WO2023247416A1 - Composés de type tétraarylbenzidine et leur utilisation en électronique organique - Google Patents

Composés de type tétraarylbenzidine et leur utilisation en électronique organique Download PDF

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WO2023247416A1
WO2023247416A1 PCT/EP2023/066410 EP2023066410W WO2023247416A1 WO 2023247416 A1 WO2023247416 A1 WO 2023247416A1 EP 2023066410 W EP2023066410 W EP 2023066410W WO 2023247416 A1 WO2023247416 A1 WO 2023247416A1
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formula
compound
phenyl
alkyl
groups
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Yves AESCHI
Thorsten Beck
Ulrich Berens
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Dottikon Es Holding Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • the present invention relates to compounds of the tetraarylbenzidine-type, bearing specific (het)aryl groups at the nitrogen atoms bound to the 1 ,1 '-biphenylene backbone, and to methods for their preparation.
  • the invention further relates to the use of the tetraarylbenzidine derivatives in organic electronics, in particular as hole transport material (HTM) or electron blocking material (EBM).
  • HTM hole transport material
  • EBM electron blocking material
  • Organic electronics is concerned principally with the development, characterization and application of new materials and manufacturing processes for the production of electronic components based on organic small molecules or polymers with desirable electronic properties. These include in particular organic field-effect transistors (OFETs), like organic thin-film transistors (OTFTs), organic electroluminescent devices like organic light-emitting diodes (OLEDs), organic solar cells (OSCs), e.g.
  • OFETs organic field-effect transistors
  • OFTs organic thin-film transistors
  • OLEDs organic light-emitting diodes
  • OSCs organic solar cells
  • organic photoconductor organic photoconductor
  • OPFQD organic field-quench devices
  • LECs light-emitting electrochemical cells
  • organic laser diodes organic laser diodes.
  • organic semiconductive materials can be formed either from compounds with good electron donor properties (p-conductors) or from compounds with good electron acceptor properties (n-conductors).
  • organic semiconductors In contrast to inorganic semiconductors, organic semiconductors have a very low intrinsic charge carrier concentration. Organic semiconductor matrix materials are therefore usually doped in order to achieve good semiconductor properties.
  • Organic photovoltaics denotes the direct conversion of radiative energy, principally solar energy, to electrical energy using organic components.
  • the light does not directly generate free charge carriers in organic solar cells, but rather excitons are formed first, i.e. electrically neutral excited states in the form of electron-hole pairs.
  • excitons can be separated at suitable photoactive interfaces (organic donor-acceptor interfaces or interfaces to an inorganic semiconductor).
  • suitable photoactive interfaces organic donor-acceptor interfaces or interfaces to an inorganic semiconductor.
  • excitons which have been generated in the volume of the organic material can diffuse to this photoactive interface.
  • the diffusion of excitons to the active interface thus plays a critical role in organic solar cells.
  • materials which have maximum transport widths and high mobilities for light-induced excited states (high exciton diffusion lengths) and which are thus advantageously suitable for use as an active material in so-called excitonic solar cells.
  • JP 2009158535 A describes an organic light-emitting device (OLED) having high efficiency and long service life, comprising a hole injection layer 3 that contains aryl amine polymers, inter alia of the formulae (A1 ) and (A2)
  • EP 0879868 A2 describes organic compounds of the general formula (B) wherein X is a substituted or unsubstituted arylene group or a substituted or unsubstituted heterocyclic group and at least two of the Ar 1 , Ar 2 , Ar 3 , and Ar 4 groups are a substituted or unsubstituted fluorenyl group, and the remainder represents a substituted or unsubstituted aryl group.
  • those compounds can be used inter alia as hole transport materials to provide electroluminescent devices showing versatility of wavelenths and high durability.
  • the groups X and Ar 1 , Ar 2 , Ar 3 , and Ar 4 can be selected from a plethora of different groups.
  • aryl groups also encompasses heterocyclic groups without giving a concrete example.
  • compounds (B) that bear heterocyclic groups that have only one single nitrogen atom or nitrogen atom group generally show conductivities that still need improvement.
  • NDTs naphthoindacenodithiophenes
  • C NDT-containing polymers
  • An-An? are independently of each other substituted or unsubstituted homocycles or heterocycles, selected from phenyl, carbazol, fluorene, spirobifluorene, diphenylether, selenophene, furane, thiophen, pyrrole or phosphole, a-q are independently of each other 0 or 1 with the proviso that a + b + rigid + p + q > 6, wherein in at least one position a unit of two neighbouring Ar groups of the formula (E) (E) is present, where X is selected from N-R3, O, P-R3, S or Se, where R3 are independently of each other H, alkyl or aryl and
  • R, R1 , R2 independently of each other are H, alkyl, alkoxy or thioalkyl, where R1 and R2 are not both H.
  • Ar is a substituted or unsubstituted biphenyl group, substituted or unsubstituted fluorenyl group or substituted or unsubstituted tetrahydropyrenyl group,
  • R1-R3 are selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted Ce-4o aryl, substituted or unsubstituted C3-20 heteroaryl, substituted or unsubstituted C1.24 alkylsilyl and substituted or unsubstituted Ce-40 arylsilyl, n is an integer of 0-20, and
  • Heti and Het2 are substituted or unsubstituted C3-20 heteroaryl groups.
  • the compounds (F) can be used in an electron transport layer between the anode and the cathode of organic electroluminescent devices.
  • This document does not disclose compounds of the tetraarylbenzidine-type, bearing two fluorenyl-type groups at the nitrogen atoms bound to an 1 ,1 '-biphenylene backbone.
  • KR 2016 0116220 A describes structures of the general formula (G)
  • a and B are wherein Ar 1 to Ar 6 are each independently Ce-Ceo aryl, fluorenyl, a C2-C60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P, a fused C3-C60 aliphatic ring system, a fused Ce-Ceo aromatic ring system, etc., provided that at least one of the Ar 1 to Ar 6 groups is a crosslinking group selected from vinyl groups, acryloyl groups, methacyloyl groups, cyclic ethers, siloxanes, styrenes, trifluorovinyl ethers, benzocyclobutenes, cinnamates, chaicones, and oxetanes.
  • Ar 1 to Ar 6 are each independently Ce-Ceo aryl, fluorenyl, a C2-C60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P, a fused C3-
  • the tetraarylbenzidine-type compounds of the invention are advantageously suitable as hole conductors (p-semiconductors, electron donors) in organic photovoltaics. They are also especially suitable as electron blocking material (EBM).
  • EBM electron blocking material
  • a first object of the invention is a compound of the general formula (I) and mixtures thereof, wherein both R A groups have the same meaning and are selected from unsubstituted or substituted heterocyclic groups, comprising one or more rings wherein at least one ring is aromatic, wherein the heterocyclic group comprises as ring members 1 , 2, 3, 4 or more heteroatoms or heteroatom containing groups, selected from O, S, N and NR d , wherein the substituents R d in each case are independently of one another selected from hydrogen, straight-chain or branched C C4-alkyl, phenyl, 1- naphthyl, 2-naphthyl, 1 -fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 1- carbazolyl, 2-carbazolyl, 3-carbazoly and 4-carbazolyl, wherein phenyl, 1- naphthyl, 2-naphthyl, 1 -fluorenyl
  • R 1 , R", R 1 " and R IV are independently selected from hydrogen, phenyl and C1-C4- alkyl, wherein R 1 and R 1 " have the same meaning and R" and R IV have the same meaning,
  • R 1a and R 1b independently of one another, are selected from hydrogen, straightchain or branched Ci-Ce-alkyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 , 2 or 3 different or identical substituents selected from Ci-C4-alkyl.
  • a further object of the invention is the use of at least one compound of the general formula (I) as defined above and in the following as a hole transport material (HTM) in organic electronics, as an electron blocking material (EBM) in organic electronics, in organic solar cells (OSCs), solid-state dye sensitized solar cells (DSSCs) or Perovskite solar cells, in particular as a hole transport material in organic solar cells, as replacement of the liquid electrolyte in dye sensitized solar cells, as a hole transport material in Perovskite solar cells, in organic light-emitting diodes (OLEDs), in particular for displays on electronic devices and lighting.
  • HTM hole transport material
  • EBM electron blocking material
  • OSCs organic solar cells
  • DSSCs solid-state dye sensitized solar cells
  • Perovskite solar cells in particular as a hole transport material in organic solar cells, as replacement of the liquid electrolyte in dye sensitized solar cells, as a hole transport material in Perovskite solar cells, in organic light-emit
  • a further object of the invention is an electroluminescent arrangement, comprising an upper electrode, a lower electrode, wherein at least one of said electrodes is transparent, an electroluminescent layer and optionally an auxiliary layer, wherein the electroluminescent arrangement comprises at least one compound of the formula (I), as defined above or in the following.
  • the electroluminescent arrangement comprises at least one compound of the formula (I) in a hole-transporting layer or in an electron blocking layer.
  • the electroluminescent arrangement is an organic lightemitting diode (OLED).
  • OLED organic lightemitting diode
  • a further object of the invention is an organic solar cell, comprising: a cathode, an anode, one or more photoactive regions comprising at least one donor material and at least one acceptor material in separate layers or in form of a bulk heterojunction layer, optionally at least one further layer selected from exciton blocking layers, electron conducting layers and hole transport layers, wherein the organic solar cell comprises at least one compound of the formula (I) as defined above or in the following.
  • a further object of the invention is a process (in the following denoted as "Route 1") for the preparation of a compound of the formula (I), comprising the steps a11 ) providing a compound of the formula (II. a11 ) (Il.a11) wherein
  • X is Cl, Br, I, CH 3 SO 3 , CF 3 SO 3 , CH 3 -C 6 H 4 -SO 3 or C 6 H 5 -SO 3>
  • R 1a and R 1b are defined as above and in the following, b11 ) reacting the compound of the formula (ll.al 1 ) with an aromatic amine of the formula (III. b11)
  • R 1a and R 1b are defined as above and in the following, b12) reacting the aromatic amine of the formula (IV.a12) with a compound of the formula (V.b12)
  • R A is defined as above and in the following,
  • X is Cl, Br, I, CH 3 SO 3 , CF 3 SO 3 , CH 3 -C 6 H 4 -SO 3 or C 6 H 5 -SO 3 , in the presence of a palladium complex catalyst and a base, to obtain a compound (VI) b) reacting the compound of the formula (VI) with a compound of the formula (VII) wherein
  • X is Cl, Br, I, CH3SO3, CF3SO3, CH3-C6H4-SO3 or C 6 H 5 -SO 3)
  • R 1 , R", R 1 " and R IV are as defined above and in the following, in the presence of a palladium complex catalyst and a base to obtain a compound (I).
  • a further object of the invention is a process (in the following denoted as "Route 2") for the preparation of a compound of the formula (I), comprising the steps a2) providing a compound of the formula (VII) wherein
  • X is Cl, Br, I, CH3SO3, CF3SO3, CH3-C6H4-SO3 or C 6 H5-SO 3
  • R 1 , R", R 111 and R IV are as defined above and in the following, b2) reacting the compound of the formula (VII) with an aromatic compound of the formula (VIII)
  • R A is defined as above and in the following, in the presence of a palladium complex catalyst and a base to obtain a compound of the formula (IX) c2) reacting the compound of the formula (IX) with a compound of the formula (Il.a11) wherein
  • X is Cl, Br, I, CH3SO3, CF3SO3, CH3-C 6 H 4 -SO 3 or C 6 H 5 -SO 3 ,
  • R 1a and R 1b are defined as above and in the following, in the presence of a palladium complex catalyst and a base to obtain a compound (I).
  • a further object of the invention is a process (in the following denoted as "Route 3") for the preparation of a compound of the formula (I), comprising the steps a3) providing a compound of the formula (X) wherein
  • R 1 , R", R" 1 and R IV are independently selected from hydrogen and Ci-C 4 -alkyl, wherein R 1 and R 1 " have the same meaning and R" and R IV have the same meaning,
  • R 1a and R 1b independently of one another, are selected from hydrogen, straightchain or branched Ci-Ce-alkyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 , 2 or 3 different or identical substituents selected from Ci-C4-alkyl, where R 1a and R 1b may also together form an alkylene group (CH2) r with r being 4 or 5, b3) reacting the compound of the formula (X) with a compound of the formula (V.b12)
  • X is Cl, Br, I, CH3SO3, CF3SO3, CH3-C6H4-SO3 or C 6 H 5 -SO 3 , in the presence of a palladium complex catalyst and a base, to obtain a compound (I).
  • the compounds of the formula (I) are characterized by a good thermal stability and environmental stability.
  • compounds (I) have a high glass transition temperature. They are usually sublimable and allow the fabrication of devices by physical vapor deposition.
  • the compounds of the formula (I) are in particular suitable as organic semiconductors. Preferred applications of the compounds (I) are as hole transport material (HTM) or electron blocking material (EBM).
  • the tetraarylbenzidine-type compounds of the invention are advantageously suitable as hole conductors (p-semiconductors, electron donors) in organic photovoltaics.
  • the material from example 10 of this invention displays a glass temperature of 159.5 °C, is amorphous (XRD) and and shows at similar concentrations of NDP-9 a significantly higher conductivity as the known material (EP0879868 A2) of example 7.
  • the invention further allows providing compounds of the formula (I), where the size of the semiconductor band gap is adjusted to very effectively utilize the solar light.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, particularly chlorine, bromine or iodine.
  • halo denotes in each case fluoro, chloro, bromo or iodo.
  • C n -Cm-alkyl refers to a branched or unbranched saturated hydrocarbon group having n to m carbon atoms, e.g. 1 to 2 (“Ci-C2-alkyl”), 1 to 4 (“Ci-C4-alkyl”) or 1 to 6 (“Ci-Ce-alkyl”).
  • Ci-C 2 -Alkyl is methyl or ethyl.
  • Ci-C4-alkyl examples are, in addition to those mentioned for Ci-C2-alkyl, propyl, isopropyl, butyl, 1 -methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1 ,1 -dimethylethyl (tert-butyl).
  • Ci-Ce-alkyl examples are, in addition to those mentioned for Ci-C4-alkyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl,
  • C n -C m -alkoxy refers to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 2 carbon atoms or 1 to 4 carbon atoms (as mentioned above) attached via an oxygen atom at any bond in the alkyl group to the remainder of the molecule.
  • Ci-C2-Alkoxy is methoxy or ethoxy.
  • C1-C4- alkoxy are, in addition to those mentioned for Ci-Ca-alkoxy, n-propoxy, 1 -methylethoxy (isopropoxy), butoxy, 1 -methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1 ,1 -dimethylethoxy (tert-butoxy).
  • C n -C m -cycloalkyl refers to a monocyclic n- to m- membered saturated cycloaliphatic radical having, e.g. 3 to 8 carbon atoms.
  • Examples for Cs-Cs-cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • C n -Cm-cycloalkoxy refers to a monocyclic n- to m-membered saturated cycloaliphatic radical, e.g. Cs-Cs-cycloalkyl (as mentioned above) bonded through O linkage to the skeleton.
  • aryl refers to monocyclic, bicyclic, tricyclic and tetracyclic aromatic hydrocarbon radicals with 6 to 18 ring carbon atoms, in which the rings are all condensed (fused) or two of the aromatic rings may also be joined to one another by a chemical bond and a divalent radical selected from -CH2-, -O-, -S- or -N(H)-.
  • Examples include phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, dibenzofuranyl (dibenzofuryl), dibenzothienyl, carbazolyl, 11 H-benzo[b]fluorenyl, naphtho[2,3-b]benzofuryl, naphtho[2,3-b]benzothienyl and 5H-benzo[b]carbazolyl.
  • Aryl may be substituted at one, two, three, four, more than four or all substitutable positions.
  • Suitable substituents are in general Ci-Ce-alkyl, Ci-C4-alkoxy, carbazol-9-yl (N-bound carbazolyl), which is unsubstituted or substituted by Ci-C4-alkyl, Ci-C4-alkoxy and phenyl, wherein phenyl on its part may be substituted by 1 , 2, 3 or 4 different or identical substituents selected from Ci-C4-alkyl and Ci-C4-alkoxy.
  • suitable substituents attached at aryl are in general also diphenylamino, Cs-Cs-cycloalkyl, phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl and phenanthryl, wherein each of the cyclic rings in the eight last-mentioned groups are unsubstituted or substituted by 1 , 2, 3, 4 or 5 different or identical substituents selected from Ci-C4-alkyl, Ci-C4-alkoxy and carbazol-9-yl which is unsubstituted or substituted by Ci-C 4 -alkyl, Ci-C4-alkoxy and phenyl, wherein phenyl on its part may be substituted by 1 , 2, 3 or 4 different or identical substituents selected from Ci-C4-alkyl and Ci-C4-alkoxy.
  • two substituents bonded to the same carbon atom of fluorenyl or 11 H-benzo[b]fluorenyl together may form an alkylene group (CH2)r with r being 4, 5, 6 or 7 thus forming a 5- to 8-membered saturated carbocycle, in which 1 or 2 hydrogen atoms in this group may be replaced by a group Ci- -alkyl or Ci-C4-alkoxy or two substituents bonded to the same carbon atom of fluorenyl or 11 H-benzo[b]fluorenyl together may form an alkylene group (CH2) r with r being 4, 5, 6 or 7 thus forming a 5- to 8-membered saturated carbocycle, which may be benz-annelated with one or two benzene groups, where the benzene ring(s) is (are) optionally substituted by 1 , 2, 3 or 4 identical or different C1-C4- alkyl or Ci-C4-alkoxy.
  • heterocyclic group containing at least one aromatic ring denotes monocyclic and polycyclic ring systems containing at least one aromatic ring, wherein the ring system comprises as ring members 1 , 2, 3, 4 or more heteroatoms or heteroatom containing groups, selected from O, S, N and NR d , wherein the substituents R d in each case are independently of one another selected from hydrogen, straight-chain or branched Ci-C4-alkyl, straight-chain or branched Ci-C4-alkoxy, phenyl, 1 -naphthyl, 2-naphthyl, 1 -fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 1-carbazolyl, 2- carbazolyl, 3-carbazoly and 4-carbazolyl, wherein phenyl, 1-naphthyl, 2-naphthyl, 1- fluorenyl, 2-fluorenyl
  • bicyclic, tricyclic and tetracylic ring systems comprising 1 , 2, 3 or 4 rings selected from saturated, partially unsaturated, or fully unsaturated carbocycles and heterocycles with the proviso that 1 , 2, 3 or 4 of the rings are aromatic.
  • heterocycle includes preferably 5- to 8-membered, more preferably 5- to 7-membered, in particular 5- or 6-membered, monocyclic heterocyclic rings.
  • the heterocycles may be saturated, partially unsaturated, or fully unsaturated.
  • the term “fully unsaturated” also includes “aromatic”.
  • a fully unsaturated heterocycle is thus an aromatic heterocycle, preferably a 5- or 6-membered aromatic heterocycle comprising one or more, e.g. 1 , 2, 3, or 4, preferably 1 , 2, or 3 heteroatoms selected from N, O and S as ring members.
  • Non-aromatic heterocyles usually comprise 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms or heteroatom containing groups, selected from O, S, N and NR d as ring members, preferably selected from N, O and S as ring members.
  • a non-hydrogen radical is in the place of hydrogen radical of any substitutable atom of the moiety. If there are more than one substitution on a moiety, each non-hydrogen radical may be identical or different unless otherwise stated.
  • Preferred compounds according to the invention are compounds of the formula (I), wherein R 1a and R 1b are independently of one another selected from hydrogen and straight-chain or branched Ci-C 4 -alkyl. More preferably, R 1a and R 1b are independently of one another selected from hydrogen, methyl and ethyl.
  • both radicals R 1a in formula (I) have the same meaning.
  • both radicals R 1b in formula (I) have the same meaning.
  • all radicals R 1a and R 1b in formula (I) have the same meaning.
  • all radicals R 1a and R 1b in formula (I) are hydrogen. In a second preferred embodiment, all radicals R 1a and R 1b in formula (I) are methyl. In a third preferred embodiment, all radicals R 1a and R 1b in formula (I) are phenyl.
  • R', R", R 1 " and R IV are independently selected from hydrogen, Ci-C4-alkyl and Cr C4-alkoxy.
  • R 1 , R", R 111 and R IV are independently selected from hydrogen, Ci-C 2 -alkyl and Ci-C2-alkoxy.
  • R 1 , R", R 1 " and R IV are all hydrogen.
  • the compound of the formula (I) is selected from compounds (LA),
  • R A groups have the same meaning and are selected from unsubstituted or substituted heterocyclic groups.
  • R A groups are selected from groups of the formulae (AR-I) to (AR-XCV)
  • # in each case denotes the bonding site to the nitrogen atom; x is 0, 1 or 2; y1 is 0, 1 or 2; y2 is 0, 1 or 2; y3 is 0, 1 or 2;
  • R 2 independently of one another are selected from straight-chain or branched C1-C4- alkyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 , 2 or 3 different or identical substituents selected from Ci-C4-alkyl, phenyl, tolyl, xylyl and mesityl;
  • R 3 independently of one another are selected from straight-chain or branched C1-C4- alkyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 , 2 or 3 different or identical substituents selected from Ci-C4-alkyl, phenyl, tolyl, xylyl and mesityl;
  • R 4 is selected from straight-chain or branched Ci-C4-alkyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 , 2 or 3 different or identical substituents selected from Ci-C4-alkyl, phenyl, tolyl, xylyl and mesityl;
  • R 5 independently of one another are selected from straight-chain or branched C1-C4- alkyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 , 2 or 3 different or identical substituents selected from Ci-C4-alkyl, phenyl, tolyl, xylyl and mesityl; in formulae AR-LXXXVIII, AR-LXXXIX, AR-XC, AR-XCI, AR-XCII and AR-XCIII: R 23 , R 24 , R 25 and R 26 , if present, independently of one another, are selected from hydrogen, straight-chain or branched Ci-C4-alkyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 , 2 or 3 different or identical substituents selected from Ci-C4-alkyl, R e is hydrogen or Ci-Ce-alkyl, and
  • R f is hydrogen or Ci-Cs-alkyl
  • R 21 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29a and R 29b are selected from hydrogen, straight-chain or branched Ci-C4-alkyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 , 2 or 3 different or identical substituents selected from Ci-C4-alkyl, where R 29a and R 29b together may also form an alkylene group (CH2)r with r being 4, 5 or 6.
  • each radical R 2 is preferably selected from methyl, ethyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 or 2 different or identical substituents selected from methyl, ethyl, phenyl, tolyl, xylyl and mesityl.
  • each radical R 3 is preferably selected from methyl, ethyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 or 2 different or identical substituents selected from methyl, ethyl, phenyl, tolyl, xylyl and mesityl.
  • radical R 4 is preferably selected from methyl, ethyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 or 2 different or identical substituents selected from methyl, ethyl, phenyl, tolyl, xylyl and mesityl.
  • each radical R 5 is preferably selected from methyl, ethyl and phenyl, wherein phenyl is unsubstituted or substituted by 1 or 2 different or identical substituents selected from methyl, ethyl, phenyl, tolyl, xylyl and mesityl.
  • the value for y1 is preferably 0 or 1.
  • the value for y2 is preferably 0 or 1 .
  • the value for y3 is preferably 0 or 1 .
  • each R 23 , R 24 , R 25 and R 26 is selected from hydrogen, Ci-Cz-alkyl, Ci-C2-alkoxy, phenyl, 1 -naphthyl, 2-naphthyl, 9- fluorenyl and 9-carbazolyl, wherein phenyl, 1 -naphthyl, 2-naphthyl, 9-fluorenyl or 9- carbazolyl are unsubstituted or substituted by 1 , 2 or 3 different or identical substituents selected from Ci-C2-alkyl and Ci-C 2 -alkoxy, R e is hydrogen or methyl, and
  • R f is hydrogen or methyl.
  • each radical R 21 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29a and R 29b is selected from hydrogen, Ci-C2-alkyl, Ci-C2-alkoxy, phenyl, 1 -naphthyl, 2-naphthyl, 1 -fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 1-carbazolyl, 2- carbazolyl, 3-carbazoly and 4-carbazolyl, wherein phenyl, 1 -naphthyl, 2-naphthyl, 1- fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 1-carbazolyl, 2-carbazolyl, 3-carbazoly and 4-carbazolyl are unsubstituted or substituted by 1 or 2 different
  • both R A groups are a group of the formula AR-LXII, or both R A groups are a group of the formula AR-LXIII, or both R A groups are a group of the formula AR-LXIV, or both R A groups are a group of the formula AR-LXVI, or both R A groups are a group of the formula AR-LXVII, or both R A groups are a group of the formula AR-LXVIII, or both R A groups are a group of the formula AR-LXXXVIII, or both R A groups are a group of the formula AR-XCIV or both R A groups are a group of the formula AR-XLVIL
  • both R A groups are a group of the formula AR-LXIV, wherein R 5 are all hydrogen, or both R A groups are a group of the formula AR-LXVIII, wherein R 5 are all hydrogen, or both R A groups are a group of the formula AR-LXXXVIII, wherein R 23 , R 25 and R 26 are hydrogen and R e and R f are methyl, or both R A groups are a group of the formula AR-XCIV, wherein R 21 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 are hydrogen and R 29a and R 29b are methyl, both R A groups are a group of the formula AR-XLVII, wherein y2 is 0.
  • the compounds of the formula (I) are selected from the compounds specified in the examples.
  • Variant 1 (synthesis of compound (VI) via substeps a11 ) and b11 )
  • step b11 the compound (II. a11 ) is reacted with a primary aromatic amine of the formula (111. b11 ) in the presence of a palladium catalyst in terms of a Buchwald- Hartwig reaction.
  • Primary aromatic amines of the formula (lll.bl 1 ) are readily available, e.g. via nitration of an aryl or heteroaryl compound followed by reduction of the obtained nitro compound.
  • Suitable palladium catalyst or catalyst precursors are for example palladium(O) bis(dibenzylideneacetone) (Pd(dba)2), tris-(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), [1 ,1-bis(diphenylphosphino)-ferrocene]dichloropalladium(ll) (PdCl2(dppf)), palladium chloride (PdCh), bis(acetonitrile)palladium chloride (Pd(ACN)2C ), [1 ,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium dichloride (PEPPSI-iPr), dichloro[1 ,3-bis(2,6-di-3-pentylphenyl)imidazol-2-ylidene](3-chloro
  • the reaction is usually carried out in the presence of a ligand.
  • the ligand is any molecule capable of coordinating to the palladium precursor and facilitating the Buchwald-Hartwig reaction, preferably an dialkylbiarylphosphines or tri-tert-butyl phosphine.
  • dialkylbiarylphosphine ligands examples include 2- dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl (DavePhos), 2- dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos), 2-dicyclohexylphosphino- 2',6'-dimethoxybiphenyl (Sphos), 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl (tBuXPhos), (2-biphenyl)dicyclohexylphosphine, 2-(dicyclohexylphosphino)biphenyl (CyJohnPhos), (2-biphenyl)di-tert-butylphosphine (JohnPhos), 2-dicyclohexyl- phosphino-2',
  • the reaction is performed in the presence of a base such as an alkali alkoxide, earth alkali alkoxide, alkali carbonate or earth alkali carbonate, alkali metal amide or trialkyl amine.
  • a base such as an alkali alkoxide, earth alkali alkoxide, alkali carbonate or earth alkali carbonate, alkali metal amide or trialkyl amine.
  • the base is sodium tert-butoxide, cesium carbonate, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, lithium diisopropylamide or lithium dicyclohexylamide.
  • the base is sodium tert-butoxide.
  • the reaction is generally carried out in a solvent.
  • suitable solvents are for example aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, ethers, such as diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran and dimethoxyethane, amides such as dimethylformamide or N-methylpyrrolidone.
  • the reaction temperature generally ranges between 50° and 130°C.
  • the reactions generally are run under an inert atmosphere (e.g. under dry nitrogen or argon).
  • Variant 2 (synthesis of compound (VI) via substeps a12) and b12)
  • Primary aromatic amines of the formula (IV.a12) wherein R 1a and R 1b are defined as above and in the following can be obtained by routine methods or are commercially available.
  • 2-Amino-9,9-dimethylfluorene can be purchased e.g. from Alfa Aesar.
  • steps b12 compounds (IV.a12) are subjected to an arylation reaction with an aromatic compound R A -X (V.b12).
  • the reaction conditions are analogous to the conditions of the Buchwald-Hartwig reaction of step b11 ).
  • reaction step b two reaction equivalents of compound (VI) are reacted with a benzidine derivative of the formula (VII)
  • a benzidine derivative of the formula (VII) is provided in step a2) and reacted with a primary aromatic amine of the formula (VIII) in step b2). Again, the reaction conditions are analogous to the conditions of the Buchwald-Hartwig reaction of step b11). Intermediate (IX) is subjected to a further Buchwald-Hartwig reaction in step c2) with two equivalents of fluorene derivative (ll.al 1).
  • a compound of the formula (X) bearing two secondary amino groups can be provided and reacted with two equivalents of compound of the formula (V.b12) R A -X in a Buchwald-Hartwig reaction.
  • JP 2009043896 A and JP 2009158535 A describe a compound (D) and a synthesis starting from 2-iodo-9,9-dimethylfluorene.
  • Goldberg reaction with acetamide leads to 2-(N-acetyl)-9,9-dimethylfluorene that can be coupled by further Goldberg reaction with 4,4'-diiodo-1 ,1 '-biphenyl, followed by saponification of the resulting bis(N-acetyl) derivative.
  • the compounds according to the invention are in particular suitable for use in an electronic device.
  • An electronic device here is taken to mean a device which comprises at least one layer which comprises at least one organic compound.
  • the present invention therefore furthermore relates to the use of the compounds of formula (I) or a mixture of at least two different compounds thereof as a hole transport material (HTM) in organic electronics, as an electron blocking material (EBM) in organic electronics, in organic solar cells (OSCs), solid-state dye sensitized solar cells (DSSCs) or Perovskite solar cells, in particular as a hole transport material in organic solar cells, as replacement of the liquid electrolyte in dye sensitized solar cells, as a hole transport material in Perovskite solar cells, in organic light-emitting diodes (OLEDs), in particular for displays on electronic devices and lighting, for electrophotography, in particular as photoconductive material in an organic photoconductor (OPC), for organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs) and organic laser diodes.
  • the compounds according to the invention are especially suitable as a hole transport material (HTM) in organic electronics. H
  • the compounds according to the invention may be employed as the sole HTM or in combination with at least one further HTM.
  • Suitable further hole transport materials are well-known in the art.
  • Preferred hole transport materials for combination are spiro- OMeTAD, 2,2',7,7'-tetrakis-(N,N'-di-4-methoxy-3,5-dimethylphenylamme)-9,9'- spirofluorene, tris(p-anisyl)amine, N,N,N',N'-tetrakis(4-methoxyphenyl)-1 ,T-biphenyl- 4,4'-diamine, 2,7-bis[N,N-bis(4-methoxy-phenyl)amino]-9,9-spirobifluorene, poly(3- hexylthiophene) (P3HT), poly(3,4-ethylenedioxythiophene)-poly( styrenesul
  • Typical hole transport materials for perwoskite solar cells have been the subject of reviews, e.g. Z. Shariatinia, “Recent progress in development of diverse kinds of hole transport materials for the perovskite solar cells: A review”, Renewable and Sustainable Energy Reviews, 2020, 119,109608, D0l:10.1016/j.rser.2019.109608.
  • Suitable additives are pyridine compounds such as tert-butylpyridine, imidazoles as disclosed in WO2013/026563, claims 1 to 15 and disclosed on pages 15 to 17 or polymer additives such as poly(4-vinylpyridine) or its copolymer with e.g. vinylstyrene or alkylmethacrylate.
  • pyridine compounds such as tert-butylpyridine, imidazoles as disclosed in WO2013/026563, claims 1 to 15 and disclosed on pages 15 to 17 or polymer additives such as poly(4-vinylpyridine) or its copolymer with e.g. vinylstyrene or alkylmethacrylate.
  • a preferred pyridine compound is tert-butylpyridine.
  • the compounds according to the invention used as the HTMs may be combined with lithium salts as described in Phys. Chem., Chem. Phys, 2013, 15, 1572-2579.
  • the compounds according to the invention used as HTMs may be combined with a p-dopant such as N(C 6 H5Br) 3 , SbCh, V2O5, M0O3, WO3, Re 2 O3, F 4 - TCNQ (tetrafluoro-tetracyanoquinodimethane), HAT-CN (1 ,4, 5, 8, 9,11 -hexaazatri- phenylene-hexacarbonitrile) F6-TCNNQ (1 ,3,4,5,7,8-hexafluorotetracyanonaphtho- quinodimethane, obtainable from Novaled), NDP-9 (a p-dopant obtainable from Novaled) or Co complex salts.
  • a p-dopant such as N(C 6 H5Br) 3 , SbCh, V2O5, M0O3, WO3, Re 2 O3, F 4 - TCNQ (tetrafluoro-tetracyanoquinodimethane), H
  • Suitable dopants are described in Chem. Mater., 2013, 25, 2986-2990 or J. Am. Chem. Soc, 2011 , 133, 18042. Also suitable [3]-radialenes as described in EP 2 180 029 A1 can be applied. Suitable are also the cerium (IV) complexes described in WO 2021/048044 A1 and the Cerium-ethylenediamine ketone- type and Cerium-salene-type complexes described in WO 2022101343 A1.
  • the invention furthermore relates to an electroluminescent arrangement comprising an upper electrode, a lower electrode, wherein at least one of said electrodes is transparent, an electroluminescent layer and optionally an auxiliary layer, wherein the electroluminescent arrangement comprises at least one compound of the formula (I).
  • the electroluminescent arrangement comprises at least one compound of the formula (I).
  • the preferences stated above likewise apply to the substrate.
  • the at least one compound of the formula (I) or (I. a) is employed in a hole-transporting layer or electron blocking layer.
  • the invention furthermore relates to an electroluminescent arrangement in form of an organic light-emitting diode (OLED).
  • an electron blocking layer is disposed adjacent to an emissive layer. Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer.
  • An electron blocking layer may be disposed between emissive layer and an hole transport layer, to block electrons from leaving emissive layer in the direction of hole transport layer.
  • a hole blocking layer may be disposed between emissive layer and electron transport layer, to block holes from leaving emissive layer in the direction of electron transport layer.
  • the OLEDs can be employed for various applications, for example for monochromatic or polychromatic displays, for lighting applications or for medical and/or cosmetic applications, for example in phototherapy.
  • the organic electroluminescent device particularly in form of an OLED, comprises a cathode, an anode and at least one emitting layer. Apart from these layers, it may also comprise further layers, for example in each case one or more holeinjection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers and/or charge-generation layers. Interlayers, which have, for example, an exciton-blocking function, may likewise be introduced between two emitting layers. However, it should be noted that each of these layers does not necessarily have to be present.
  • the organic electroluminescent device here may comprise one emitting layer or a plurality of emitting layers. If a plurality of emission layers is present, these preferably have in total a plurality of emission maxima between 380 nm and 750 nm, resulting overall in white emission, i.e. various emitting compounds which are able to fluoresce or phosphoresce are used in the emitting layers. Particular preference is given to systems having three emitting layers, where the three layers exhibit blue, green and orange or red emission (for the basic structure see, for example, WO 2005/011013). It is possible here for all emitting layers to be fluorescent or for all emitting layers to be phosphorescent or for one or more emitting layers to be fluorescent and one or more other layers to be phosphorescent.
  • the compound according to the invention in accordance with the embodiments indicated above can be employed here in different layers, depending on the precise structure. Preference is given to an organic electroluminescent device comprising a compound of the formula (I) or the preferred embodiments as hole-transport material in a hole-transport or hole-injection or electron-blocking layer or as matrix material for fluorescent or phosphorescent emitters, in particular for phosphorescent emitters.
  • the preferred embodiments indicated above also apply to the use of the materials in organic electronic devices.
  • the compound of the formula (I) or the preferred embodiments is employed as hole-transport or hole-injection material in a hole-transport or hole-injection layer.
  • the emitting layer here can be fluorescent or phosphorescent.
  • a hole-injection layer generally is a layer which facilitates electron injection from the anode to the organic layer.
  • the hole-injection layer can be situated directly adjacent to the anode.
  • a hole-transport layer transports the holes from the anode to the emitting layer and is located between a hole-injection layer and an emitting layer.
  • doped hole transport layers can be employed.
  • the architecture of actual OLEDs often improves quantum efficiency by using a graded heterojunction.
  • the graded heterojunction architecture the composition of hole and electron-transport materials varies continuously within the emissive layer with a dopant emitter.
  • the graded heterojunction architecture combines the benefits of both conventional architectures by improving charge injection while simultaneously balancing charge transport within the emissive region.
  • the compounds of the formula (I) or the preferred embodiments thereof are employed in an electron-blocking layer.
  • An electron-blocking layer may be used to reduce the number of charge carriers (electrons) that leave the emissive layer.
  • An electron-blocking layer usually is a layer which is directly adjacent to an emitting layer on the anode side.
  • An electron blocking layer may be disposed between emissive layer and hole transport layer to block electrons from leaving the emissive layer in the direction of hole transport layer.
  • the compound of the formula (I) or the preferred embodiments thereof are particularly preferably employed in a hole-transport layer or electron blocking layer.
  • the compound of the formula (I) or the preferred embodiments thereof are employed as matrix material for a fluorescent or phosphorescent compound, in particular for a phosphorescent compound, in an emitting layer.
  • the organic electroluminescent device here may comprise one emitting layer or a plurality of emitting layers, where at least one emitting layer comprises at least one compound according to the invention as matrix material.
  • the compound of the formula (I) or the preferred embodiments thereof are employed as matrix material for an emitting compound in an emitting layer, it is preferably employed in combination with one or more phosphorescent materials (triplet emitters).
  • Phosphorescence in the sense of this invention is taken to mean the luminescence from an excited state having a spin multiplicity >1 , in particular from an excited triplet state.
  • all luminescent complexes containing transition metals or lanthanoids in particular all luminescent iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.
  • the mixture comprising the compound of the formula (I) or the preferred embodiments and the emitting compound comprises between 99.9 and 1% by weight, preferably between 99 and 10% by weight, particularly preferably between 97 and 60% by weight, in particular between 95 and 80% by weight, of the compound of the formula (I) or the preferred embodiments, based on the entire mixture comprising emitter and the compound of the formula (I).
  • the mixture comprises between 0.1 and 99% by weight, preferably between 1 and 90% by weight, particularly preferably between 3 and 40% by weight, in particular between 5 and 20% by weight, of the emitter, based on the entire mixture comprising emitter and the compound of the formula (I).
  • a further object of the invention is the use of at least one compound of the general formula (I) as defined above in organic solar cells (OSCs).
  • the compounds of the general formula (I) are used in particular as a hole transport material or electron blocking material in organic solar cells.
  • Organic solar cells generally have a layer structure and generally comprise at least the following layers: anode, photoactive layer and cathode. These layers are generally applied to a substrate suitable for this purpose.
  • the structure of organic solar cells is described, for example, in US 2005/0098726 and US 2005/0224905.
  • the invention provides an organic solar cell which comprises a substrate with at least one cathode and at least one anode, and at least one compound of the general formula (I) as defined above as a material of at least one of the layers.
  • the organic solar cell of the invention comprises at least one photoactive region.
  • a photoactive region may comprise two layers, each of which has a homogeneous composition and forms a flat donor-acceptor heterojunction.
  • a photoactive region may also comprise a mixed layer and form a donor-acceptor heterojunction in the form of a donor-acceptor bulk heterojunction
  • the invention also refers to an organic solar cell, comprising: a cathode, an anode, one or more photoactive regions comprising at least one donor material and at least one acceptor material in separate layers or in form of a bulk heterojunction layer, optionally at least one further layer selected from exciton blocking layers, electron conducting layers, hole transport layers, wherein the organic solar cell comprises at least one compound of the formula (I) as defined above or of a composition comprising at least two different compounds of the general formula (I) as defined above.
  • the heterojunction can have a flat configuration (see: Two layer organic photovoltaic cell, C. W. Tang, Appl. Phys. Lett., 48 (2), 183-185 (1986) or N. Karl, A. Bauer, J. Holzapfel, J. Natanner, M. Mbbus, F. Stolzle, Mol. Cryst. Liq. Cryst., 252, 243-258 (1994).).
  • the heterojunction can be a bulk heterojunction, also referred to as an interpenetrating donor-acceptor network.
  • Organic photovoltaic cells with a bulk heterojunction are described, for example, by C. J. Brabec, N. S. Sariciftci, J. C. Hummelen in Adv. Funct. Mater., 11 (1), 15 (2001 ) or by J. Xue, B. P. Rand, S. Uchida and S. R. Forrest in J. Appl. Phys. 98, 124903 (2005).
  • the compounds of the general formula (I) can be used in cells with MiM, pin, pn, Mip or Min structure
  • M metal
  • p p-doped organic or inorganic semiconductor
  • n n-doped organic or inorganic semiconductor
  • i intrinsically conductive system of organic layers; see, for example, J. Drechsel et al., Org. Electron., 5 (4), 175 (2004) or Maennig et al., Appl. Phys. A 79, 1-14 (2004)).
  • Tandem cells are described, for example, by P. Peumans, A. Yakimov, S. R. Forrest in J. Appl. Phys, 93 (7), 3693-3723 (2003).
  • a tandem cell consists of two or more than two subcells.
  • a single subcell, some of the subcells or all subcells may have photoactive donor-acceptor heterojunctions.
  • Each donor-acceptor-heterojunction may be in the form of a flat heterojunction or in the form of a bulk heterojunction.
  • the subcells which form the tandem cell may be connected in parallel or in series. There is preferably an additional recombination layer in each case between the individual subcells.
  • the individual subcells have the same polarity, i.e. generally either only cells with normal structure or only cells with inverse structure are combined with one another.
  • Suitable substrates for organic solar cells are, for example, oxidic materials, polymers and combinations thereof.
  • Preferred oxidic materials are selected from glass, ceramic, SiO?, quartz, etc.
  • Preferred polymers are selected from polyethylene terephthalates, polyolefins (such as polyethylene and polypropylene), polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth)acrylates, polystyrenes, polyvinyl chlorides and mixtures and composites.
  • Suitable electrodes are in principle semiconductors, metal alloys, semiconductor alloys and combinations thereof.
  • Preferred metals are those of groups 2, 8, 9, 10, 11 or 13 of the periodic table, e.g. Pt, Au, Ag, Cu, Al, In, Mg or Ca.
  • Preferred semiconductors are, for example, doped Si, doped Ge, indium tin oxide (ITO), fluorinated tin oxide (FTO), gallium indium tin oxide (GITO), zinc indium tin oxide (ZITO), etc.
  • Preferred metal alloys are for example alloys based on Pt, Au, Ag, Cu, etc.
  • the material used for the electrode facing the light is preferably a material at least partly transparent to the incident light.
  • This preferably includes electrodes which have glass and/or a transparent polymer as a carrier material.
  • the electrical contact connection is generally effected by means of metal layers and/or transparent conductive oxides (TCOs). These preferably include ITO, doped ITO, FTO (fluorine doped tin oxide), AZO (aluminum doped tin oxide), ZnO, TiOa, Ag, Au, Pt.
  • the material used for the electrode facing away from the light is a material which at least partly reflects the incident light.
  • the organic solar cells according to the invention are present as an individual cell with flat heterojunction and normal structure.
  • the cell has the following structure: an at least partly transparent conductive layer (top electrode, anode) a hole-conducting layer (hole transport layer, HTL) a layer which comprises a donor material a layer which comprises an acceptor material an exciton-blocking and/or electron-conducting layer a second conductive layer (back electrode, cathode)
  • the organic solar cells according to the invention are present as an individual cell with a flat heterojunction and inverse structure.
  • the cell has the following structure: an at least partly transparent conductive layer (cathode) an exciton-blocking and/or electron-conducting layer a layer which comprises an acceptor material a layer which comprises a donor material a hole-conducting layer (hole transport layer, HTL) a second conductive layer (back electrode, anode)
  • the organic solar cells according to the invention are present as an individual cell with normal structure and have a bulk heterojunction.
  • the cell has the following structure: an at least partly transparent conductive layer (anode) a hole-conducting layer (hole transport layer, HTL) a mixed layer which comprises a donor material and an acceptor material, which form a donor-acceptor heterojunction in the form of a bulk heterojunction an electron-conducting layer an exciton-blocking and/or electron-conducting layer a second conductive layer (back electrode, cathode)
  • an at least partly transparent conductive layer anode
  • HTL hole transport layer
  • HTL hole transport layer
  • mixed layer which comprises a donor material and an acceptor material, which form a donor-acceptor heterojunction in the form of a bulk heterojunction
  • an electron-conducting layer an exciton-blocking and/or electron-conducting layer
  • second conductive layer back electrode, cathode
  • the organic solar cells according are present as an individual cell with inverse structure and have a bulk heterojunction.
  • donor-acceptor heterojunctions examples are a donoracceptor double layer with a flat heterojunction, or the heterojunction is configured as a hybrid planar-mixed heterojunction or gradient bulk heterojunction or annealed bulk heterojunction.
  • the production of a hybrid planar-mixed heterojunction is described in Adv. Mater. 17, 66-70 (2005).
  • mixed heterojunction layers which were formed by simultaneous evaporation of acceptor and donor material are present between homogeneous donor and acceptor material.
  • the donor-acceptor-heterojunction is in the form of a gradient bulk heterojunction. In the mixed layers composed of donor and acceptor materials, the donor-acceptor ratio changes gradually.
  • the donor-acceptor-heterojunction is configured as an annealed bulk heterojunction; see, for example, Nature 425, 158- 162, 2003.
  • the process for producing such a solar cell comprises an annealing step before or after the metal deposition. As a result of the annealing, donor and acceptor materials can separate, which leads to more extended percolation paths.
  • a further object of the invention is the use of at least one compound of the general formula (I) or (LA) as defined above in solid-state dye sensitized solar cells (DSSCs) or Perovskite solar cells. These compounds are used in particular as replacement of the liquid electrolyte in dye sensitized solar cells and as a hole transport material in Perovskite solar cells.
  • the compounds of the formula (I) or (LA) can be used advantageously as HTMs in perovskite solar cells. They can also be used to replace the liquid electrolyte of conventional DSSCs to provide solid-state DSSC devices.
  • the compounds of the invention are then preferably employed in a photosensitized nanoparticle layer comprising a sensitizing dye or a perovskite and at least one compound of the general formula (I) according to the invention.
  • the compounds of the invention are employed in a DSSC.
  • the construction of a DSSC is generally based on a transparent substrate, which is coated with a transparent conductive layer, the working electrode.
  • An n-conductive metal oxide is generally applied to this electrode or in the vicinity thereof, for example a nanoporous TiO2 layer of approximately 2 to 20 pm thickness.
  • a monolayer of a light-sensitive dye is typically adsorbed, which can be converted to an excited state by light absorption.
  • This layer which carries the lightsensitive dye is generally referred to as the light absorbing layer of the DSSC.
  • the counter electrode may optionally have a catalytic layer of a metal, for example platinum, with a thickness of a few pm.
  • Suitable are in principle all sensitizing dyes, as long as the LUMO energy state is marginally above the conduction bandedge of the photoelectrode to be sensitized.
  • Examples of dyes are disclosed in Nanoenergy, de Souza, Flavio Leandro, Leite, Edson Roberto (Eds.), Springer, ISBN 978-3-642-31736-1 , pages 58 to 74 or black dyes as described in US 8,383,553.
  • Preferred dyes are described in WO 2015049031 A1 which is incorporated herein by reference.
  • the compounds of the invention are employed in a Perovskite solar cell.
  • Suitable Perovskites for Perovskite solar cells (PSCs) are known in the art.
  • the perovskite material comprised in the devices according to the invention may be part of the charge transport layer but may also be part of another layer or scaffold within the device.
  • Suitable perovskite materials may comprise two halides corresponding to formula Xa p.x Xb(x), wherein Xa and Xb are each independently selected from Cl, Br, or I, and x is greater than 0 and less than 3.
  • Suitable pervoskite materials are also disclosed in WO 2013/171517, claims 52 to 71 and claims 72 to 79, which is entirely incorporated herein by reference.
  • Suitable pervoskite materials are CsSnl 3 , CH 3 NH 3 Pbl2CI, CH 3 NH 3 Pbl 3 , CH 3 NH 3 Pb(li- x Br x ) 3 , CH 3 NH 3 Snl 2 CI, CH 3 NH 3 Snl 3 or CH 3 NH 3 Sn(li- x Br x ) 3 , with 0 ⁇ x ⁇ 1.
  • Preferred perovskite materials are disclosed in WO 2013/171517 on page 18, lines 5 to 17.
  • the charge transport layer according to the invention as described before or the device according to the invention as described before or below may furthermore comprise an insulator such as alumina as described in Michael M. Lee et al, Science, 338, 643, 2012.
  • the charge transport layer according to the invention or the device according to the invention as described before or below may furthermore comprise semiconductor oxide nanoparticles.
  • the charge transport layer according to the invention or the device according to the invention preferably comprises semiconductor oxide nanoparticles.
  • the semiconductor is based on material selected from the group of Si, TiO 2 , SnO 2 , Fe 2 O 3 , WO 3 , ZnO, Nb 2 O 5 , CdS, ZnS, PbS, Bi 2 S 3 , CdSe, GaP, InP, GaAs, CdTe, CulnS 2 , and/or CulnSe 2 .
  • the charge transport layer according to the invention as described before is present on a glass support or plastic or metal foil, optionally together with a dense layer of TiO 2 .
  • the support is conductive.
  • the present invention furthermore relates to a electronic device or optoelectronic device comprising a charge transport layer as described or preferably described before.
  • the invention relates furthermore to a solid-state dye-sensitized solar cell comprising a charge transport layer as described or preferably described before.
  • Suitable device structures according to the invention comprising further a mixed halide perovskite are described in WO 2013/171517, claims 52 to 71 and claims 72 to 79, which is entirely incorporated herein by reference.
  • Suitable device structures according to the invention comprising further a dielectric scaffold together with perovskite material are described in WO 2013/171518, claims 1 to 90 or WO 2013/171520, claims 1 to 94 which are entirely incorporated herein by reference.
  • Suitable device structures according to the invention comprising further a semiconductor and a perovskite material are described in WO 2014/020499, claims 1 and 3 to 14, which is entirely incorporated herein by reference
  • the surface-increasing scaffold structure described therein comprises nanoparticles which are applied and/or fixed on a support layer, e.g. porous IO 2 .
  • Suitable device structures according to the invention comprising a planar heterojunction are described in WO 2014/045021 , claims 1 to 39, which is entirely incorporated herein by reference.
  • Such a device is characterized in having a thin film of a light-absorbing or light-emitting perovskite disposed between n-type (electron conducting) and p-type (hole-conducting) layers.
  • the thin film is a compact thin film.
  • the invention relates to a method of preparing an electrochemical device and/or optoelectronic device as described or preferably described before, the method comprising the steps of:
  • the substrate may be rigid or flexible.
  • NDP-9, NHT-18, Novaled n-dopant can be purchased from Novaled AG, Germany; NMR for nuclear magnetic resonance;
  • Room temperature means a temperature range of from ca. 20 to 25 °C.
  • Over night means a time period in the range of from 14 to 20 h.
  • aqueous ammonium chloride solution (ca. 20%, 10 ml / mmol product) is added to the reaction mixture.
  • aqueous ascorbic acid solution (5 %, ca. 10 ml / mmol) is added to the reaction mixture.
  • silica gel (ca. 2 g / mmol) is added to the reaction mixture.
  • the suspension is stirred until it appears to be homogenous. It is then filtered over a pad of silica gel (20- 30 g), which is then washed with about the same volume of toluene as the volume of the column. After removal of the solvent from the combined filtrates, the product is purified further as described for the corresponding examples.
  • This compound was prepared as described in JP2011140579A from 5-bromo-2- iodotoluene (38.0 g, 128 mmol, 1 .0 eq.) via transformation into the corresponding boromc acid (4-bromo-2-methylphenyl)boronic acid followed by Suzuki coupling of this acid with 5-bromo-2-iodotoluene.
  • the crude product was purified by distillation in vacuum followed by crystallization from ethanol to give the product as a colorless solid (15.9 g, 40%) in a purity of 99.3% (according to GC).
  • the amine was synthesized as described in KR 2016149879 A via the coupling of 2- bromodibenzo[b,d]thiophene with 9,9-dimethyl-9H-fluoren-2-amine using Amphos instead of P(t-Bu) 3 as ligand.
  • the aryl bromide 4,4'-dibromo-1 ,T-biphenyl (27.5 g, 88.1 mmol, 1.0 eq.) and the arylamine 9,9-dimethyl-9H-fluoren-2-amine (37.8 g, 181 mmol, 2.05 eq.) were coupled in toluene (350 mL), using sodium tert-butanolate (17.8 g, 185 mmol, 2.1 eq.), Amphos (0.477 g, 1.76 mmol, 2 mol-%) and Pd 2 (dba) 3 (0.404 g, 0.441 mmol, 0.5 mol-%). After two hours at reflux, the reaction was complete.
  • the crude product was purified by crystallization from toluene to give the product as an off white solid (39.6 g, 79%) in a purity of 99.1 % according to HPLC@340 nm. Further purification by a second crystallization from toluene gave the product as an off white solid (31 .8 g, 63%) in a purity 99.8% according to HPLC@340 nm.
  • the aryl bromide 4, 4'-dibromo-1 ,1 '-biphenyl (3.30 g, 10.6 mmol, 1.0 eq.) and the diarylamine bis(9,9-dimethyl-9H-fluoren-2-yl)amine (8.92 g, 22.2 mmol, 2.1 eq.) were coupled in toluene (120 mL), using sodium tert- butanolate (2.24 g, 23.3 mmol, 2.2 eq.), Amphos (0.058 g, 0.21 mmol, 2 mol-%) and Pd 2 (dba) 3 (0.048 g, 0.05 mmol, 0.5 mol-%).
  • the aryl bromide 4,4'-dibromo-1 ,1 '-biphenyl (3.65 g, 11.7 mmol, 1.0 eq.) and the diarylamine from example 3 (10.3 g, 24.6 mmol, 2.1 eq.) were coupled in toluene (120 mL), using sodium tert-butanolate (2.47 g, 25.7 mmol, 2.2 eq.), Amphos (0.063 g, 0.23 mmol, 2 mol-%) and Pd 2 (dba) 3 (0.054 g, 0.06 mmol, 0.5 mol-%).
  • the product was worked up according to procedure C.
  • the crude product was purified by double crystallization from toluene/acetone to provide the product as a yellowish solid (8.1 g, 70%) in a purity of 97.1% according to HPLC@340 nm.
  • the aryl bromide 4,4'-dibromo-1 ,T-biphenyl (3.00 g, 9.6 mmol, 1.0 eq.) and the diarylamine from example 4 (7.18 g, 20.2 mmol, 2.1 eq.) were coupled in toluene (100 ml_), using sodium tert-butanolate (2.03 g, 21 .2 mmol, 2.2 eq.), Amphos (0.052 g, 0.19 mmol, 2 mol-%) and Pd 2 (dba) 3 (0.044 g, 0.05 mmol, 0.5 mol-%).
  • the aryl bromide 2-bromodibenzo[b,d]furan (17.8 g, 72.1 mmol, 2.05 eq.) and the product from example 6 (20.0 g, 35.2 mmol, 1.0 eq.) were coupled in toluene (250 mL), using sodium tert-butanolate (7.10 g, 73.8 mmol, 2.1 eq.), Amphos (0.191 g, 0.703 mmol, 2 mol-%) and Pd 2 (dba)3 (0.161 g, 0.176 mmol, 0.5 mol-%).
  • the crude product was purified by crystallization from acetone to provide the product as a yellowish solid (31.5 g, 99%) in a purity of 96.7% according to HPLC@340 nm.
  • a second crystallization from toluene provided the product as a slightly yellowish solid with a purity of 97.8% according to HPLC@340 nm.
  • the crude product was triturated twice with toluene/acetone to render the product as a slightly yellowish solid (22.5 g, 71 %) in a purity of 98.8% according to HPLC@340 nm.
  • Example 11 (alternative route for example 10)
  • the compound of example 10 can also be prepared via the alternative route of coupling 4,4’-dibromobiphenyl and the secondary amine from example 2 as follows:
  • the aryl bromide 4,4'-dibromo-1 ,T-biphenyl (4.50 g, 14.4 mmol, 1.0 eq.) and the diarylamine from example 2 (11.1 g, 29.6 mmol, 2.05 eq.) were coupled in toluene (100 mL), using sodium terf-butanolate (2.91 g, 30.3 mmol, 2.1 eq.), Amphos (0.078 g, 0.288 mmol, 2 mol-%) and Pd2(dba) 3 (0.066 g, 0.072 mmol, 0.5 mol-%).
  • the product was worked up according to procedure D to give a first crop of product (7.5 g, 58%) purity 91.0% (according to HPLC@340 nm).
  • the aryl bromide 4,4'-dibromo-1 ,1'-biphenyl (5.00 g, 16.0 mmol, 1.0 eq.) and the diarylamine from example 5 (12.9 g, 32.9 mmol, 2.05 eq.) were coupled in toluene (120 mL), using sodium tert-butanolate (3.23 g, 33.7 mmol, 2.1 eq.), Amphos (0.087 g, 0.32 mmol, 2 mol-%) and Pd2(dba) 3 (0.074 g, 0.08 mmol, 0.5 mol-%).
  • aqueous ascorbic acid solution (5 %, 100 mL) was added to the reaction mixture.
  • the resulting pale green suspension was filtered, and the filter cake was washed twice with toluene (each times 55 mL).
  • the filter cake (crude product) was extracted with THF in a Soxhlet apparatus for 35 hours. Removal of the solvent from the extract provided the crude product as a green- yellowish solid (12.9 g, 86%). This residue was re-dissolved in o-dichlorobenzene (160 ml) and activated carbon (1 g Norit CGP Super) was added. Filtration over a pad of silica gave a clear yellow solution from which the solvent was removed on the rotavapor to provide the crude product as a yellowish solid (11.0 g, 74%) purity 96.8% (according to HPLC@340 nm).
  • aqueous ascorbic acid solution (5 %, 100 mL) was added to the reaction mixture.
  • the crude product was further purified by crystallization from acetone to provide the product as a yellowish solid (10.1 g, 70%) in a purity of 99.4% according to HPLC@340 nm.
  • the aryl bromide from example 1 (5.00 g, 14.7 mmol, 1.0 eq.) and the diarylamine from example 2 (11.3 g, 30.1 mmol, 2.05 eq.) were coupled in toluene (100 mL), using sodium ferf-butanolate (2.97 g, 30.9 mmol, 2.1 eq.), tri tert butylphosphonium tetrafluoroborate (0.011 g, 0.037 mmol, 0.25 mol-%) and Pd 2 (dba) 3 (0.014 g, 0.015 mmol, 0.1 mol-%).
  • the crude product was purified by crystallization from toluene/acetone to provide the product as an off white solid (11.1 g, 82%) in a purity of 99.0% (according to HPLC@340 nm).
  • Example 15 (comparative example according to EP 0879868 A2) N 4 ,N 4 ’-bis(9,9-dimethyl-9H-fluoren-2-yl)-N 4 ,N 4 '-di(pyridin-3-yl)-[1 ,1 ’-biphenyl]-4,4'- diamine
  • This secondary amine was synthesized via the coupling of 2-bromo-9,9-dimethyl-9H- fluorene with pyridin-3-amine.
  • the product was obtained as colorless crystals (99.8% purity according to HPLC@340 nm) in 29% yield.
  • the onset method was mainly used for the analysis of samples which did not show a clear redox event or only one of the two events.
  • linear extrapolation using IVIIIM Soft was used to determine the E ons via a tangent to the slope of the oxidation event. The intersection between the tangent line and the starting slope was used for the further calculation of the HOMO.
  • Ferrocene was used as the reference system, from which the Fermi energy level (4.4 eV) was determined on the day of each measurement to avoid deviation within the measurement series.
  • the HOMO was determined by the formula [1]:
  • the EI/ 2 method for evaluating the HOMO was used for completely reversible redox events.
  • the basic parameters of the cyclovoltammogram were determined (MUM Soft) and E-i/ 2 was calculated from them. The value obtained was used to determine the HOMO in formula [1] (instead of the Eon).
  • the conductivities were measured using NDP-9 as the p-dopant.
  • Glass substrates 35 mm x 50 mm
  • ITO indium tin oxide
  • the trench was filled with the compound of formula (I) and NDP-9 as p- dopant material by co-evaporation of the compound of formula (I) and the p-dopant material.
  • Each doped layer had a thickness of 50 nm. After applying a voltage from 10 V between two ITO stripes, the conductivity was determined.
  • sample geometry A having a length of trench of 188 mm
  • sample geometry B having a length of trench of 146 mm

Abstract

La présente invention concerne des composés du type tétraarylbenzidine, portant des groupes (het)aryle spécifiques au niveau des atomes d'azote liés au squelette 1,1'-biphénylène, et des procédés pour leur préparation. L'invention concerne en outre l'utilisation des dérivés de tétraarylbenzidine en électronique organique, en particulier en tant que matériau de transport de trous (HTM) ou matériau de blocage d'électrons (EBM).
PCT/EP2023/066410 2022-06-21 2023-06-19 Composés de type tétraarylbenzidine et leur utilisation en électronique organique WO2023247416A1 (fr)

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