EP4634166A1 - Matériaux pour dispositifs électroniques - Google Patents

Matériaux pour dispositifs électroniques

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Publication number
EP4634166A1
EP4634166A1 EP23820941.5A EP23820941A EP4634166A1 EP 4634166 A1 EP4634166 A1 EP 4634166A1 EP 23820941 A EP23820941 A EP 23820941A EP 4634166 A1 EP4634166 A1 EP 4634166A1
Authority
EP
European Patent Office
Prior art keywords
groups
atoms
aromatic ring
radicals
ring systems
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23820941.5A
Other languages
German (de)
English (en)
Inventor
Rouven LINGE
Elvira Montenegro
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP4634166A1 publication Critical patent/EP4634166A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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]
    • H10K50/18—Carrier blocking layers
    • H10K50/181—Electron blocking layers
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • 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
    • H10K85/633—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
    • 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

Definitions

  • the present application relates to aromatic amines which have certain aromatic or heteroaromatic ring systems on the amine nitrogen atom.
  • the compounds are suitable for use in electronic devices.
  • Electronic devices within the meaning of this application are understood to mean so-called organic electronic devices which contain organic semiconductor materials as functional materials.
  • OLEDs organic electroluminescent devices.
  • OLEDs organic electroluminescent devices.
  • the term OLEDs refers to electronic devices which have one or more layers containing organic compounds and which emit light when an electrical voltage is applied.
  • the structure and general functional principle of OLEDs are known to those skilled in the art. There is great interest in improving the performance data of electronic devices, in particular OLEDs. A completely satisfactory solution has not yet been found in these areas.
  • Emission layers and layers with a hole-transporting function have a major influence on the performance data of electronic devices.
  • New compounds are still being sought for use in these layers, in particular hole-transporting compounds and compounds that can serve as hole-transporting matrix material, in particular for phosphorescent emitters, in an emitting layer.
  • compounds are particularly sought that have a high glass transition temperature, high stability, and high conductivity for holes.
  • a high stability of the compound is a prerequisite for achieving a long service life of the electronic device.
  • Compounds are also being sought whose use in electronic devices improves the performance data of the Devices, in particular, lead to high efficiency, long service life and low operating voltage.
  • triarylamine compounds such as spirobifluorenamines and fluorenamines are known in particular as hole transport materials and hole-transporting matrix materials for electronic devices.
  • aromatic amines according to the formulas below, which are characterized in that they have certain aromatic or heteroaromatic ring systems on the amine nitrogen atom, are excellently suitable for use in electronic devices. They are particularly suitable for use in OLEDs, again particularly for use therein as hole transport materials and for use as hole-transporting matrix materials, in particular for phosphorescent emitters.
  • the compounds lead to long service life, high efficiency and low operating voltage of the devices.
  • the compounds found preferably have a high glass transition temperature, high stability, a low sublimation temperature, good solubility, good synthetic accessibility and high conductivity for holes.
  • radical R 3 is bound to each of the four free positions on the ring, whereby the radicals R 3 can be the same or different at each occurrence.
  • radical R 1 is bonded to the corresponding ring and there are four or five free positions to which the radicals are bonded, which may be the same or different on each occurrence.
  • the following definitions apply to the chemical groups used in the present application. They apply unless more specific definitions are given.
  • An aryl group in the sense of this invention is understood to be either a single aromatic cycle, i.e.
  • benzene or a condensed aromatic polycycle, for example naphthalene, phenanthrene or anthracene.
  • a condensed aromatic polycycle in the sense of the present application consists of two or more individual aromatic cycles condensed together. Condensation between cycles is understood to mean that the cycles share at least one edge with each other.
  • An aryl group in the sense of this invention contains 6 to 40 aromatic ring atoms. Furthermore, an aryl group does not contain a heteroatom as an aromatic ring atom, but only carbon atoms.
  • a heteroaryl group in the sense of this invention is understood to be either a single heteroaromatic cycle, for example pyridine, pyrimidine or thiophene, or a condensed heteroaromatic polycycle, for example quinoline or carbazole.
  • a condensed heteroaromatic polycycle in the sense of the present application consists of two or more individual aromatic or heteroaromatic cycles condensed together, where at least one of the aromatic and heteroaromatic cycles is a heteroaromatic cycle. Condensation between cycles is to be understood as meaning that the cycles share at least one edge with each other.
  • a heteroaryl group in the sense of this invention contains 5 to 40 aromatic ring atoms, of which at least one is a heteroatom.
  • the heteroatoms of the heteroaryl group are preferably selected from N, O and S.
  • An aryl or heteroaryl group, which can be substituted in each case with the above-mentioned radicals, is understood to mean in particular groups which are derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene, fluoranthene, benzanthracene, benzphenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine,
  • aromatic ring system in the sense of this invention is a system which does not necessarily only contain aryl groups, but which can additionally contain one or more non-aromatic rings which are condensed with at least one aryl group. These non-aromatic rings contain exclusively carbon atoms as ring atoms. Examples of groups covered by this definition are tetrahydronaphthalene, fluorene and spirobifluorene.
  • aromatic ring system includes systems consisting of two or more aromatic ring systems that are connected to one another via single bonds, for example biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quaterphenyl and 3,5-diphenyl-1-phenyl.
  • An aromatic ring system in the sense of this invention contains 6 to 40 C atoms and no heteroatoms in the ring system.
  • the definition of "aromatic ring system” does not include heteroaryl groups.
  • a heteroaromatic ring system corresponds to the above definition of an aromatic ring system, with the difference that it must contain at least one heteroatom as a ring atom.
  • the heteroaromatic ring system does not have to contain exclusively aryl groups and heteroaryl groups, but can additionally contain one or more non-aromatic rings which are condensed with at least one aryl or heteroaryl group.
  • the non-aromatic rings can contain exclusively C atoms as ring atoms, or they can additionally contain one or more heteroatoms, the heteroatoms preferably being selected from N, O and S.
  • An example of such a heteroaromatic ring system is benzopyranyl.
  • the term "heteroaromatic ring system” refers to systems which consist of two or more aromatic or heteroaromatic ring systems which are connected to one another via single bonds, such as 4,6-diphenyl-2-triazinyl.
  • a heteroaromatic ring system in the sense of this invention contains 5 to 40 ring atoms which are selected from carbon and heteroatoms, at least one of the ring atoms being a heteroatom.
  • heteroatoms of the heteroaromatic ring system are preferably selected from N, O and S.
  • the terms “heteroaromatic ring system” and “aromatic ring system” as defined in the present application differ from one another in that an aromatic ring system cannot have a heteroatom as a ring atom, while a heteroaromatic ring system must have at least one heteroatom as a ring atom.
  • This heteroatom can be present as a ring atom of a non-aromatic heterocyclic ring or as a ring atom of an aromatic heterocyclic ring.
  • every aryl group is included in the term "aromatic ring system” and every heteroaryl group is included in the term "heteroaromatic ring system”.
  • An aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms is understood to mean, in particular, groups which are derived from the groups mentioned above under aryl groups and heteroaryl groups as well as from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, indenocarbazole, or from combinations of these groups.
  • a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms or an alkenyl or alkynyl group with 2 to 40 C atoms in which individual H atoms or CH2 groups can also be substituted by the groups mentioned above in the definition of the radicals, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neo-pentyl, n-hexyl, cyclohexyl, neo-hexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-e
  • alkoxy or thioalkyl group with 1 to 20 C atoms in which individual H atoms or CH2 groups can be substituted by the groups mentioned above in the definition of the radicals, is understood to mean preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methyl-butoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-buty
  • the formulation that two or more radicals can form a ring with one another is to be understood in the context of the present application to mean, among other things, that the two radicals are linked to one another by a chemical bond. Furthermore, the above formulation is also to 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.
  • Z is CR 1 . According to an alternative preferred embodiment, Z is the same or different on each occurrence and is selected from CR 1 and N, where a maximum of one Z group per ring is N.
  • the group Y is present and is the same or different on each occurrence and is selected from a bond, C(R 1 ) 2 , O or S, preferably a bond or C(R 1 ) 2 , particularly preferably a bond.
  • i 1 and Y stands for a bond.
  • a spirobifluorene framework is formed.
  • W is O on each occurrence.
  • Ar L is selected identically or differently on each occurrence from aromatic ring systems having 6 to 25 aromatic ring atoms which are substituted by radicals R 2 and heteroaromatic ring systems having 5 to 25 aromatic ring atoms which are substituted by radicals R 2 ; and particularly preferably selected identically or differently on each occurrence from phenyl, biphenyl, naphthyl and fluorenyl, each of which is substituted by radicals R 2 ; and most preferably selected from phenyl which is substituted with radicals R 2.
  • Ar L is preferably selected on each occurrence, identically or differently, from groups of the following formulas:
  • Ar L is selected on each occurrence, identically or differently, from phenyl, biphenyl, naphthyl and fluorenyl, which are each substituted by radicals R 2 , preferably phenyl and biphenyl, particularly preferably phenyl.
  • Ar 1 is selected on each occurrence, identically or differently, from aromatic ring systems having 6 to 40 aromatic ring atoms which are substituted by radicals R 4 , and heteroaromatic ring systems having 5 to 40 aromatic ring atoms which are substituted by radicals R 4 .
  • Ar 1 is selected on each occurrence, identically or differently, from aromatic ring systems having 6 to 25 aromatic ring atoms which are substituted by radicals R 4 , and heteroaromatic ring systems having 5 to 25 aromatic ring atoms which are substituted by radicals R 4 .
  • Preferred groups Ar 1 are selected at each occurrence, identically or differently, from monovalent groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, in particular 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine, and triazine, where each of the monovalent groups is substituted with radicals R 4 .
  • the groups Ar 1 are further selected on each occurrence, identically or differently, from combinations of 2 to 4 groups which are derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, in particular 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine, and triazine, where each of the monovalent groups is substituted by radicals R 4 .
  • the groups Ar 1 are selected on each occurrence, identically or differently, from monovalent groups derived from benzene, biphenyl, terphenyl, quaterphenyl, fluorene, benzofluorene, spirobifluorene, particularly preferably biphenyl, terphenyl, fluorene, spirobifluorene, where each of the monovalent groups is substituted with radicals R 4.
  • Ar 1 is preferably selected on each occurrence, identically or differently, from groups of the following formulas: where the dashed line represents the bond to the nitrogen atom and where the groups at the positions shown unsubstituted can be substituted with radicals R 4 , and preferably have only H in the positions shown unsubstituted.
  • Preferred among the abovementioned groups are the groups Ar 1 -1 to Ar 1 -106 and Ar 1 -139 to Ar 1 -271, particularly preferred are the groups Ar 1 -2 to Ar 1 -106 and Ar 1 -139 to Ar 1 -271.
  • both of the groups Ar 1 are selected from groups Ar 1 -2, Ar 1 -5, Ar 1 -48, Ar 1 - 50, Ar 1 -74, Ar 1 -78, Ar 1 -140, Ar 1 -141, Ar 1 -144, Ar 1 -149, Ar 1 -193, Ar 1 -195, Ar 1 -257 to Ar 1 -264, Ar 1 -265, Ar 1 -266 , Ar 1 -268 and Ar 1 -271.
  • both groups Ar 1 are selected from groups of the formulas (Ar 1 - 1) to (Ar 1 -10) and (Ar 1 -139) to (Ar 1 -171), as defined above.
  • the groups Ar 1 are selected from groups Ar 1 -2, Ar 1 -5, Ar 1 -48, Ar 1 -50, Ar 1 -78, Ar 1 -140, Ar 1 - 141, Ar 1 -149, Ar1-139 to Ar 1 -171, Ar 1 -193, Ar 1 -265, Ar 1 -266, Ar 1 -268 and Ar 1 -271, particularly preferably Ar 1 -2, Ar 1 -139 and Ar 1 -141.
  • the groups Ar 1 do not contain a carbazole group as a substituent R 4 , R 6 or R 7 .
  • the two groups Ar 1 are only connected via the nitrogen atom to which both groups Ar 1 are bonded, but not via substituents R 4 , R 6 or R 7 , which can form a ring system.
  • Ar 2 is selected on each occurrence, identically or differently, from aromatic ring systems having 6 to 40 aromatic ring atoms which are substituted by radicals R 5 , and heteroaromatic ring systems having 5 to 40 aromatic ring atoms which are substituted by radicals R 5 .
  • Ar 2 is selected on each occurrence, identically or differently, from aromatic ring systems having 6 to 25 aromatic ring atoms which are substituted by radicals R 5 , and heteroaromatic ring systems having 5 to 25 aromatic ring atoms which are substituted by radicals R 5.
  • Preferred groups Ar 2 are selected on each occurrence, identically or differently, from groups which are divalent in the ortho position and are derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, in particular 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine, and triazine, where each of the divalent groups is substituted by radicals R 5 .
  • the groups Ar 2 are preferably selected on each occurrence, identically or differently, from combinations of 2 to 4 groups which are derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, in particular 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine, and triazine, where each of the groups is substituted by radicals R 5 .
  • the groups Ar 2 are selected on each occurrence, identically or differently, from groups which are divalent in the ortho position and are derived from benzene, biphenyl, terphenyl, quaterphenyl, fluorene, benzofluorene, spirobifluorene, particularly preferably biphenyl, terphenyl, fluorene, spirobifluorene, where each of the divalent groups is substituted by radicals R 5.
  • Ar 2 is preferably selected on each occurrence, identically or differently, from groups of the following formulas:
  • the dashed lines represent the bond to the nitrogen atom or the bond to the group V
  • the groups can be substituted by radicals R 5 at the positions shown unsubstituted, and preferably have only H in the positions shown unsubstituted.
  • both of the groups Ar 2 are selected from groups Ar 2 -2, Ar 2 -4, Ar 2 -35, Ar 2 - 37, Ar 2 -107, Ar 2 -109, Ar 2 -110 , Ar 2 -111, Ar 2 -125, Ar 2 -126, Ar 2 -213, Ar 2 -214, Ar 2 -215 and Ar 2 -220.
  • both groups Ar 2 are selected from groups of the formulas (Ar 2 - 1) to (Ar 2 -7) and (Ar 2 -104) to (Ar 2 -151), as defined above.
  • Preferred among the formulas (Ar 2 -1) to (Ar 2 -7) are the formulas (Ar 2 -1), (Ar 2 -2), (Ar 2 -3), (Ar 2 -4) and (Ar 2 -5).
  • it can preferably be provided that one or both of the groups Ar 2 , preferably both of the groups Ar 2 are selected from groups Ar 2 -2, Ar 2 -4, Ar 2 -35, Ar 2 -37, Ar 2 -107, Ar 2 -109, Ar 2 -110, Ar 2 -111, Ar 2 -125, Ar 2 -126, Ar 2 -213, Ar 2 -214, Ar 2 -215 and Ar 2 -220, particularly preferably Ar 2 -2, Ar 2 -104 and Ar 2 -105.
  • the groups Ar 2 do not contain a carbazole group as substituent R 5 , R 6 or R 7 .
  • V is selected from a bond, O, Si(R 5 ) 2 and C(R 5 ) 2 , preferably a bond, Si(R 5 ) 2 and C(R 5 ) 2 .
  • V is particularly preferably a bond.
  • a carbazole-like structure is formed together with the groups Ar 2 and the nitrogen atom.
  • R 1 is selected at each occurrence, identically or differently, from H, D, F, CN, Si(R 6 ) 3, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aryl groups having 6 to 25, preferably 6 to 14 aromatic ring atoms, and heteroaryl groups having 5 to 40 aromatic ring atoms, where the alkyl groups mentioned, the aryl groups mentioned and the heteroaryl groups mentioned are each substituted by radicals R 6 .
  • these groups which are other than H and D, are selected from F, CN, Si(R 6 )3, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aryl groups having 6 to 25, preferably 6 to 14 aromatic ring atoms, and heteroaryl groups having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, particularly preferably 6 to 14 aromatic ring atoms, where the alkyl groups mentioned, the aryl groups mentioned and the heteroaryl groups mentioned are each radicals R 6 .
  • none or one of the groups R 1 in each formula is other than H and D and particularly preferably none of the groups R 1 in each formula is other than H and D.
  • all radicals R 1 in formulas (I) and (II) are H or D, particularly preferably H.
  • the compounds according to one of the formulas (I) and (II) have at least one group R 1 which is selected from aromatic ring systems having 6 to 40 aromatic ring atoms which are substituted by radicals R 6 ; particularly preferably, the compounds according to one of the formulas (I) and (II) have at least one group R 1 which is selected from aryl groups having 6 to 25, preferably 6 to 14 aromatic ring atoms which are substituted by radicals R 6 . In an alternative embodiment, it can be particularly preferred that the compounds according to one of the formulae (I) and (II) have at least one group R 1 which is a phenyl group which is substituted by radicals R 6 .
  • R 2 is selected on each occurrence, identically or differently, from H, D, F, CN, Si(R 6 )3, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C- atoms, aryl groups having 6 to 25, preferably 6 to 14 aromatic ring atoms, and heteroaryl groups having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, particularly preferably 6 to 14 aromatic ring atoms, wherein the alkyl groups mentioned, the aryl groups mentioned and the heteroaryl groups mentioned are each substituted by radicals R 6 .
  • R 2 groups per formula other than H and D there are no, one, two or three R 2 groups per formula other than H and D.
  • these groups, which are other than H and D are selected from F, CN, Si(R 6 ) 3, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aryl groups having 6 to 25, preferably 6 to 14 aromatic ring atoms, and heteroaryl groups having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, particularly preferably 6 to 14 aromatic ring atoms, where the alkyl groups mentioned, the aryl groups mentioned and the heteroaryl groups mentioned are each substituted by radicals R 6 .
  • R 3 groups per formula are not equal to H and D.
  • these groups which are not equal to H and D, are selected from F, CN, Si(R 6 )3, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aryl groups having 6 to 25, preferably 6 to 14 aromatic ring atoms, and heteroaryl groups having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, particularly preferably 6 to 14 aromatic ring atoms, where the alkyl groups mentioned, the aryl groups mentioned and the heteroaryl groups mentioned are each substituted by radicals R 6 .
  • none or one of the R 3 groups in each formula is not equal to H and D and particularly preferably none of the R 3 groups in each formula is not equal to H and D.
  • all R 3 radicals in formulas (I) and (II) are equal to H or D, particularly preferably equal to H.
  • the compounds according to one of the formulas (I) and (II) have at least one R 3 group which is selected from aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted by R 6 radicals; particularly preferably, the compounds according to one of the formulas (I) and (II) have at least one R 3 group which is selected from aryl groups with 6 to 25, preferably 6 to 14 aromatic ring atoms which are substituted by R 6 radicals. In an alternative embodiment, it can particularly preferably be provided that the compounds according to one of the formulas (I) and (II) have at least one R 3 group which is a phenyl group which is substituted by R 6 radicals.
  • radicals R 1 and R 3 in formulas (I) and (II) are H or D.
  • none, one, two, three or four of the groups R 4 per radical Ar 1 are not equal to H and D.
  • these groups which are not equal to H and D, are selected from F, CN, Si(R 6 ) 3, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aryl groups having 6 to 25, preferably 6 to 14 aromatic ring atoms and heteroaryl groups having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, particularly preferably 6 to 14 aromatic ring atoms, where the alkyl groups mentioned, the aryl groups mentioned and the heteroaryl groups mentioned are each substituted by radicals R 6 .
  • R 4 groups in each formula are not H and D, and particularly preferably none or one of the R 4 groups in each formula is not H and D.
  • none, one, two, three or four of the groups R 5 per radical Ar 2 are not equal to H and D. Preference is given to these groups which are not equal to H and D.
  • R 5 groups in each formula are selected from F, CN, Si(R 6 ) 3 , straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aryl groups having 6 to 25, preferably 6 to 14 aromatic ring atoms and heteroaryl groups having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, particularly preferably 6 to 14 aromatic ring atoms, where the alkyl groups mentioned, the aryl groups mentioned and the heteroaryl groups mentioned are each substituted by radicals R 6 .
  • none, one or two of the R 5 groups in each formula are not equal to H and D and particularly preferably none or one of the R 5 groups in each formula is not equal to H and D.
  • formula (I) corresponds to one of the following formulas: where the occurring groups are defined as above.
  • Preferred embodiments of the above formulas correspond to the following formulas: where the groups occurring are defined as above.
  • Formula (II) preferably corresponds to one of the following formulas:
  • R H or organic radical
  • Q reactive group
  • Ar optionally substituted aromatic or heteroaromatic, corresponding to the previously defined groups Ar L , Ar 1 , Ar 2 and V
  • the subject of the present application is therefore a process for preparing a compound according to the present application, characterized in that an indenodibenzofuran derivative substituted with a reactive group a) is reacted in a coupling reaction with a secondary amine, or b) is reacted in a coupling reaction with an aromatic or heteroaromatic which carries a reactive group.
  • the reactive group on the indenodibenzofuran derivative preferably contains boron and the reactive group on the aromatic or heteroaromatic is preferably selected from Cl, Br and I.
  • the reactive group on the indenodibenzofuran derivative is selected from Cl, Br and I and the reactive group on the aromatic or heteroaromatic preferably contains boron.
  • a reactive group is reacted in a coupling reaction with an aromatic or heteroaromatic compound which carries a boron-containing group.
  • an indenodibenzofuran derivative substituted with a boron-containing group is reacted in a coupling reaction with an aromatic or heteroaromatic compound which carries a reactive group.
  • Reactive groups are known to the person skilled in the art for the specific reaction.
  • One of the reactive groups is preferably selected from Cl, Br and I, particularly preferably from Br and I.
  • the coupling reaction in the reaction under a) is preferably a Hartwig-Buchwald coupling reaction.
  • the coupling reaction under b) is preferably a Suzuki coupling reaction.
  • a reactive group is preferably selected as set out above and a further reactive group is preferably a boron atom-containing group, preferably a boric acid or boric acid ester group.
  • the indenodibenzofuran derivative substituted with one reactive group is prepared starting from a dibenzofuran derivative substituted with two reactive groups, which is reacted with a carbonyl compound in an organometallic addition reaction.
  • Compounds with a boron atom-containing group, preferably a boric acid or boric acid ester group can preferably be obtained by reaction with organometallic compounds, preferably organometallic lithium compounds.
  • Unsubstituted indenodibenzofuran derivatives can also be used here.
  • indenodibenzofuran derivatives with a reactive group selected from Cl, Br and I, particularly preferably from Br and I can also be obtained from unsubstituted indenodibenzofuran derivatives by reaction with organometallic compounds, preferably organometallic lithium compounds.
  • organometallic compounds preferably organometallic lithium compounds.
  • Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boronic acids, boronic acid esters, amines, alkenyl or alkynyl groups with a terminal CC double bond or C-C triple bond, oxiranes, oxetanes, groups which undergo a cycloaddition, for example a 1,3-dipolar cycloaddition, such as dienes or azides, carboxylic acid derivatives, alcohols and silanes.
  • the invention therefore further relates to oligomers, polymers or dendrimers containing one or more compounds according to formula (I) or (II), where the bond(s) to the polymer, oligomer or dendrimer can be located at any position substituted by R 1 , R 2 , R 3 , R 4 or R 5 in formula (I) or (II).
  • the compound is part of a side chain of the oligomer or polymer or part of the main chain.
  • An oligomer in the sense of this invention is understood to mean a compound which is made up of at least three monomer units.
  • a polymer in the sense of the invention is understood to mean a compound which is made up of at least ten monomer units.
  • the polymers, oligomers or dendrimers according to the invention can be conjugated, partially conjugated or non-conjugated.
  • the oligomers or polymers according to the invention can be linear, branched or dendritic.
  • the units according to formula (I) or (II) can be linked directly to one another or they can be linked to one another via a bivalent group, for example via a substituted or unsubstituted alkylene group, via a heteroatom or via a bivalent aromatic or heteroaromatic group.
  • branched and dendritic structures for example, three or more units according to formula (I) or (II) can be linked to one another via a trivalent or higher-valent Group, for example via a trivalent or higher valent aromatic or heteroaromatic group, to form a branched or dendritic oligomer or polymer.
  • a trivalent or higher-valent Group for example via a trivalent or higher valent aromatic or heteroaromatic group
  • the same preferences apply to the repeat units according to formula (I) or (II) in oligomers, dendrimers and polymers as described above for compounds according to formula (I) or (II).
  • the monomers according to the invention are homopolymerized or copolymerized with other monomers.
  • Suitable and preferred comonomers are selected from fluorenes, spirobifluorenes, paraphenylenes, carbazoles, thiophenes, dihydrophenanthrenes, cis- and trans-indenofluorenes, ketones, phenanthrenes or even several of these units.
  • the polymers, oligomers and dendrimers usually contain other units, for example emitting (fluorescent or phosphorescent) units, such as, for example, B. vinyltriarylamines or phosphorescent metal complexes, and/or charge transport units, in particular those based on triarylamines.
  • the polymers, oligomers and dendrimers according to the invention have advantageous properties, in particular long lifetimes, high efficiencies and good color coordinates.
  • the polymers and oligomers according to the invention are generally prepared by polymerizing one or more types of monomer, of which at least one monomer in the polymer leads to repeat units of the formula (I) or (II). Suitable polymerization reactions are known to the person skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions that lead to CC or CN linkages are the following: (A) SUZUKI polymerization; (B) YAMAMOTO polymerization; (C) STILLE polymerization; and (D) HARTWIG-BUCHWALD polymerization.
  • formulations of the compounds according to the invention are required for processing the compounds according to the invention from the liquid phase. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferable to use mixtures of two or more solvents for this purpose.
  • Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin,
  • the invention therefore further relates to a formulation, in particular a solution, dispersion or emulsion, containing at least one compound according to formula (I) or (II) or at least one polymer, oligomer or dendrimer containing at least one unit according to formula (I) or (II) and at least one solvent, preferably an organic solvent.
  • a formulation in particular a solution, dispersion or emulsion, containing at least one compound according to formula (I) or (II) or at least one polymer, oligomer or dendrimer containing at least one unit according to formula (I) or (II) and at least one solvent, preferably an organic solvent.
  • a formulation in particular a solution, dispersion or emulsion, containing at least one compound according to formula (I) or (II) or at least one polymer, oligomer or dendrimer containing at least one unit according to formula (I) or (II) and at least one solvent, preferably an organic solvent.
  • the invention therefore further relates to the use of a compound according to formula (I) or (II) in an electronic device.
  • the electronic device is preferably selected from the group consisting of organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and particularly preferably organic electroluminescent devices (OLEDs).
  • OICs organic integrated circuits
  • OFETs organic field-effect transistors
  • OLETs organic thin-film transistors
  • OLETs organic solar cells
  • OFQDs organic field quench devices
  • OLEDs organic light-emitting electrochemical cells
  • the invention further relates to an electronic device containing at least one compound according to formula (I) or (II).
  • the electronic device is preferably selected from the above-mentioned devices.
  • an organic electroluminescent device containing an anode, cathode and at least one emitting layer, characterized in that at least one organic layer is contained in the device which contains at least one compound according to formula (I) or (II).
  • an organic electroluminescent device comprising an anode, a cathode and at least one emitting layer, characterized in that at least one organic layer in the device is selected from hole-transporting and emitting layers, at least one compound according to formula (I) or (II).
  • a hole-transporting layer is understood to mean all layers that are arranged between the anode and the emitting layer, preferably hole injection layer, hole transport layer, and electron blocking layer.
  • a hole injection layer is understood to mean a layer that is directly adjacent to the anode.
  • a hole transport layer is understood to mean a layer that is present between the anode and the emitting layer, but is not directly adjacent to the anode, and preferably not directly adjacent to the emitting layer either.
  • An electron blocking layer is understood to mean a layer that is present between the anode and the emitting layer and is directly adjacent to the emitting layer.
  • An electron blocking layer preferably has a high-energy LUMO and thus prevents electrons from escaping from the emitting layer.
  • the electronic device can contain further layers.
  • hole injection layers are selected, for example, from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, interlayers, charge generation layers and/or organic or inorganic p/n junctions.
  • hole injection layers for example, from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, interlayers, charge generation layers and/or organic or inorganic p/n junctions.
  • hole blocking layers are selected, for example, from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, interlayers, charge generation layers and/or organic or inorganic p/n junctions.
  • electron transport layers for example, from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, interlayers, charge generation layers and/or organic or inorganic
  • the sequence of the layers of the electronic device is preferably as follows: -Anode- -Hole injection layer- -Hole transport layer- -optionally further hole transport layers- -emitting layer- -optional hole blocking layer- -electron transport layer- -electron injection layer- -cathode-. It should be pointed out again that not all of the layers mentioned have to be present and/or that additional layers can be present.
  • the organic electroluminescent device according to the invention can contain several emitting layers. These emission layers particularly preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, i.e.
  • emitting compounds are used in the emitting layers which can fluoresce or phosphoresce and which emit blue, green, yellow, orange or red light.
  • Three-layer systems are particularly preferred, i.e. systems with three emitting layers, where one of the three layers shows blue emission, one of the three layers shows green emission and one of the three layers shows orange or red emission.
  • the compounds according to the invention are preferably present in a hole transport layer or in the emitting layer. It should be noted that instead of several color-emitting emitter compounds, a single emitter compound that emits in a broad wavelength range can also be suitable for generating white light. It is preferred that the compound of formula (I) or (II) is used as hole transport material.
  • the emitting layer can be a fluorescent emitting layer or it can be a phosphorescent emitting layer.
  • the emitting layer is preferably a blue fluorescent layer or a green phosphorescent layer. If the device containing the compound of formula (I) or (II) contains a phosphorescent emitting layer, it is preferred that this layer contains two or more, preferably exactly two, different matrix materials (mixed matrix system). Preferred embodiments of mixed matrix systems are described in more detail below. If the compound according to formula (I) or (II) is used as a hole transport material in a hole transport layer, a hole injection layer or an electron blocking layer, the compound can be used as a pure material, i.e.
  • a hole transport layer containing the compound of formula (I) or (II) additionally contains one or more other hole transport compounds.
  • These other hole transport compounds are preferably selected from triarylamine compounds, particularly preferably from mono-triarylamine compounds. They are very particularly preferably selected from the preferred embodiments of hole transport materials given below.
  • the compound of formula (I) or (II) and the one or more further hole-transporting compounds are preferably each present in a proportion of at least 10%, particularly preferably each present in a proportion of at least 20%.
  • a hole-transporting layer containing the compound of formula (I) or (II) additionally contains one or more p-dopants.
  • the p-dopants used are preferably those organic electron acceptor compounds which can oxidize one or more of the other compounds in the mixture.
  • p-dopants are quinodimethane compounds, azaindenofluorenediones, azaphenalenes, azatriphenylenes, I 2 , metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or a metal of the 3rd main group, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd and Pt with ligands containing at least one oxygen atom as a bonding site.
  • transition metal oxides as dopants preferably oxides of rhenium, molybdenum and tungsten, particularly preferably Re 2 O 7 , MoO 3 , WO 3 and ReO 3.
  • the p-dopants are preferably present largely evenly distributed in the p-doped layers. This can be achieved, for example, by co-evaporation of the p-dopant and the hole transport material matrix.
  • the p-dopant is preferably present in a proportion of 1 to 10% in the p-doped layer.
  • the following compounds are particularly preferred as p-dopants: N NC CN ( ) ( ) ( )
  • a hole injection layer is present in the device which corresponds to one of the following embodiments: a) it contains a triarylamine and a p-dopant; or b) it contains a single electron-poor material (electron acceptor).
  • the triarylamine is a mono-triarylamine, in particular one of the preferred triarylamine derivatives mentioned below.
  • the electron-poor material is a hexaazatriphenylene derivative, as described in US 2007/0092755.
  • the compound of formula (I) or (II) can be contained in a hole injection layer, in a hole transport layer, and/or in an electron blocking layer of the device. If the compound is present in a hole injection layer or in a hole transport layer, it is preferably p-doped, i.e. it is present in the layer mixed with a p-dopant, as described above.
  • the compound of formula (I) or (II) is preferably contained in an electron blocking layer. In this case, it is preferably not p-doped. In this case, it is also preferably present as a single compound in the layer, without the addition of another compound.
  • the compound of formula (I) or (II) is used in an emitting layer as a matrix material in combination with one or more emitting compounds, preferably phosphorescent emitting compounds.
  • the phosphorescent emitting compounds are preferably selected from red phosphorescent and green phosphorescent compounds.
  • the proportion of the matrix material in the emitting layer in this case is between 50.0 and 99.9 vol. %, preferably between 80.0 and 99.5 vol. %, and particularly preferably between 85.0 and 97.0 vol. %. Accordingly, the proportion of the emitting compound is between 0.1 and 50.0 vol. %, preferably between 0.5 and 20.0 vol. % and particularly preferably between 3.0 and 15.0 vol. %.
  • An emitting layer of an organic electroluminescent device can also contain systems comprising several matrix materials (mixed matrix systems) and/or several emitting compounds.
  • the emitting compounds are generally those compounds whose proportion in the system is the smaller and the matrix materials are those compounds whose proportion in the system is the larger.
  • the proportion of a single Matrix material in the system should be smaller than the proportion of a single emitting compound.
  • the compounds according to formula (I) or (II) are used as a component of mixed matrix systems, preferably for phosphorescent emitters.
  • the mixed matrix systems preferably comprise two or three different matrix materials, particularly preferably two different matrix materials.
  • one of the two materials is a material with hole-transporting properties and the other material is a material with electron-transporting properties. It is also preferred if one of the materials is selected from compounds with a large energy difference between HOMO and LUMO (wide band gap materials).
  • the compound of formula (I) or (II) in a mixed matrix system preferably represents the matrix material with hole-transporting properties. Accordingly, if the compound of formula (I) or (II) is used as a matrix material for a phosphorescent emitter in the emitting layer of an OLED, a second matrix compound is present in the emitting layer which has electron-transporting properties.
  • the two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1 and very particularly preferably 1:4 to 1:1.
  • the desired electron-transporting and hole-transporting properties of the mixed matrix components can also be combined mainly or completely in a single mixed matrix component, with the other mixed matrix component(s) fulfilling other functions.
  • the following material classes are preferably used in the above-mentioned layers of the device: Phosphorescent emitters:
  • the term phosphorescent emitters typically includes compounds in which the light emission is caused by a spin-forbidden Transition occurs, for example a transition from an excited triplet state or a state with a higher spin quantum number, for example a quintet state.
  • Particularly suitable phosphorescent emitters are compounds which emit light when suitably excited, 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.
  • Preferably used as phosphorescent emitters are compounds which contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds which contain iridium, platinum or copper.
  • all luminescent iridium, platinum or copper complexes are regarded as phosphorescent compounds.
  • Fluorescent emitters are selected from the class of arylamines.
  • An arylamine or an aromatic amine in the sense of this invention is understood to mean a compound which contains three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen.
  • at least one of these aromatic or heteroaromatic ring systems is a condensed ring system, particularly preferably with at least 14 aromatic ring atoms.
  • Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines.
  • aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position.
  • aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10-position.
  • Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably being bonded in the 1-position or in the 1,6-position.
  • emitting compounds are indenofluorenamines or diamines, benzoindenofluorenamines or diamines, and dibenzoindenofluorenamines or diamines, as well as indenofluorene derivatives with condensed aryl groups. Also preferred are pyrene-arylamines. Also preferred are benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives which are linked to furan units or to thiophene units.
  • Matrix materials for fluorescent emitters Preferred matrix materials for fluorescent emitters are selected from the classes of oligoarylenes (e.g.
  • 2,2',7,7'-tetraphenylspirobifluorene in particular oligoarylenes containing condensed aromatic groups, oligoarylenevinylenes, polypodal metal complexes, hole-conducting compounds, electron-conducting compounds, in particular ketones, phosphine oxides, and sulfoxides; atropisomers, boronic acid derivatives or benzanthracenes.
  • Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides and sulfoxides.
  • Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzphenanthrene and/or pyrene or atropisomers of these compounds.
  • Oligoarylene in the sense of this invention is understood to mean a compound in which at least three aryl or arylene groups are bonded to one another.
  • Matrix materials for phosphorescent emitters are, in addition to the compounds of formula (I) or (II), aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, e.g.
  • Electron-transporting materials Suitable electron-transporting materials are, for example, the compounds disclosed in Y. Shirota et al., Chem.
  • All materials that are used in the electron transport layer according to the prior art as electron transport materials can be used as materials for the electron transport layer.
  • Particularly suitable are aluminum complexes, for example Alq3, zirconium complexes, for example Zrq4, lithium complexes, for example Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives and phosphine oxide derivatives.
  • Hole-transporting materials Other compounds which, in addition to the compounds of formula (I) or (II), are preferably used in hole-transporting layers of the OLEDs according to the invention are indenofluorenamine derivatives, amine derivatives, hexaazatriphenylene derivatives, amine derivatives with condensed aromatics, monobenzoindenofluorenamines, dibenzoindenofluorenamines, spirobifluorene amines, fluorene amines, spiro-dibenzopyran amines, dihydroacridine derivatives, spirodibenzofurans and spirodibenzothiophenes, phenanthrene diarylamines, spiro-tribenzotropolones, spirobifluorenes with meta-phenyldiamine groups, spiro-bisacridines,
  • Preferred hole-transporting compounds are shown in the table on pages 76-80 of WO2020/109434A1.
  • the following compounds HT-1 to HT-35 are particularly well suited for use in a layer with hole transport function of an OLED. This applies not only to OLEDs according to the definitions and claims of the present application, but to OLEDs in general:
  • the compounds HT-1 to HT-35 can generally be used in any hole transport layer of OLEDs.
  • hole transport layer here means any layer of an OLED that is located between the anode and the emitting layer.
  • OLED is not specifically restricted and applies to all OLEDs, in particular to the OLED structures that were common at the time of filing the present application.
  • the compounds HT-1 to HT-35 can be produced by processes that are disclosed in the application texts listed in the table above under the respective compounds HT-1 to HT-35. The teaching on the use of the compounds and the processes for producing the compounds that are contained in the above-mentioned application texts are hereby expressly incorporated into the present disclosure by reference.
  • the compounds HT-1 to HT-35 exhibit excellent properties when used in OLEDs, in particular an excellent lifetime and efficiency. This is particularly the case when they are used in a hole transport layer of the OLED.
  • metals with low work function metal alloys or multilayer structures made of different metals are preferred, such as alkaline earth metals, Alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys of an alkali or alkaline earth metal and silver are also suitable, for example an alloy of magnesium and silver.
  • Suitable materials for this include alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g. LiF, Li 2 O, BaF 2 , MgO, NaF, CsF, Cs 2 CO 3 , etc.). Lithium quinolinate (LiQ) can also be used for this purpose.
  • the layer thickness of this layer is preferably between 0.5 and 5 nm.
  • Materials with a high work function are preferred as anode.
  • the anode preferably has a work function greater than 4.5 eV vs. vacuum.
  • Metals with a high redox potential are suitable for this, such as Ag, Pt or Au.
  • Metal/metal oxide electrodes e.g. Al/Ni/NiOx, Al/PtOx
  • at least one of the electrodes must be transparent or partially transparent in order to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER).
  • Preferred anode materials here are conductive mixed metal oxides.
  • ITO Indium tin oxide
  • IZO indium zinc oxide
  • the anode can also consist of several layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.
  • the electronic device is characterized in that one or more layers are coated using a sublimation process.
  • the materials are Vacuum sublimation systems at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 mbar. However, it is also possible for the initial pressure to be even lower, for example less than 10 -7 mbar.
  • an electronic device characterized in that one or more layers are coated using the OVPD (Organic Vapour Phase Deposition) process or with the aid of carrier gas sublimation.
  • the materials are applied at a pressure of between 10 -5 mbar and 1 bar.
  • OVJP Organic Vapour Jet Printing
  • the materials are applied directly through a nozzle and thus structured (e.g. BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).
  • an electronic device characterized in that one or more layers are coated from solution, such as by spin coating, or using any printing process, such as e.g. B.
  • soluble compounds according to formula (I) or (II) are required. High solubility can be achieved by suitable substitution of the compounds. It is further preferred that, to produce an electronic device according to the invention, one or more layers of solution and one or more layers are applied by a sublimation process. After the layers have been applied, the device is structured, contacted and finally sealed, depending on the application, in order to exclude damaging effects of water and air.
  • the electronic devices containing one or more compounds according to formula (I) or (II) can be used in displays, as light sources in lighting applications and as light sources in medical and/or cosmetic applications.
  • reaction mixture After complete conversion, the reaction mixture is allowed to cool to room temperature and filtered through aluminum oxide and washed with toluene. After removing the solvents, the crude product is dissolved in toluene/heptane 1:1 and filtered through silica gel. Further purification is carried out by repeated crystallization from heptane/toluene to an HPLC purity >99.9%. Finally, the product is obtained as a solid after two sublimations under high vacuum.
  • the following compounds are prepared analogously manufactured: B) Device examples 1) General manufacturing process for the OLEDs and characterization of the OLEDs Glass plates coated with structured ITO (indium tin oxide) with a thickness of 50 nm form the substrates onto which the OLEDs are applied.
  • the OLEDs basically have the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL1) / optional second hole transport layer (HTL2) / electron blocking layer (EBL) / emission layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL1) / optional second electron transport layer (ETL2) / electron injection layer (EIL) and finally a cathode.
  • the cathode is formed by a 100 nm thick aluminum layer.
  • the exact structure of the OLEDs can be found in the following tables. The materials required to manufacture the OLEDs are shown in a table below. All materials are thermally vapor-deposited in a vacuum chamber.
  • the emission layer consists of at least one matrix material (host material) and an emitting dopant (dopant, emitter), which is mixed into the matrix material or materials by co-evaporation in a certain volume proportion.
  • a specification such as H:SEB (95%:5%) means that the material H is present in a volume proportion of 95% and SEB in a proportion of 5% in the layer.
  • the electron transport layer and the hole injection layer also consist of a mixture of two materials.
  • the structures of the materials used in the OLEDs are shown in Table 7.
  • the compound HTM-B which is also used, is a 2-aminofluorene, which has a substituent on one of the aromatic six-membered rings of the fluorene.
  • the compound EBM-B which is also used, contains an amino group and a 1-spirobifluorenyl group.
  • the OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, the external quantum efficiency (EQE, measured in %) as a function of the luminance, calculated from current-voltage-luminance characteristics assuming a Lambertian radiation characteristic, and the service life are determined.
  • the EQE specification @ 10mA/cm2 refers to the external quantum efficiency that is achieved at 10mA/cm2.
  • the lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain level when operating at a constant current density.
  • a specification of LT90 means that the specified lifetime corresponds to the time after which the luminance has dropped to 90% of its initial value.
  • the specification @60 mA/cm 2 means that the relevant lifetime is measured at 60 mA/cm 2.
  • the OLEDs show very good properties as hole transport materials, especially in an EBL layer, where they lead to very high external quantum efficiencies as well as low operating voltage and very good lifetime.
  • the OLEDs show good results for lifetime, efficiency and operating voltage, as shown in the following table: 3)
  • Examples for use in the electron blocking layer of a green phosphorescent OLED OLEDs with the following structure are manufactured:
  • OLEDs 5 and 6 show that the compounds according to the invention are excellently suited as electron blockers for green phosphorescent OLEDs.
  • the OLEDs show very good properties as hole transport or electron blocking materials and, above all, have low operating voltages with good external quantum efficiencies and an outstanding lifetime.
  • the OLEDs show good results for lifetime, efficiency and operating voltage, as shown in the following table:
  • Example of use as a hole transport layer of a blue fluorescent OLED An OLED with the following structure is manufactured:
  • the example (OLED 7) shows that the compound HTM-1 according to the invention is ideally suited as a hole transport material for blue fluorescent OLEDs.
  • the OLED shows very good properties as a hole transport material and low operating voltage with good external quantum efficiencies and an outstanding lifetime.
  • the OLED shows good results for lifetime, efficiency and operating voltage, as shown in the following table: HTM-2 can also be used in a stack as shown in Table 5, whereby the OLED performs well.
  • the following blue fluorescent OLEDs containing a compound according to the invention are produced in the EBL:
  • OLEDs 8 and 9 show that the compounds according to the invention are excellently suited as electron blocking materials for blue fluorescent OLEDs.
  • the OLEDs achieve a low operating voltage with good external quantum efficiency and a good lifetime: 6)
  • the following green phosphorescent OLEDs containing a compound according to the invention HTM-1, HTM-2 or HTM-3 are produced in the EBL:
  • OLEDs 10-12 show that the compounds according to the invention are excellently suited as materials in the electron blocking layer of green phosphorescent OLEDs.
  • the OLEDs achieve a low operating voltage with good external quantum efficiency and an outstanding lifetime: 7) Furthermore, the following blue fluorescent OLED containing the compound HTM-3 according to the invention is produced in the HTL:
  • This OLED shows that the compound HTM-3 according to the invention is suitable as a hole transport material for blue fluorescent OLEDs.
  • the OLED is characterized by very good efficiency as well as good voltage and lifetime: 8)
  • the compounds HTM-1 and HTM-2 are used as hole transport material for a blue fluorescent OLED and compared with the compounds CE-1 and CE-2 in an otherwise identical stack structure: Examples 14 and 15 show that the compounds according to the invention are excellently suited as hole transport materials for blue fluorescent OLEDs.
  • Example 14 shows in comparison with Experiment 1 that the compound HTM-1 according to the invention leads to a lower operating voltage, higher efficiency and longer lifetime of the OLED than the comparison compound CE-1.
  • Example 15 shows in comparison with Experiment 2 that here too the compound HTM-2 according to the invention leads to a lower operating voltage, higher efficiency and longer lifetime of the OLED than the compound CE-2.

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

Abstract

La présente invention concerne des composés de formule (I) ou (II), des procédés de préparation de composés de ce type, des dispositifs électroniques, en particulier des OLED, contenant un ou plusieurs de ces composés, et l'utilisation desdits composés dans des dispositifs électroniques, en particulier dans des OLED.
EP23820941.5A 2022-12-12 2023-12-11 Matériaux pour dispositifs électroniques Pending EP4634166A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22212783 2022-12-12
PCT/EP2023/085018 WO2024126322A1 (fr) 2022-12-12 2023-12-11 Matériaux pour dispositifs électroniques

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EP4634166A1 true EP4634166A1 (fr) 2025-10-22

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KR (1) KR20250121402A (fr)
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Publication number Priority date Publication date Assignee Title
US20070092755A1 (en) 2005-10-26 2007-04-26 Eastman Kodak Company Organic element for low voltage electroluminescent devices
KR102015765B1 (ko) * 2012-02-14 2019-10-21 메르크 파텐트 게엠베하 유기 전계발광 소자용 스피로비플루오렌 화합물
JP6567520B2 (ja) 2013-08-15 2019-08-28 メルク パテント ゲーエムベーハー 電子素子のための材料
WO2015090504A2 (fr) 2013-12-19 2015-06-25 Merck Patent Gmbh Composés spiraniques hétérocycliques
KR102660538B1 (ko) * 2015-07-22 2024-04-24 메르크 파텐트 게엠베하 유기 전계발광 소자용 재료
WO2020109434A1 (fr) 2018-11-30 2020-06-04 Merck Patent Gmbh Composés pour dispositifs électroniques
WO2020159333A1 (fr) 2019-02-01 2020-08-06 주식회사 엘지화학 Composé et dispositif électroluminescent organique le comprenant

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WO2024126322A1 (fr) 2024-06-20
CN120390742A (zh) 2025-07-29

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