WO2007072691A1 - COMPOSE A SYSTEME D’ELECTRONS π ET AU BORE ORGANIQUE ET INTERMEDIAIRE POUR LE PREPARER - Google Patents

COMPOSE A SYSTEME D’ELECTRONS π ET AU BORE ORGANIQUE ET INTERMEDIAIRE POUR LE PREPARER Download PDF

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WO2007072691A1
WO2007072691A1 PCT/JP2006/324467 JP2006324467W WO2007072691A1 WO 2007072691 A1 WO2007072691 A1 WO 2007072691A1 JP 2006324467 W JP2006324467 W JP 2006324467W WO 2007072691 A1 WO2007072691 A1 WO 2007072691A1
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group
substituted
monovalent
heterocyclic
aryl
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Japanese (ja)
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Shigehiro Yamaguchi
Atsushi Wakamiya
Kenji Mori
Cui-Hua Zhao
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National University Corporation Nagoya University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • 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, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • 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
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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
    • 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
    • H10K85/658—Organoboranes
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • 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

Definitions

  • the present invention relates to a novel organoboron ⁇ -electron compound and synthetic intermediates thereof.
  • organic EL organic electroluminescent devices
  • organic lasers organic lasers
  • the organic light-emitting material is required to emit light with a high quantum yield, and it is widely known that the construction of a highly planar ⁇ -electron skeleton is effective for this purpose.
  • ⁇ -electron compounds having a condensed polycyclic system such as anthracene and perylene, a stilbene skeleton, an oligo-phenylene skeleton, etc.
  • the ⁇ -electron compound described above generally has a highly planar ⁇ -electron skeleton, the higher the concentration, the stronger the intermolecular interaction in the solution state, the more the quenching occurs. In particular, in the solid state, this strong intermolecular interaction increases the degree of quenching. For this reason, quantum efficiency tends to decrease significantly in the solid state, and the number of luminescent materials having a high quantum yield in the solid state is extremely limited. For this reason, development of a new light-emitting material that emits light with a high quantum yield in the solid state is desired!
  • the present invention has been made in view of the above-described problems, and an object thereof is to provide a novel organoboron ⁇ -electron compound. Another object of the present invention is to provide a novel organoboron ⁇ -electron compound in which a boron substituent is introduced as a side chain to the ⁇ -conjugated skeleton. It is another object of the present invention to provide a synthetic intermediate for such an organic boron ⁇ -electron compound.
  • the organoboron ⁇ -electron compound of the present invention is a compound represented by the following formula (1) in which two boron substituents are introduced at the para position in benzene or substituted benzene.
  • the boron substituent represents BI ⁇ R 2 and one BR 3 R 4 in the formula (1).
  • the “para-position” as used herein means that the relative positions of the two substituents on the benzene ring or substituted benzene ring are at the 1- and 4-positions.
  • the boron substituents R 1 , R 2 , R 3 and R 4 used as the side chain have steric hindrance to the ⁇ -electron skeleton, and the ⁇ -electron skeleton is twisted. .
  • the ⁇ -electron skeleton has non-planarity, and it is assumed that the degree of intermolecular interaction in the solid state can be controlled.
  • the boron substituent is used as a side chain, the ⁇ -electron system can be extended in a direction different from the main chain direction. Thereby, a favorable color development is shown as a luminescent material. Therefore, these organic boron ⁇ -electron compounds can be used together with luminescent materials (e.g., light emitting layers of organic EL devices and organic lasers) Suitable for c
  • Ar 1 is benzene or substituted benzene
  • R 1 , R 2 , R 3 and R 4 are each independently a phenyl group, a substituted phenyl group, a mesityl group, a substituted mesityl group.
  • Benzene, substituted benzene, thiophene, substituted thiophene, pyrrole, substituted pyrrole, furan, substituted furan, pyridine, substituted pyridine, naphthalene, substituted naphthalene, anthracene, substituted anthracene, phenanthrene, substituted phenanthrene, oligoaryl group, substituted oligoaryl group , Oligo heteroaryl group, substituted oligohet Lower reel group, ⁇ , ⁇ — Jetul oligoaryl group, (X, ⁇ — Jetul oligo hetero reel group, ⁇ , ⁇ — Dibulol oligo reel group, (X, ⁇ — Divinyl oligo hetero reel group ⁇ 2 and ⁇ 3 are each independently a monovalent group such as phenylacetylene, substituted phenylacetylene, styryl, substituted styryl, hetero
  • R 1 , R 2 , R 3 and R 4 are 2, 4, 6-trimethyl phenol group (mesityl (Mes) group), 2, 4, 6-tris (trifluoromethyl) phenol-
  • a bulky group such as a ruthel group, 2,4,6-triisopropylphenol group, 2,4,6-tritert-butylphenol group is preferred, and a mesityl group is particularly preferred.
  • ⁇ may be 0 or 1.
  • Another organic boron ⁇ -electron compound of the present invention is represented by the following formula (7).
  • R 1 and R 2 are each independently a phenyl group, an orthoalkylphenol group, a substituted orthoalkylphenyl group, a 2,6-dialkylphenol group, , Substituted 2, 6-Dialalkylphenol, 2, 4, 6-Trialkylphenol, Substituted 2, 4, 6-Trialkylphenol, 2, 6-Diarylphenol, Substitution 2 , 6-diarylphenol, 2, 4, 6- triarylphenyl, substituted 2, 4, 6-triarylphenol, chael, substituted phenyl, furyl, substituted furyl Group, pyrrolyl group, substituted pyrrolyl group, pyridyl group, substituted pyridyl group, naphthyl group, substituted naphthyl group, anthryl group, substituted anthryl group, phenanthryl group, substituted phenanthryl group, pyrenyl group, and substituted pyrenyl group strength.
  • One kind is a phenyl group
  • R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or 1 carbon atom.
  • R 5 and R 6 are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a substituted aryl group, an aryloxy group, an aryloxy group, an arylalkyl group, an arylalkylthio group, or an arylalkylthio group.
  • 1 is a value from 1 to 20
  • m is a value from 0 to 20
  • n is a value from 1 to 100.
  • FIG. 1 is an explanatory diagram of the results of X-ray crystallographic analysis of compound (4a).
  • FIG. 2 is an explanatory diagram of an X-ray crystallographic analysis result of compound (4b).
  • FIG. 3 is an explanatory diagram of the results of X-ray crystallographic analysis of compound (11).
  • FIG. 4 is an explanatory diagram of the results of X-ray crystallographic analysis of compound (22).
  • FIG. 5 is a graph showing an absorption spectrum and a fluorescence spectrum of compound (22).
  • FIG. 6 is a graph showing the fluorescence spectrum of compound (23).
  • FIG. 7 is a graph showing the results of cyclic voltammetry measurement for compounds (22) and (26). is there.
  • FIG. 8 is a graph showing the fluorescence spectrum of compound (24).
  • FIG. 9 is a graph showing an absorption spectrum and a fluorescence spectrum of compound (29).
  • FIG. 10 is a graph showing an absorption spectrum and a fluorescence spectrum of compound (30).
  • FIG. 11 is a graph showing an absorption spectrum and a fluorescence spectrum of compound (31).
  • FIG. 12 is a graph showing an absorption spectrum and a fluorescence spectrum of compound (32).
  • the organoboron ⁇ -electron compound of the present invention is a compound represented by the above formula (1) in which two boron substituents are introduced at the para position in benzene or substituted benzene. Further, specific examples of the organic boron ⁇ -electron compound of the present invention represented by the above formula (1) are represented by the following formula (2) or (3).
  • this organoboron ⁇ -electron compound an acetylene bond or an ethylene bond is introduced, and therefore the ⁇ -electron system is likely to spread in the main chain direction compared to an organoboron ⁇ -electron compound in which these bonds are not introduced. As a result, light emission tends to occur in the visible region, so it is preferred as a luminescent material.
  • the compound of the above formula (1) can be produced, for example, using a synthetic intermediate of the following formula (4).
  • a route for synthesizing this synthetic intermediate of formula (4) chlorine, bromine or iodine introduced into the 2,5-positions of Ar 2 using an organometallic reagent is placed on the metal.
  • One possible route is to introduce a boron substituent into Ar 2 by reacting with a halogenated boron compound such as dimesityl boron fluoride.
  • an organometallic reagent for example, organic lithium (n-BuLi, sec-BuLi, tert-BuLi, etc.), organic magnesium halide, etc. can be used.
  • the end of the compound of formula (4) is an ethi-lou or metal ion. Route that couples the product and dinologene reel with a palladium catalyst, and a route that couples a halogenated end with jet leur or dimetalated aryl using a palladium catalyst. Can be mentioned.
  • the organic boron ⁇ -electron compound of formula (2) can be synthesized by using the synthetic intermediate of formula (5), and the organic of formula (3) can be synthesized by using the synthetic intermediate of formula (6).
  • Boron ⁇ -electron compounds can be synthesized.
  • the reaction conditions such as the reaction solvent, reaction temperature, reaction time, molar concentration of substrate and reagent to be used may be appropriately set according to the reagent to be used.
  • Ar 2 is benzene or substituted benzene
  • R 5 , R 6 , R 7 and R 8 are each independently a phenyl group, a substituted phenol group, a mesityl group, Substituted mesityl group, 2,6-xylyl group, substituted 2,6-xylyl group, orthotolyl group, substituted orthotolyl group, 2, 4, 6-triisopropyl group, substituted 2,4,6-triisopropyl group, 2, 4, 6-tri-t-butylphenol, substituted 2, 4, 6-tri-t-butylphenol, 2, 4, 6-tris (trifluoromethyl) phenol, substituted 2, 4, 6— Tris (trifluoromethyl) phenol group, 2,6-dialkylphenol group, substituted 2,6-dialkylphenol group, 2,4,6-trialkylphenol group, substituted 2,4 , 6-trialkylphenol, 2, 6-diarylphenol, substituted 2, 6-diarylphenol, 2,
  • R 11 and R 12 are each independently a hydrogen atom, a trialkylsilyl group, an alkyldiarylsilyl group, a dialkylarylsilyl group, a triarylsilyl group, or a trialkylstane.
  • R 13 and R 14 are each independently a hydrogen atom, a trialkylsilyl group, an alkyldiarylsilyl group, a dialkylarylsilyl group, a triarylsilyl group, or a trialkylstane.
  • R 1 and R 2 may each independently be a 2,4,6-trialkylphenol group or a substituted 2,4,6-trialkylphenol group.
  • at least one of R 5 and R 6 may be a group represented by the following formula (8) or the following formula (9).
  • R 3 and R 4 may be a hydrogen atom.
  • 1 and m may be 1, and n may be 1 or 2.
  • 1, m and n are all 1, and R 5 and R 6 may be an aryl group, a substituted aryl group or a monovalent substituted heterocyclic group.
  • the aryl group may be a phenyl group
  • the substituted aryl group may be a substituted phenyl group
  • the substituted heterocyclic group may be a substituted phenyl group (eg, a diarylaminochel group such as a diphenylamino group).
  • R 7 and R 8 are each independently a phenyl group or a substituted phenyl group.
  • R 9 and R 1G are each independently a phenyl group or a substituted phenyl group.
  • the organoboron ⁇ -electron compound of the present invention represented by the above formula (7) has a steric hindrance to the ⁇ -electron skeleton of the boron substituent—BR 2 R 1 and R 2 used as the side chain. It is thought to affect. For this reason, the ⁇ -electron skeleton is twisted and has non-planarity, and the intermolecular structure in the solid state It is assumed that the degree of interaction can be controlled. As a result, the compound of the above formula (7) can have a high quantum yield in the solid state.
  • the organoboron ⁇ -electron compound of the present invention is suitable as a luminescent material. Furthermore, by introducing boron, which is Lewis acid, into the side chain, the oligothiophene compound that originally tends to have hole transportability can be given electron transportability. Therefore, the organoboron ⁇ -electron compound of the present invention is suitable as a charge transport material.
  • R 1 and R 2 in the above formula (7) include a phenyl group, an orthoalkylphenol group, a 2,6-dialkylphenol group, a 2,4,6-trialkylphenol group, Group, 2,6-diaryl furol group, 2, 4, 6-triaryl furol group, chael group, furyl group, pyrrolyl group, pyridyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group and These substituents are exemplified.
  • the orthoalkylphenyl group includes an orthotolyl group, and an orthotamal group
  • the 2,6-dialkylphenyl group includes a 2,6-xylyl group.
  • 6-trialkylphenol groups include mesityl group, 2, 4, 6-triisopropylphenol group, 2, 4, 6-tree tert-butylphenol group, 2, 4, 6-tris (trifluoro) ) Methylphenol group, etc.
  • the 2,6-diarylphenol group is 2,6-bis (2-methylphenyl) phenol group, 2,6-bis (2-isopropylphenol) ) Phenol group, 2, 6-bis (2, 6-dimethylphenol) phenolic group, 2, 6-bis (2,6-diisopropylphenyl) phenol group, 2, 6-bis (2, 6-dimethylphenol) — 4 —tert-butylphenol group, etc.
  • 2, 4, 6-triarylphenol group is 2, 4, 6-triphenyl Examples include a phenolic group and a 2,4,6-triphenylphenol group.
  • the mesityl group is preferably 2, 4, 6-triisopropylphenol group, 2, 4, 6-tri tert-butylphenol group, 2, 4, A bulky group such as a 6-tris (trifluoro) methylphenol group, more preferably a 2,4,6-trialkylphenol group, and still more preferably a mesityl group.
  • the methoxy group provides steric protection on the boron, and also causes steric hindrance to the ⁇ -electron skeleton and firmly fixes the steric structure.
  • R 3 and R 4 include a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 1 to 16 carbon atoms, an alkoxy group, an alkylthio group, a fluoroalkyl group, an alkyl group, Roxy group, aryloxy group, arylalkyl group, arylalkylalkoxy group, arylalkylthio group, aryl group, azo group, carboxyl group, acyl group, alkoxycarbonyl group, formyl group, nitro group, cyano group, arylaryl sulfone -Luoxy group, alkylsulfonyloxy group, and norogen atom, aryl group, monovalent heterocyclic group, alkenyl group, alkyl group, amino group, silyl group, phosphino group, silyloxy group, boryl group, and these And the like.
  • R 3 and R 4 are preferably hydrogen atoms.
  • one of R 3 and R 4 is a hydrogen atom and the other is a substituted boryl group (for example, —BR 2 ), and R 5 and R 6 are substituted heterocyclic groups (for example, a substituted chenyl group such as a trialkylsilyl ether group). Is preferred.
  • R 5 and R 6 include a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylalkyl group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, An aryl group, a cyan group, an azo group, a carboxyl group, an acyl group, an alkoxycarbo group, a formyl group, a nitro group, an arylsulfoloxy group, an alkylsulfoloxy group and a halogen atom, an aryl group, an oligoaryl group, Monovalent heterocyclic group, monovalent oligoheterocyclic group, alkaryl group, alkyl group, amino group, silyl group, stannyl group, boryl group, phosphino group, silyloxy group, and their substituents Is mentioned.
  • which group is used may be appropriately selected according to the target color of light emission. For example, when the number of thiophene rings in the ⁇ -electron skeleton is relatively small (for example, 2 to 4), when the target emission color is blue or light blue, hydrogen atoms are introduced at both ends, and the green Sometimes a group with high electron accepting properties is introduced at both ends, when it is yellow, a group with high electron accepting properties is introduced at one end, and a group with high electron donating properties is introduced at the other end, and when it is orange or red, both ends are introduced.
  • examples of the group having a high electron accepting property include a boron substituent such as a dimesitylboryl group, and examples of the group having a high electron donating property include a diphenylaminophenyl group.
  • At least one of R 5 and R 6 in the above formula (7) is a group represented by the above formula (8). It may be.
  • a boron substituent having an electron accepting property as a terminal group the electron accepting property of the organic boron ⁇ -electron compound can be improved, and the electron injection efficiency can be enhanced. Therefore, it is suitable as an electron transporting material. Also, the quantum yield of light emission in the solid state is increased.
  • groups represented by the above formula (8) are introduced into both ends of R 5 and R 6 , the electron accepting property and the electron injecting efficiency are improved, and a more suitable electronic structure as an electron transporting material is obtained. Can be given.
  • R 7 and R 8 have a viewpoint power to obtain a good light emission by expanding the ⁇ -electron system, preferably a phenyl group or a substituted full group, and more preferably a mesityl group, 2, 4, 6 triisopropyl
  • a bulky group such as a phenol group, 2, 4, 6 tri tert butyl butyl group, 2, 4, 6 tris (trifluoro) methyl phenol group, and more preferably a mesityl group. This is because the three-dimensional structure is stabilized by three-dimensionally protecting boron on the mesityl group.
  • R 5 and R 6 in the formula (7) may be a group represented by the formula (9).
  • the electron donating property of the organic boron ⁇ -electron compound can be improved, and the hole injection efficiency can be increased.
  • the quantum yield of light emission in the solid state is increased.
  • the hole injection efficiency tends to be low in the oligothiophene part! The effect of introducing a group is high.
  • the hole injection efficiency is increased even when the number of thiophene rings is small, and not only the electron transport property but also the hole transport property can be provided. Therefore, it is suitable as a charge transport material.
  • groups represented by the above formula (9) are introduced into both ends of R 5 and R 6 , the hole injection efficiency is improved, and a more suitable electronic structure as a hole transporting material is provided. be able to.
  • R 9 and R 1C> are more preferably a phenyl group or a substituted phenyl group, and even more preferably a phenyl group, from the viewpoint of the luminous efficiency in the solid state.
  • 1, m and n in the above formula (7) are not particularly limited as long as they are integers.
  • R 5 and R may be selected as appropriate according to the target color of light emission.
  • n is preferably 2 or more.
  • the compound of the above formula (7) is an electron transporting material. It is also suitable as a hole transporting material.
  • the compound of formula (7) has bipolar properties because it exhibits hole transportability in the oligothiophene moiety and easily exhibits electron transportability in the borylthiophene moiety. Is done.
  • 1 and m may be 1 and ⁇ may be 1 or 2.
  • 1, m and ⁇ in the above formula (7) may be all 1, and R 5 and R 6 may be an aryl group, a substituted aryl group, or a monovalent substituted heterocyclic group (R 5 and R 6 may be the same or different).
  • the aryl group is a phenyl group
  • the substituted aryl group is a substituted phenyl group (for example, 4-diphenylaminophenyl group, 4-1 rubazolyl file group, mesityl group, etc.)
  • the substituted heterocyclic group is substituted with a substituted chain group.
  • a diarylaminochel group such as a diphenylaminochelyl group.
  • organoboron ⁇ -electron compounds in which 1, m and ⁇ are both 1 and R 5 and R 6 are both diarylaminophenyl groups have the ability to exhibit a fluorescence maximum at around 660 nm, that is, in the red region.
  • Compounds having such properties are not well known so far because of low band gap theory, and are highly useful in this respect.
  • the compound of the above formula (7) can be obtained by using, for example, organic lithium (n-BuLi, sec BuLi, tert- BuLi, etc.) such as noro-oligothiophene substituted at the 3- or 4-position of the thiophene ring with a halogen atom.
  • a route may be considered in which a boron substituent is introduced into the side chain of oligothiophene by lithiation with a boron compound and reacting with a boron halide compound.
  • the reaction conditions such as the reaction solvent, reaction temperature, reaction time, mole concentration of the substrate and reagent to be used may be appropriately set according to the reagent to be used.
  • an alkyl group, an orthoalkylphenol group, a 2,6 dialkylphenol group, 2 , 4, 6 Trialkyl alkyl groups, alkylthio groups, arylalkyl groups, arylalkylthio groups, alkylsulfo-oxy groups, and the like include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n Butyl group, isobutyl group, sec butyl group, tert-butyl group, etc., alkoxy group, aryloxy group, alkoxycarbo- Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a tert-butoxy group.
  • alkenyl group examples include a vinyl group, an aryl group, a butyr group, and a styryl group.
  • alkynyl group examples include an ethuryl group, a propargyl group, a phenylacetyl group, an aryl group, an aryloxy group, an aryl group, an aryl alkyl group, an aryl alkyl alkoxy group, an aryl alkylthio group, an aryl sulfo group.
  • 2, 6-diarylphenol, 2,4,6-triarylphenol, etc. include phenyl, 2,6-xylyl, mesityl, duryl, biphenyl, and the like.
  • terfel group naphthyl group, anthryl group, pyrenyl group, tolyl group, acyl group, fluorophenol group, diphenyl group
  • examples include a phenol group, a dimethylaminophenol group, a jetylaminophenol group, a phenanthrenyl group, and the oligoaryl group includes an oligoparaphenylene, an oligofluorene, and an Rigo (paraphenolic lenylene).
  • Oligo para-phenylene-ethylene
  • monovalent heterocyclic groups include furyl, chenyl, pyrrolyl, pyridyl, benzochel, quinolyl, etc.
  • oligoheterocyclic group examples include oligofuran, oligothiophene, oligopyridine, oligobenzobenzothiophene, and the halogen atom includes a fluorine atom, a chlorine atom, and the like.
  • substituents of those prefixed with “substitution” include, for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
  • a halogen atom a methyl group, an ethyl group, a ⁇ -propyl group, an isopropyl group, a ⁇ -butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an alkyl group; a cyclopentyl group Cyclic alkyl groups such as a cyclohexyl group; Alkenyl groups such as a vinyl group, an aryl group, a butenyl group, and a styryl group; an alkynyl group such as an ethynyl group, a propargyl group, and a fluoracetinyl group; a methoxy group, an ethoxy group, Alkoxy groups such as isopropoxy group and tert-butoxy group; alkoxy groups such as buroxy group and arryloxy group; eturoxy group And alkenyloxy groups such as phenacety
  • a nitro group, a formyl group, a nitroso group, a formyloxy group, an isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a cyano group and the like can be mentioned. Further, these substituents may be bonded to each other at any position to form a ring.
  • the organoboron ⁇ -electron compound of the present invention can be used as a light-emitting material such as an organic EL device or an organic laser.
  • a light-emitting material such as an organic EL device or an organic laser.
  • An organic EL element has a structure in which three thin films, a hole transport layer, a light-emitting layer, and an electron transport layer, are sandwiched between two electrodes. Holes injected from the anode are transferred to the light-emitting layer through the hole-transport layer.
  • Each layer that constitutes the organic EL element is formed by forming the material that constitutes each layer into a thin film by a known vapor deposition method or spin coating method.
  • the vapor deposition conditions depend on the type of material that should form each layer and the purpose of the molecular accumulation film. Different forces depending on the crystal structure and the associating structure, etc.
  • boat heating temperature 50 ⁇ 40 0 ° C, vacuum degree 10-6 ⁇ : LO-3Pa, deposition rate 0.01 ⁇ 50nmZs, substrate temperature -50 ⁇ + 300 ° C, film thickness 5 ⁇ 5000nm can be selected as appropriate! / ⁇ .
  • a thin film with anode material strength on an appropriate substrate is formed by vapor deposition to a thickness of 1 ⁇ m or less, preferably in the range of 10 to 2 OOnm.
  • a thin film made of a material is formed by vapor deposition to form a hole transport layer.
  • a thin film made of the organoboron ⁇ -electron compound of the present invention is formed on the formed hole transport layer by an evaporation method to form a light emitting layer, and a thin film made of an electron transport material is further formed thereon by an evaporation method. It is formed as an electron transport layer.
  • an organic EL device can be obtained by forming a cathode on the formed electron transport layer by a vapor deposition method so as to have a thickness of 1 ⁇ m or less as a negative material force.
  • the production order may be reversed, and the cathode, the electron transport layer, the light emitting layer, the hole transport layer, and the anode may be produced in this order.
  • the anode of the organic EL element is composed of, for example, an electrode material having a high work function.
  • a metal such as gold, an alloy such as copper iodide, indium tinoxide, Dielectric transparent material power such as zinc oxide is also configured.
  • the cathode of the organic EL element may be composed of an electrode material having a low work function.
  • calcium, magnesium, lithium, aluminum, magnesium alloy, aluminum Z lithium mixture, magnesium / A silver mixture, indium force may also be configured.
  • the hole transport layer of the organic EL element is composed of, for example, a polymer having a main chain or a side chain of an aromatic tertiary amine such as N-carbcarbazole, polycarbcarbazole, or the like, TPD, or aromatic tertiary amine.
  • Triarylamine derivatives such as bis (4 di-p-triaminophenol) cyclohexane and N, N, 1-diphenyl-N, N, -dinaphthyl-4,4, -diaminobiphenyl, copper phthalocyanine, etc. Phthalocyanine derivatives, polysilanes, and the like.
  • the electron transport layer of the organic EL device includes, for example, tris (8-hydroxyquinolinate) aluminum (Alq), a polymer of certhiazole, 1, 3, 4 oxazole derivatives, 1, 2, 4
  • Example 1 may be a triazole derivative.
  • Figure 1 shows the results.
  • the benzene ring introduced with a boron substituent and the benzene ring bonded to this benzene ring via an acetylene bond are dihedral angles. 37. 28 ° was formed, and it was confirmed that the ⁇ -electron skeleton was twisted. This is presumed that steric hindrance was caused by the boron substituent into which two mesityl groups were introduced, and this steric hindrance caused a twist between the two benzene rings.
  • the steric structure of Compound 4a was firmly fixed by the boron substituent.
  • a spin coat film and a powder of the obtained Compound 4a were prepared.
  • a spin coat film was prepared on a quartz substrate using a THF solution prepared by setting the concentration of compound 4a to about 1 mgZO. 25 mL.
  • the powder was obtained by distilling off the solvent under reduced pressure after purification.
  • the obtained spin coat film and powder are measured for absorption spectrum and fluorescence spectrum using a fluorescence spectrometer F4500 (manufactured by Hitachi), and using a quantum yield measuring device C9920-01 (manufactured by Hamamatsu Photonitas).
  • the fluorescence quantum yield was measured.
  • Table 1 shows the measurement results. First, as shown in Table 1, the absorption spectrum of the spin coat film showed an absorption maximum at 360 nm. When photoexcited at this wavelength, it showed a fluorescence maximum at 484 nm. Also, The powder showed an absorption maximum at 360 nm and a fluorescence maximum at 498 nm.
  • FIG. 2 shows the results.
  • the benzene rings in the ⁇ -electron skeleton of compound 4b the benzene ring introduced with a boron substituent and the benzene ring bonded to this benzene ring via an acetylene bond are dihedral angles. 47. 53 ° was formed, and it was confirmed that the ⁇ -electron skeleton was twisted.
  • Compound 22 was obtained in a yield of 63% as 3.59 g (8.68 mmol) of a yellowish green solid.
  • Trace melting point measurement When the melting point of the obtained solid was measured with a constant apparatus (manufactured by Yanakone, MP-S3), the melting point was 129.3-129.8 ° C.
  • the spectrum data is as follows.
  • a spin coat film of the obtained Compound 22 was prepared.
  • the spin coat film was prepared by preparing a THF solution in which the concentration of compound 22 was about 1 mgZO.25 mL, and 0.3 mL of this solution was dropped on a quartz plate placed on a spin coater (Mikasa, 1H-D7), This was prepared by rotating for 60 seconds at lOOOrpm and then further rotating for 20 seconds at 300rpm.
  • FIG. 7 shows the results of cyclic voltammetry performed on the obtained compound 22. Cyclic voltammetry uses n- Bu N + PF 6 "(0.1 M) as the indicator electrolyte.
  • a spin coat film of Compound 24 was prepared in the same manner as in Example 6 (3) above, and the absorption spectrum, fluorescence spectrum and fluorescence quantum yield were in the same manner as in Example 6 (4) and (5) above. The rate was measured. As a result, the spin coat film showed an absorption maximum at 41 lnm and a fluorescence maximum at 509 ⁇ m (see Table 2). In the solution state, the absorption maximum was shown at 406 nm and the fluorescence maximum was shown at 480 nm. In addition, as shown in FIG. 8, the fluorescence spectrum shifted slightly longer in the solid state than in the solution state, but the shape of the spectrum was substantially the same. Compared with compound 23 of Comparative Example 1 (see FIG.
  • the fluorescence spectrum in the spin coat film showed a long-wavelength shifted peak corresponding to excimer emission, whereas the fluorescence spectrum was compared with compound 23.
  • the waveform of the fluorescence spectrum was almost unchanged compared to that of the THF solution, and no excimer emission was observed. From this, it can be said that Compound 24 can more effectively suppress the interaction between molecules in the solid state (spin coat film).
  • Cii l (% ⁇ om Z 'louiuieoo ⁇ ' ⁇ Z 9) lOHO- ( ⁇ qp) Pd (louiuios ⁇
  • the present invention is not limited to the above-described embodiment, and can be implemented in various modes as long as it belongs to the technical scope of the present invention.
  • the present invention can be used in the field of organic electronics such as organic EL and organic lasers.

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  • Engineering & Computer Science (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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Abstract

L’invention concerne un composé à système d’électrons π et au bore organique répondant à la formule (1), dans laquelle deux substituants bore sont introduits sur un noyau benzénique substitué ou non en position para. Dans ledit composé, un squelette de système d’électrons π est gêné sur le plan stérique par les substituants bore R1 à R4 de manière à provoquer une torsion dudit squelette. Lorsque le composé passe sous un état solide et que son rendement quantique de fluorescence (φ) est mesuré, de bons résultats sont obtenus. Ainsi, le composé peut émettre de la lumière avec un rendement élevé même à l’état solide ; il est par conséquent adapté pour être utilisé en tant que matériau luminescent (par exemple : couche luminescente ou laser organique pour élément électroluminescent organique).
PCT/JP2006/324467 2005-12-16 2006-12-07 COMPOSE A SYSTEME D’ELECTRONS π ET AU BORE ORGANIQUE ET INTERMEDIAIRE POUR LE PREPARER WO2007072691A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008152939A1 (fr) * 2007-06-15 2008-12-18 Idemitsu Kosan Co., Ltd. Dérivé aromatique d'un composé du bore, dispositif électroluminescent organique, et solution contenant un matériau électroluminescent organique fabriquée avec celui-ci
WO2010126233A1 (fr) * 2009-04-28 2010-11-04 Dow Advanced Display Materials,Ltd. Nouveaux composés électroluminescents organiques et dispositif électroluminescent organique les utilisant
CN106518901A (zh) * 2016-09-14 2017-03-22 南京邮电大学 一种发光的四配位梯形有机硼化合物及其制备方法和应用
JP2021031391A (ja) * 2019-08-15 2021-03-01 地方独立行政法人東京都立産業技術研究センター π共役系ホウ素化合物、π共役系ホウ素化合物の製造方法および電子装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102618752B1 (ko) * 2016-10-25 2023-12-27 엘지디스플레이 주식회사 상전이 광 이성질체 화합물, 발광다이오드 표시장치 및 그 제조 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000294373A (ja) * 1999-04-05 2000-10-20 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子用材料およびそれを使用した有機エレクトロルミネッセンス素子
JP2003031368A (ja) * 2001-07-11 2003-01-31 Konica Corp 有機エレクトロルミネッセンス素子及び表示装置
WO2004099291A1 (fr) * 2003-05-08 2004-11-18 Osram Opto Semiconductors Gmbh Boranes peraryles polymeriques non conjugues, leur utilisation comme emetteurs et/ou materiaux de transport organiquement semi-conducteurs, leur procede de production et leurs utilisations
JP2005216823A (ja) * 2004-02-02 2005-08-11 Sharp Corp 有機エレクトロルミネッセンス素子

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000294373A (ja) * 1999-04-05 2000-10-20 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子用材料およびそれを使用した有機エレクトロルミネッセンス素子
JP2003031368A (ja) * 2001-07-11 2003-01-31 Konica Corp 有機エレクトロルミネッセンス素子及び表示装置
WO2004099291A1 (fr) * 2003-05-08 2004-11-18 Osram Opto Semiconductors Gmbh Boranes peraryles polymeriques non conjugues, leur utilisation comme emetteurs et/ou materiaux de transport organiquement semi-conducteurs, leur procede de production et leurs utilisations
JP2005216823A (ja) * 2004-02-02 2005-08-11 Sharp Corp 有機エレクトロルミネッセンス素子

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008152939A1 (fr) * 2007-06-15 2008-12-18 Idemitsu Kosan Co., Ltd. Dérivé aromatique d'un composé du bore, dispositif électroluminescent organique, et solution contenant un matériau électroluminescent organique fabriquée avec celui-ci
WO2010126233A1 (fr) * 2009-04-28 2010-11-04 Dow Advanced Display Materials,Ltd. Nouveaux composés électroluminescents organiques et dispositif électroluminescent organique les utilisant
CN102574871A (zh) * 2009-04-28 2012-07-11 罗门哈斯电子材料韩国有限公司 新颖的有机电致发光化合物和使用该化合物的有机电致发光器件
CN106518901A (zh) * 2016-09-14 2017-03-22 南京邮电大学 一种发光的四配位梯形有机硼化合物及其制备方法和应用
JP2021031391A (ja) * 2019-08-15 2021-03-01 地方独立行政法人東京都立産業技術研究センター π共役系ホウ素化合物、π共役系ホウ素化合物の製造方法および電子装置
JP7372652B2 (ja) 2019-08-15 2023-11-01 地方独立行政法人東京都立産業技術研究センター アクセプター材料、π共役系ホウ素化合物の製造方法および電子装置

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