferably described below.
  • Preferred compounds of formula (1) correspond to formulas (1a) and (1b).
  • Particularly preferred compounds of formula (1) correspond to formula (1a).
  • n is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2 and most preferably 0.
  • n1 is 0, 1 or 2, preferably 0 or 1, particularly preferably 0.
  • R# when it occurs, is preferably an aryl group having 6 to 18 carbon atoms or a heteroaryl group having 9 to 13 ring atoms, which can be substituted by one or more radicals R, where R is one of the above or below preferred
  • R# is preferably phenyl, carbazole- N-yl or aryl-carbazolyl, where the abbreviation "aryl” means an aromatic or heteroaromatic ring system having 5 to 30 ring atoms, which is fused with one or
  • Aryl is preferably phenyl, 1,3-biphenyl, 1,4-biphenyl, dibenzofuranyl or dibenzothiophenyl. "Aryl” is particularly preferably phenyl.
  • the substituent Rx is preferably an aromatic ring system with 6 to 20 ring atoms or for a heteroaromatic ring system with 6 to 20 ring atoms, each of which may be substituted by one or more radicals R, where the radical R has a meaning that has been mentioned above or is preferred below.
  • pyridine pyrimidine, triazine, quinazoline, dibenzofuran, dibenzothiophene, carbazole, indolocarbazole or indenocarbazole, each of which can be substituted by one R radical or more R radicals, where the R radical has a meaning that is mentioned above or is preferred below and carbazole, indolocarbazole and indenocarbazole
  • N atom 5 can be bound via their N atom or one of their C atoms. If carbazole, indolocarbazole and/or indenocarbazole are bonded via C, their N atom carries an “aryl” substituent, as described above, which is preferably selected from phenyl, 1,3-biphenyl, 1,4-biphenyl, dibenzothiopenyl, 9 ,9-dimethylfluorenyl or triphenylenyl, where the attachment of "aryl" to the corresponding N atom is not restricted unless otherwise noted.
  • aryl substituent
  • Rx is substituted with one or more radicals R
  • R is preferably selected independently from the group D, CN, phenyl, 1,4-biphenyl, 1,3-biphenyl, N-arylcarbazolyl and Dibenzofuranyl selected, where "aryl" in
  • N-Aryl-carbazolyl has an aforementioned meaning or an aforementioned preferred meaning, and/or two substituents R form an aromatic ring.
  • substituent Rx as previously described or as preferably described, this substituent is deuterated. In a preferred embodiment of the substituent Rx, as previously described or preferably described, the substituent has
  • Rx is a radical R or two radicals R or it is unsubstituted, the radical R having a previously mentioned or preferably mentioned meaning.
  • a preferred aromatic ring system as Rx is, for example, phenyl, 1,3-biphenyl, 1,4-biphenyl, spirobifluorenyl, 9,9-dimethylfluorenyl, 9-phenyl-9-methylfluorenyl, triphenylenyl or fluoranthenyl.
  • Vi is preferably O or N-aryl.
  • Vi O is particularly preferred.
  • Ars represents an aryl group with 6 to 30 carbon atoms, which can be substituted by one or more R radicals, or a heteroaryl group having 9 to 30 atoms, the atoms comprising C atoms and at least one heteroatom, which can be substituted by one or more R radicals.
  • R is selected identically or differently on each occurrence from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, with one or more non-adjacent CH2 groups can be replaced by O or S and one or more H atoms can be replaced by D, F, or CN or an aroma ⁇
  • 25 matic or heteroaromatic ring system having 5 to 30 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 having 1 to 4 carbon atoms ; two or more adjacent substituents R## can together form a mono- or polycyclic, aliphatic or aromatic ring system which can each be substituted by one or more R radicals and which, in the case of a heteroaromatic ring system, together with the radical of the partial formula ( 1-0) has 9 to 30 atoms, where R has a previously mentioned or preferred meaning and w is 0, 1, 2, 3, 4 or 5.
  • w is preferably 0, 1 or 2.
  • Ars and the partial formula (1-0) preferably means phenyl, triphenylenyl, fluoranthenyl, dibenzofuranyl, 9,9-dimethylfluorenyl, carbazole -N-yl substituted with one or more o o
  • R radicals can be substituted, where R has a previously indicated meaning. If the substituent Ars is substituted with one or more R radicals, as described above, R is preferably selected independently in each case from the group D, CN, phenyl and triphenylenyl, particularly preferably phenyl.
  • Ars is preferably phenyl, phenyl substituted once with R, triphenylenyl , fluoranthenyl, dibenzofuranyl, 9,9-dimethylfluorenyl or carbazol-N-yl.
  • Ar2 represents an aryl group 6 to 30 carbon atoms, which can be substituted by one or more radicals R or a heteroaryl group having 9 to 30 atoms, the atoms comprising carbon atoms and at least one heteroatom, which with
  • one or more radicals R may be substituted.
  • Ar2 preferably represents the partial formula (2-0)
  • R is selected identically or differently on each occurrence from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, with one or P21177 SC
  • CH2 groups can be replaced by O or S and one or more H atoms can be replaced by D, F, or CN or an aromatic or heteroaromatic ring system with 5 to 30 ring atoms in which a or more H atoms can be replaced by D, F, CI, Br, I or CN and by a
  • alkyl groups each having 1 to 4 carbon atoms may be substituted; two or more adjacent substituents R## can together form a mono- or polycyclic, aliphatic or aromatic ring system which can each be substituted by one or more R radicals and which, in the case of a heteroaromatic ring system, together with the radical of the partial formula ( 2-0) has 9 to 30 atoms, where R has a previously mentioned or preferably mentioned meaning and w is 0, 1, 2, 3, 4 or 5.
  • w is preferably 0, 1 or 2.
  • Ar2 and the partial formula (2-0) preferably means phenyl, triphenylenyl, fluoranthenyl, dibenzofuranyl, 9,9-dimethylfluorenyl, Carbazol-N-yl substituted with one or more o o
  • R 25 radicals R can be substituted, where R has a previously indicated meaning. If the substituent Ar2 is substituted with one or more R radicals, as described above, R is preferably selected independently in each case from the group D, CN, phenyl and triphenylenyl, particularly preferably phenyl.
  • Ar2 is preferably phenyl, phenyl substituted once with R, triphenylenyl, fluoranthenyl, dibenzofuranyl, 9,9-dimethylfluorenyl or carbazole N-yl.
  • Examples of suitable host materials of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h) and (1i) are as follows structures mentioned in Table 1.
  • Particularly suitable compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h) and (1i) are the compounds E1 to E51 of Table 2.
  • the compounds according to the invention can be prepared by synthesis steps known to those skilled in the art, such as, for. B. bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc., are shown.
  • Suitable compounds with a diazadibenzofuran or diazadibenzothiophene group can often be obtained commercially, the starting compounds set out in the examples being obtainable by known methods, so that reference is made thereto.
  • a conversion results for example, according to the following schemes, without any restriction being intended as a result.
  • the sub-steps of the individual schemes can be combined in any way.
  • the compounds of the formula (1) can be obtained in high purity, preferably more than 99% (determined by means of 1 H-NMR and/or HPLC).
  • formulations of the compounds according to the invention or mixtures of compounds according to the invention with other functional materials such as matrix materials, fluorescent emitters, phosphorescent emitters and / or emitters that show TADF , necessary.
  • these formulations can be, for example, solutions, dispersions or emulsions. It may be preferable to use mixtures of two or more solvents for this.
  • Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -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 -dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin
  • the compounds of the formula (1) according to the invention are suitable for use in an organic electroluminescent device, in particular as a matrix material.
  • 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.
  • a further subject of the invention is therefore a mixture containing at least one compound of the formula (1) or at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e ), (1f), (1g), (1h) and (1i), or a compound of Table 1 or one of the compounds E1 to E51 and at least one other compound selected from the group of matrix materials, the phosphorescent
  • the fluorescent emitter and/or the emitter showing TADF (thermally activated delayed fluorescence).
  • TADF thermalally activated delayed fluorescence
  • Another subject of the present invention is also a formulation containing at least one compound according to the invention, as described above, or a mixture according to the invention, as described above, and at least one solvent.
  • the solvent can be a solvent mentioned above or a mixture of these solvents.
  • Another subject of the present invention is an organic electroluminescent device comprising an anode, a cathode and at least one organic layer containing at least one compound of the formula (1) or at least one preferred compound of one of the formulas (1), (1a), (1 b), (1c),
  • the organic electroluminescent device according to the invention is, for example, an organic light-emitting transistor ( ⁇ LET), an organic field quench device (OFQD), an organic light-emitting electrochemical cell (OLEC, LEG, LEEC), an organic
  • 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), a
  • EML light-emitting layer
  • HIL hole-injection layer
  • HTL hole-transport layer
  • HBL hole-blocking layer
  • ETL electron-transport layer
  • EIL electron-injection layer
  • the device according to the invention can also contain several layers of this group, preferably selected from EML, HIL, HTL, ETL, EIL and HBL.
  • interlayers can be introduced between two emitting layers, which, for example
  • emission layers are present, these preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, i. H. in the emitting layers different emitting compounds are used which can fluoresce or phosphoresce.
  • 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 also layers which are made up entirely of inorganic materials.
  • Electroluminescent device are interrelated with each other. This concerns, for example, the energy levels of the orbitals (HOMO, LIIMO) or the position of triplet and singlet energies, but also other material properties.
  • HOMO orbitals
  • LIIMO position of triplet and singlet energies
  • the compound of the 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 containing a compound of the formula (1) or the preferred embodiments outlined above in an emitting layer as matrix material for fluorescent emitters, phosphorescent emitters or for emitters which exhibit TADF (thermally activated delayed fluorescence), in particular for phosphorescent ones emitter. Furthermore, the compound according to the invention can also be used in an electron transport layer and/or in a hole transport layer and/or in an exciton blocking layer and/or in a hole blocking layer. The is particularly preferred
  • Another object of the present invention is an organic one
  • the organic layer contains at least one light-emitting layer comprising the at least one compound of formula (1) or the at least one preferred compound of one of formulas (1), (1a), (1b), ( 1c), (1d), (1e), (1f), (1g), (1h) and (1i), or a compound of Table 1 or one of the compounds E1 to E51.
  • a 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 as preferably described, or with the compounds of Table 1 or the compounds E1 to E51 becomes.
  • a further subject of the present invention is accordingly an organic electroluminescent device as described above, wherein the organic layer contains at least one light-emitting layer which contains the at least one compound of the formula (1) or the at least one preferred compound of one of the formulas (1), (1a),
  • 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 boron esters, triazine derivatives, zinc complexes, diazasilol or tetraazasilol derivatives, diazaphosphol 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 as a co-host in the mixture, 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.
  • band gap is the distance between the HOMO and LUMO energies of a material.
  • a further object 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 contains at least one compound of the formula (1) as matrix material 1, as described above or as described as preferred, and at least one compound of the formulas (6), (7 ), (8), (9) or (10) contains 2 as matrix material, P21177 SC
  • a 1 is C(R 7 ) 2 , NR 7 , O or S;
  • A is on each occurrence independently a group of formula (3) or (4), P21177 SC
  • X2 is the same or different on each occurrence, CH, CR 6 or N, with a maximum of
  • R 6 is the same or different on each occurrence, D, CN, a straight-chain alkyl group with 1 to 20 carbon atoms or an alkenyl or alkynyl group with 2
  • alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R 7 and where one or more non-adjacent CH2 groups may be replaced by Si(R 7 )2, C ⁇ O, NR 7 , O, S or CONR 7 , or an aromatic or heteroaromatic ring system with 5
  • R 7 radicals 20 to 60 ring atoms, each of which may be substituted by one or more R 7 radicals; two radicals R 6 can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another;
  • Ar is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which with a
  • radicals R 7 may be substituted
  • Ar 5 is identical or different on each occurrence and is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which can be substituted by one or more R 7 radicals;
  • 35 or more non-adjacent CH2 groups can be replaced by Si(R 8 )2, C ⁇ O, NR 8 , O, S or CONR 8 , or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each of which is substituted by one or P21177 SC
  • radicals R 8 may be substituted; two or more radicals R 7 can together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 do not form such a ring system;
  • R 8 is identical or different on each occurrence and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 carbon atoms in which one or more H atoms have also been replaced by F can; c, c1, c2 each independently mean 0 or 1 on each occurrence, the sum of the indices c+c1+c2 meaning 1 on each occurrence; d, d1, d2 each independently mean 0 or 1 on each occurrence, the sum of the indices d+d1+d2 meaning 1 on each occurrence; q, q1, q2 each independently mean 0 or 1 on each occurrence; s is the same or different on each occurrence and is 0, 1, 2, 3 or 4;
  • s is preferably 0 or 1, particularly
  • t is preferably 0 or 1, particularly preferably 0.
  • u is preferably 0 or 1, particularly preferably 0.
  • the sum of the indices s, t and u in compounds of the formulas (6), (7), (8) or (10) is preferably at most 6, particularly preferably at most 4 and particularly preferably at most 2.
  • c, c1, c2 each independently mean 0 or 1 on each occurrence, the sum of the indices c+c1+c2 meaning 1 on each occurrence.
  • c2 preferably has the meaning 1.
  • R 6 is the same or different on each occurrence selected from the group consisting of D, F, CN, NO2, Si(R 7 )s, B(OR 7 )2, a straight- P21177 SC
  • alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, where the alkyl group can be substituted with one or more radicals R 7 , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic Ring ⁇
  • R 6 is or different on each occurrence selected from the group consisting of D, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted with one or more R 7 radicals.
  • a preferred radical R 7 is the group N(Ar)2.
  • Ars in compounds of the formulas (6), (7), (8) or (10) is preferably 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 via the 1-,
  • 20 or 4-position can be linked, 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 via the 1-, 2-,
  • 3- or 4-position can be linked, dibenzothiophene, which via the 1-, 2-, 3- or
  • 4-position can be linked, indenocarbazole, indolocarbazole, pyridine, pyrimidine,
  • the substituent R 7 attached to the nitrogen atom is preferably an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more R 8 radicals may be substituted. In a particularly preferred embodiment, this substituent R 7 is the same or different on each occurrence
  • R 7 are phenyl, biphenyl, terphenyl and quaterphenyl, the P21177 SC
  • radicals derived from triazine, pyrimidine and quinazoline which can be substituted by one or more radicals R 8 .
  • R 7 is very particularly preferably a methyl group or a phenyl group.
  • the R 7 radicals can also form a ring system with one another, which leads to a spiro system.
  • these compounds are partially or completely deuterated, particularly preferably completely deuterated.
  • Another object of the invention is also an organic electroluminescent
  • 25 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 at least one compound of formula (1) as matrix material 1, as described above or as preferred, and at least one compound of formula (11),
  • W is o, S, C(R)2, N-An
  • Each R is independently straight-chain or branched
  • Alkyl group with 1 to 4 carbon atoms which can be partially or fully deuterated, or an unsubstituted or partially or fully deuterated
  • aromatic ring system with 6 to 18 carbon atoms, where two substituents R can form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic, unsubstituted, partially deuterated or fully deuterated ring system with the carbon atom to which they are attached,
  • An is identical or different on each occurrence and is an aromatic or heteroaromatic ring system having 5 to 30 ring atoms, which may be substituted by one or more R radicals; in this case, two radicals An, which bind to the same N atom, P atom or B atom, also by a single
  • H atoms can be replaced by D, F, Cl, Br, I, CN or NO2;
  • R ' is on each occurrence, identically or differently, an aliphatic, aromatic or heteroaromatic organic radical, in particular a
  • R 20 may be substituted, an aryloxy or heteroaryloxy group having 5 to 60 ring E atoms, which may be substituted by one or more R radicals, or a combination of these systems, where optionally two or more adjacent substituents R 4 are monocyclic or polycyclic, aliphatic, aromatic
  • 25 can form tic or heteroaromatic ring system, which can be substituted with one or more radicals R;
  • R 5 is selected identically or differently on each occurrence from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, one or more not -adjacent CH2 groups can be replaced by O or S and one or more H atoms can be replaced by D, F, or CN or an aromatic or heteroaromatic ring system with 5 to 30 ring atoms in which one or more H atoms through D,
  • 35 F, CI, Br, I or CN can be replaced and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; included P21177 SC
  • R 5 can together form a mono- or polycyclic, aliphatic ring system; x, x1 each occurrence are independently 0, 1, 2, 3, or 4; y, z are each independently 0, 1 or 2;
  • a1, a2 are each independently 0, 1, 2, 3, 4 or 5; a3 is 0, 1, 2 or 3; a4 is 0, 1, 2, 3 or 4.
  • the compounds of formula (6), (7), (8), (9), (10) or (11) are preferably partially deuterated or fully deuterated.
  • N-linked substituents are partially deuterated and the third N-linked substituent is fully deuterated.
  • two of the N-linked substituents are partially deuterated and the third N-linked substituent is fully deuterated.
  • each N-linked substituent is fully deuterated.
  • this is a mixture of deuterated compounds of the formula (11), as described above or
  • the degree of deuteration of the compounds of the formula (11) being at least 50% to 90%, preferably 70% to 100%.
  • a suitable method for deuterating an arylamine or a heteroarylamine by replacing one or more H atoms with D atoms is treatment of the arylamine or heteroarylamine to be deuterated in the presence of a platinum catalyst
  • deuterium source P21177 SC
  • - 58 - means any compound containing one or more D atoms and capable of releasing them under appropriate conditions.
  • the platinum catalyst is preferably dry platinum on carbon, preferably 5%
  • the palladium catalyst is preferably dry palladium on carbon, preferably 5% dry palladium on carbon.
  • a suitable source of deuterium is D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, toluene-d8.
  • a preferred source of deuterium is D2O or a combination of D2O and a fully deuterated organic solvent.
  • a particularly preferred source of deuterium 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.
  • the 15 deuterium source is a combination of D2O and toluene-d8.
  • the reaction is preferably carried out with heating, more preferably with heating at temperatures between 100°C and 200°C. Furthermore, the reaction is preferably carried out under pressure.
  • Preferred compounds of formula (11) are represented by formulas (11a), (11b), (11c), (11d), (11e), (11f), (11g), (11h), (11i), ( 11j), (11k), (111), (11m), (11n), (11o) and (11p),
  • R c are each independently a straight-chain or branched alkyl group having 1 to 4 carbon atoms, which may be partially or fully deuterated, or
  • 5 is an unsubstituted or partially or fully deuterated aromatic ring system having 6 to 18 carbon atoms; x2 is 0, 1, 3, or 3; y1 , z1 are each independently 0, 1 or 2; y1, z1, y2, z2 are each independently 0, 1 or 2, preferably 0; ai 1 is 0, 1, 2, 3 or 4; as, a44 are each independently 0, 1, 2, 3, or 4, and a34, a45 are each independently 0, 1, 2, 3, or 4.
  • R c is preferably the same and a straight-chain or branched alkyl group having 1 to 4 carbon atoms, which can be partially or fully deuterated, or an unsubstituted or partially or fully deuterated phenyl.
  • R 4 is preferred in compounds of the formulas (11), (11a), (11b), (11c), (11d), (11e),
  • 2-, 3- or 4-position can be linked, spirobifluorenyl, which can be linked via the 1-, 2-, 3- or 4-position, naphthyl, in particular 1- or 2-linked naphthyl, or residues derived from indole , benzofuran, benzothiophene, carbazole, which over
  • the 1-, 2-, 3- or 4-position can be linked, dibenzofuran, which via the 1-, 2-,
  • 3- or 4-position can be linked, dibenzothiophene, which via the 1-, 2-, 3- or P21177 SC
  • 4-position can be linked, indenocarbazole, indolocarbazole, phenanthrene or triphenylene, each of which can be substituted by one or more radicals R 5 .
  • R 4 is preferably unsubstituted.
  • R 1 is preferred in compounds of the formulas (11), (11a), (11b), (11c), (11d), (11e),
  • 2-, 3- or 4-position can be linked, spirobifluorenyl, which can be linked via the 1-, 2-, 3- or 4-position, naphthyl, in particular 1- or 2-linked naphthyl, or residues 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 can be linked, dibenzothiophene, which via the 1-, 2-, 3- or
  • 4-position can be linked, indenocarbazole, indolocarbazole, phenanthrene or tri
  • R 1 is preferably unsubstituted.
  • x, x1, y, z, x2, y1 and z1 are preferably 0.
  • the compounds of the formulas (6), (9), (10) and (11) are particularly preferably used as further matrix material.
  • the host materials of the formula (1) mentioned above and their preferably described embodiments or the compounds of Table 1 and the compounds E1 to E51 can be combined in the device according to the invention with the matrix materials/host materials of the formulas (6), (7), (8 ), (9), (10) or (11) and their preferably described embodiments or the compounds H1 to H63 are combined.
  • the device is obtained by combining Compounds E1 to E51 with Compounds H1 to H63 as shown in Table 4 below. P21177 SC
  • the concentration of the host material of the 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 in the range from 5% by weight to 90% by weight, preferably in the range from 10 wt% to 85 wt%, more
  • the concentration of the host material of one of the formulas (6), (7), (8), (9), (10) or (11) as previously described or as described as being preferred in the mixture according to the invention or in the light-emitting layer of the invention Device is in the range of 10 wt .-% to 95 wt .-%, preferably in the range of 15 wt .-% to
  • 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 one of the formulas (6), (7), (8), (9), (10) or (11), called host material 2 in the future, as previously described or preferably described, in particular mixtures
  • 25 M1 to M3213 contains at least one phosphorescent emitter.
  • the present invention also relates to an organic electroluminescent device as described above or as preferably described, wherein the light-emitting layer, in addition to the above-mentioned host materials of the formulas
  • phosphorescent emitters typically includes compounds at
  • 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 preferably used as phosphorescence emitters, in particular compounds containing iridium or platinum.
  • all luminescent compounds containing the metals mentioned above are regarded as phosphorescent emitters.
  • Preferred phosphorescent emitters according to the present invention correspond
  • X is N or CR
  • R is H, D or a branched or linear alkyl group having 1 to 10 carbon atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, some or all of which
  • a further subject matter of the invention is therefore an organic electroluminescent device as described above or as 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 has the formula (IIIa)
  • n is preferably 1 and m is preferably 2.
  • one X is preferably selected from N and the other Xs are CR.
  • emitters of the formula (IIIa) at least one R is preferably different from H.
  • emitters of the formula (IIIa) preferably two Rs are different from H and have one of the meanings otherwise given above for the emitters of the formula (IIIa).
  • Preferred phosphorescent emitters according to the present invention correspond
  • Ri is H or D
  • R2 is H
  • Preferred phosphorescent emitters according to the present invention correspond to the formula (VI), (VII) or (VIII), where the symbols and indices for these formulas (VI), (VII) and (VIII) have the meaning:
  • Ri is H or D
  • R2 is H, D, F or a branched or linear alkyl group having 1 to 10 carbon atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 10 C atoms, the
  • Preferred examples of phosphorescent emitters are described in WO2019007867 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.
  • each mixture is preferably selected from the sum of mixtures M1 to M3213 with a compound of the formula (IIIa) or a compound of the formulas (I) to (VIII) or a compound from the table 5 combined.
  • 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 ultra ⁇
  • 15 violet 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 mean a layer whose photoluminescence maximum is in the range from 540 to 570 nm. Under an orange
  • a 20 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 mean a layer whose photoluminescence maximum is in the range from 490 to 540 nm. Under a blue
  • 25 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, the layer comprising the combination according to the invention of the host materials of the formulas (1) and one of the formulas (6), (7), (8) , (9), (10) or (11) and the corresponding emitter.
  • the photoluminescence spectrum of the layer is recorded, for example, with a commercially available photoluminescence spectrometer.
  • the photoluminescence spectrum of the selected emitter is usually measured in an oxygen-free solution, 10-5 molar, with the measurement taking place at room temperature and P21177 SC
  • any solvent is suitable in which the selected emitter dissolves in the specified concentration.
  • Particularly suitable solvents are usually toluene or 2-methyl-THF, but also dichloromethane. It is measured with a commercially available photoluminescence spectrometer. The triplet energy T1 in eV is calculated from the
  • preferred phosphorescent emitters are yellow emitters, preferably of the formula (IIIa), of the formulas (I) to (VIII) or from Table 5, whose triplet energy T ⁇
  • preferred phosphorescent emitters are green emitters, preferably
  • the triplet energy T 1 of which is preferably ⁇ 2.5 eV to ⁇ 2.3 eV.
  • particularly preferred phosphorescent emitters are green emitters, preferably of the formula (IIIa), of the formulas (I) to (VIII) or from Table 5, as above
  • Fluorescent emitters can also be contained 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, where preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, particularly preferably having at least 14 ring atoms.
  • Preferred examples of these are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines.
  • An aromatic anthracenamine is understood to mean a compound in
  • An aromatic anthracene diamine is a compound P21177 SC
  • diarylamino groups are attached directly to an anthracene group, preferably in the 9,10-position.
  • Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously, with the diarylamino groups preferably being attached to the pyrene 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. Also preferred are pyrene arylamines. Also preferred are benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives linked to furan moieties or to thiophene moieties.
  • the at least one light-emitting layer of the organic electroluminescent device can, in addition to the host materials 1 and 2, as described above or as described as being preferred, further
  • the mixed matrix systems preferably comprise three or four different matrix materials, more preferably three different matrix materials (that is, a further matrix component in addition to host materials 1 and 2 as described above).
  • a mixed matrix system can be used are selected from wide-band gap materials, bipolar host materials, electron transport materials (ETM) and hole transport materials (HTM).
  • ETM electron transport materials
  • HTM hole transport materials
  • the mixed matrix system is preferably optimized for an emitter of the formula (IIIa), of the formulas (I) to (VIII) or from Table 5.
  • the mixture contains no further components, ie functional materials, apart from the components of the host material of the 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 source of material in the vapor deposition of the host materials for the light-emitting layer and have a constant mixing ratio during the vapor deposition. This allows a layer to be vapor-deposited with a uniform distribution of the components in a simple and quick manner, without
  • the mixture in addition to the components of the host material of the formula (1) and of the host material 2, as described above, the mixture also contains a phosphorescent emitter, as described above.
  • a suitable mixing ratio during the vapor deposition it is also possible
  • this mixture can be used as the sole source of material, as previously described.
  • the components or parts 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 previously described
  • 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% by volume, more preferably between 99 and 10% by volume, particularly preferably between 98 and 60% by volume , very particularly preferably between 97 and 80% by volume of matrix material composed of at least one compound of the formula (1) and
  • the light-emitting layer in the device according to the invention preferably contains between 0.1 and 99% by volume, more preferably between 1 and 90% by volume, particularly preferably between 2 and 40% by volume,
  • the emitter 25 very particularly preferably between 3 and 20% by volume 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 % by weight are preferably used instead of the amounts in % by volume given above.
  • the light-emitting layer in the device according to the invention according to the preferred embodiments and the emitting compound preferably contains the host material 1 and the host material 2 in a volume percentage ratio of between 3:1 and 1:3, preferably between 1:2.5 and 1:1, particularly preferably between 1 :2 and
  • the present invention also relates to an organic electroluminescent device as described above or as 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
  • HIL hole injection layer
  • HTL hole transport layer
  • Preferred compounds with a hole transport function that do not correspond to one of the formulas for the host material 2, preferably for use in a hole injection layer, a hole transport layer, an electron blocking layer and/or as additional matrix material in the emissive layer according to the invention are shown in Table 6 below. As shown by the structures, the compounds of Table 6 are non-deuterated compounds.
  • the sequence of the layers in the organic electroluminescent device according to the invention is preferably the following:
  • This sequence of layers is a preferred sequence.
  • the materials used for the electron-transport layer can be any materials that are used as electron-transport materials in the electron-transport layer according to the prior art.
  • Aluminum complexes such as Alqß, zirconium complexes, such as Zrq4, are particularly suitable.
  • 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.). Also suitable are alloys of an alkali metal or alkaline earth metal and silver, for example an alloy of magnesium and silver.
  • alkaline earth metals such as Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.
  • alloys of an alkali metal or alkaline earth metal and silver for example an alloy of magnesium and silver.
  • 25 other metals are used in addition to the metals mentioned, which have a relatively high work function, such.
  • B. Ag or Al in which case combinations of the metals, such as Ca/Ag, Mg/Ag or Ba/Ag, are then generally used.
  • Lithium quinolinate (LiQ) can also be used for this.
  • the layer thickness of this layer is preferably between 0.5 and 5 nm.
  • the anode preferably has a work function of greater than 4.5 eV vs. vacuum.
  • metals with P21177 SC are preferred as the anode.
  • metal/metal oxide electrodes eg Al/Ni/NiO x , Al/PtO x
  • at least one of the electrodes must be transparent or partially transparent in order to either irradiate the organic material (organic
  • Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Conductive, doped organic materials, in particular conductive, doped polymers, are also preferred. Furthermore, the anode can also consist of several layers, for example an inner layer made of ITO and an outer layer made of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.
  • the organic electroluminescent device according to the invention is correspondingly (depending on the application) structured, contacted and finally
  • the materials are vapour-deposited in vacuum sublimation systems at an initial pressure of less than 10.sup.-5 mbar, preferably less than 10.sup.- mbar. However, it is also possible for the initial pressure to be even lower, for example less than 10 mbar.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne des dérivés de diazabenzofurocarbazole et des dérivés de diazabenzothiéonocarbazole et des dispositifs électroniques contenant lesdits composés, en particulier des dispositifs électroluminescents organiques contenant lesdits composés en tant que matériaux de matrice de triplet, éventuellement combinés à un autre matériau de matrice de triplet et à des émetteurs phosphorescents appropriés, et à des mélanges et formulations appropriés.
EP22802544.1A 2021-10-14 2022-10-11 Matériaux pour dispositifs électroluminescents organiques Pending EP4416155A1 (fr)

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PCT/EP2022/078229 WO2023061998A1 (fr) 2021-10-14 2022-10-11 Matériaux pour dispositifs électroluminescents organiques

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