WO2014111980A1 - Dérivé de triptycène utilisé comme matériau pour former un film auto-assemblé, procédé de production dudit dérivé, film produit à l'aide dudit dérivé et procédé de production dudit film - Google Patents

Dérivé de triptycène utilisé comme matériau pour former un film auto-assemblé, procédé de production dudit dérivé, film produit à l'aide dudit dérivé et procédé de production dudit film Download PDF

Info

Publication number
WO2014111980A1
WO2014111980A1 PCT/JP2013/004952 JP2013004952W WO2014111980A1 WO 2014111980 A1 WO2014111980 A1 WO 2014111980A1 JP 2013004952 W JP2013004952 W JP 2013004952W WO 2014111980 A1 WO2014111980 A1 WO 2014111980A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
film
atom
hydrogen atom
Prior art date
Application number
PCT/JP2013/004952
Other languages
English (en)
Japanese (ja)
Inventor
福島　孝典
良晃 庄子
Original Assignee
独立行政法人科学技術振興機構
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 独立行政法人科学技術振興機構 filed Critical 独立行政法人科学技術振興機構
Priority to JP2014557181A priority Critical patent/JP6219314B2/ja
Publication of WO2014111980A1 publication Critical patent/WO2014111980A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/14—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to a carbon atom of a six-membered aromatic ring
    • C07C217/24—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to a carbon atom of a six-membered aromatic ring the six-membered aromatic ring being part of a condensed ring system containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/52—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of six-membered aromatic rings being part of condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/21—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/72—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings and other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • 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
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/90—Ring systems containing bridged rings containing more than four rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate

Definitions

  • the present invention relates to a triptycene derivative useful as a material for forming a self-assembled monolayer (SAM), and an intermediate for producing the same.
  • SAM self-assembled monolayer
  • the self-assembled monomolecular film is adsorbed or chemically bonded to the surface of a solid substrate, and is formed as a monomolecular layer (film) with high orientation by interaction between molecules.
  • the self-assembled monomolecular film is referred to as a self-assembled monomolecular film or a self-assembled monomolecular film, but is referred to as a self-assembled monomolecular film or simply a SAM film in this specification. It was reported that the SAM film was formed on a glass substrate using an organosilane compound (see Non-Patent Document 1), and that it was formed on a gold substrate using an organic sulfur compound ( (See Non-Patent Document 2).
  • the SAM film is more stable than an LB (Langmuir-Blodgett) film, and can be formed by a gas phase reaction, and its application range has been widened.
  • the film thickness of the SAM film is determined by the molecular size (length) and the tilt angle with the substrate, and a film of a molecular level of about 1 nm can be precisely and easily manufactured.
  • the film thickness is generally about 0.2 nm due to one methylene unit of the alkyl chain, and a monomolecular film with a desired film thickness can be accurately produced by adjusting the length of the alkyl chain. .
  • the characteristics of the surface of the solid substrate can be modified.
  • organic field effect transistor silicon oxide is often used as an insulating layer, but a SAM film made of an organic silane compound such as octadecyltrichlorosilane (OTS) is formed on the surface of the silicon oxide.
  • OTS octadecyltrichlorosilane
  • a specific function can be imparted to the surface of the solid substrate by bonding a functional functional group to one of the molecules forming the SAM film.
  • various functions such as electron transfer / redox reaction, catalysis, photoinduced electron transfer, electrochemical luminescence, ion / molecule recognition, biosensor, biomolecular device, solar power generation, etc. can be achieved by forming a SAM film. It can be applied to the surface of a solid substrate and is expected to be applied in these fields.
  • Non-Patent Document 3 it has been reported that triptycene derivatives substituted with 1, 2, 5, or 6 long-chain alkoxy groups are regularly aligned to form a smectic liquid crystal. It is not disclosed until the three substituents are regularly aligned in the same direction, nor is it disclosed that it is suitable as a SAM film forming material.
  • the present invention provides a Janus-type triptycene derivative represented by the following general formula [I] useful as a material substance for a self-assembled film, particularly a self-assembled monolayer, and a raw material for producing the following: A Janus type triptycene derivative represented by the general formula [II] and a method for producing them are provided.
  • the present invention also provides a film forming material containing a Janus type triptycene derivative represented by the following general formula [I], and a self-organization using the Janus type triptycene derivative represented by the following general formula [I].
  • Provided are a chemical film, a solid substrate having the film on the surface, and a method for producing the film.
  • the present inventors have examined the introduction of a plurality of functional groups into trypticene in a position-specific and surface-specific manner. Then, the inventors of the present invention have found that triptycene derivatives having three identical substituents on one side of triptycene are surface-specifically accumulated in a triple benzene ring arranged in triptycene, and It has been found that when three identical substituents have relatively long carbon chains, these substituents are aligned in the same direction and accumulate to form a film. It has also been found that the film thus formed is self-organized and can be processed into a self-assembled monolayer by further processing.
  • R 1 represents a saturated or unsaturated divalent hydrocarbon group having 2 to 60 carbon atoms, and the hydrocarbon group is one or two or more. And one or more carbon atoms in the hydrocarbon group may be an oxygen atom, a sulfur atom, a silicon atom, or —NR 5 — (wherein R 5 is And a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms).
  • R 2 s may be the same or different and are each independently a group different from the group —X—R 1 —Z, wherein R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, A cyano group, an amino group, a monoalkyl-substituted amino group, a dialkyl-substituted amino group, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted alkenyl group having 2 to 10 carbon atoms An optionally substituted alkynyl group having 2 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, and an optionally substituted alkylthio group having 1 to 10 carbon atoms.
  • a formyl group an optionally substituted alkylcarbonyl group having 1 to 10 carbon atoms, an optionally substituted alkoxycarbonyl group having 1 to 10 carbon atoms, and an optionally substituted carbon
  • An alkylcarbonyloxy group of the number 1 to 10 An aryl group having 6 to 30 carbon atoms which may have a substituent, or 1 to 5 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and 2 to 10 carbon atoms
  • a heteroaryl group optionally having a 5- to 8-membered substituent,
  • Three Xs are the same group, and X is a divalent group composed of 1 to 5 atoms selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a carbon atom, and a silicon atom, and a hydrogen atom.
  • the present invention also relates to a film forming material composition comprising a Janus type triptycene derivative represented by the above general formula [I]. Furthermore, the present invention has a film in which the Janus-type triptycene derivative represented by the above general formula [I] is self-organized, particularly a self-assembled monomolecular film, and the film on the surface of a solid substrate. Concerning the structure.
  • the Janus triptycene derivative represented by the general formula [I] is dissolved in a solvent to form a solution, and the solution is applied to the surface of the solid substrate or the solid substrate is immersed in the solution,
  • the present invention relates to a method for producing a Janus triptycene derivative film represented by the above general formula [I] on the surface of a solid substrate, which is dried and further annealed as necessary.
  • the Janus triptycene derivative represented by the general formula [I] is dissolved in a solvent to form a solution, and the solution is applied to the surface of the solid substrate or the solid substrate is immersed in the solution,
  • the present invention relates to a method for producing a structure in which a film of a Janus triptycene derivative represented by the above general formula [I] is formed on the surface of a solid substrate, which is dried and further annealed as necessary.
  • the present invention provides the following general formula [II] useful as a raw material for producing the Janus triptycene derivative represented by the general formula [I].
  • Xs are the same group, and X is composed of 1 to 5 atoms selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a carbon atom, and a silicon atom and a hydrogen atom.
  • a linker group composed of a divalent atomic group The three R 3 groups are the same, and R 3 is a hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, or each alkyl group is an alkyl group having 1 to 5 carbon atoms.
  • R 4 s may be the same or different and are each independently a group different from the group —X—R 3 , wherein R 4 represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group
  • R 4 represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group
  • X in the general formula [I] is —CH 2 —, —CH ⁇ CH—, —O—, or —NR 6 — (wherein R 6 is a hydrogen atom or having 1 to 4 carbon atoms)
  • R 1 in the general formula [I] represents an alkylene group having 2 to 30 carbon atoms, an alkenylene group having 2 to 30 carbon atoms, an alkynylene group having 2 to 30 carbon atoms, or an aryl ring having 6 to 30 carbon atoms.
  • R 1 in the general formula [I] is an alkylene group having 2 to 30 carbon atoms or a divalent arylene group having 6 to 60 carbon atoms containing an aryl ring having 6 to 30 carbon atoms, The Janus type triptycene derivative according to the above (6).
  • Z in the general formula [I] is a hydrogen atom, a haloalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a hydroxyl group, —COOR 7 (where , R 7 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms), —N (R 8 ) 2 (wherein R 8 may be the same or different, and Or a hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, or an optionally substituted aryl group having 6 to 30 carbon atoms), or —P ( ⁇ O) (OR 15 ) 2 (wherein R 15 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms).
  • Z in the general formula [I] is a hydrogen atom, —CF 3 , —CH ⁇ CH 2 , —C ⁇ CH, —COOR 7 (where R 7 has a hydrogen atom or a substituent) Represents an optionally substituted alkyl group having 1 to 5 carbon atoms), —NH 2 , or —N (Ar 1 ) 2 (wherein Ar 1 may be the same or different and each independently represents a substituent; Represents an aryl group having 6 to 30 carbon atoms which may have a phenotype of the Janus type triptycene derivative according to (8).
  • R 2 in the general formula [I] may have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an optionally substituted alkoxy group having 1 to 10 carbon atoms, or a substituent.
  • the membrane has three pentyl rings arranged in a triptycene skeleton, and the three same substituents bonded in the same direction of the benzene rings of the triptycene skeleton are aligned in the same direction.
  • the film according to (12), wherein the film is a film accumulated in an integrated manner.
  • the Janus-type triptycene derivative according to any one of (1) to (11) is dissolved in a solvent, and the solution is applied to the surface of the solid substrate, or the solid substrate is immersed in the solution and then dried.
  • a method for producing a Janus type triptycene derivative film is dissolved in a solvent, and the solution is applied to the surface of the solid substrate, or the solid substrate is immersed in the solution and then dried.
  • a method for producing a Janus type triptycene derivative film is dissolved in a solvent, and the solution is applied to the surface of the solid substrate, or the solid substrate is immersed in the solution and then dried.
  • a method for producing a Janus type triptycene derivative film is dissolved in a solvent, and the solution is applied to the surface of the solid substrate, or the solid substrate is immersed in the solution and then dried.
  • a method for producing a Janus type triptycene derivative film is dissolved in a solvent, and the solution is applied to the surface of
  • a layer structure in which the film is composed of a portion where benzene rings arranged in a triple-blade shape of a triptycene skeleton are nested and a portion where the substituent —XR 1 —Z in the general formula [I] is accumulated The manufacturing method according to any one of (27) to (40), wherein: (42) The manufacturing method according to any one of (27) to (41), wherein the film is a multilayer film. (43) The production method according to (42), wherein the film is a two-layer film. (44) The production method according to (43), wherein the two-layer film has a structure in which the Z groups in the general formula [I] face each other between molecules.
  • the Janus-type triptycene derivative according to any one of (1) to (11) is dissolved in a solvent, and the solution is applied to the surface of the solid substrate, or the solid substrate is immersed in the solution and then dried.
  • a method for producing a structure in which a film of a Janus triptycene derivative represented by the above general formula [I] is formed on the surface of a solid substrate. (48) The method according to (47), further comprising annealing the dried film. (49) The production method according to (47) or (48), wherein the solvent is a polar solvent.
  • the polar solvent is dimethylformamide (DMF) or tetrahydrofuran (THF).
  • (60) A layer structure in which the film is composed of a part where benzene rings arranged in a three-blade shape of a triptycene skeleton are nested and a part where substituents —XR 1 —Z in the general formula [I] are accumulated
  • X in the general formula [II] is —CH 2 —; —O—; —S—; —SO—; —SO 2 —; —NR 6 — (wherein R 6 is a hydrogen atom, or —CO—; —OCO—; —CONR 61 — (wherein R 61 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms); Or -NR 62 CO- (wherein R 62 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms); or the Janus according to any one of (67) to (69), Type triptycene derivatives.
  • X in the general formula [II] is —CH 2 —, —CO—, —O—, or —NR 6 — (wherein R 6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
  • the Janus type triptycene derivative according to the above (71), wherein X in the general formula [II] is a divalent group represented by —CH 2 —, —CO—, or —O—.
  • R 3 in the general formula [II] is a hydrogen atom or an alkoxyalkyl group.
  • R 3 in the general formula [II] is a trialkylsilyl group.
  • R 4 in the general formula [II] may have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an optionally substituted alkoxy group having 1 to 10 carbon atoms, or a substituent.
  • R 4 in the general formula [II] is a hydrogen atom, a halogen atom, or an optionally substituted alkoxy group having 1 to 10 carbon atoms.
  • R 4 in the general formula [II] is a hydrogen atom, and —X—R 3 is a hydroxyl group, an optionally substituted alkoxy group having 1 to 10 carbon atoms, or a trialkylsilyloxy group.
  • the membrane has three pentyl rings arranged in a triptycene skeleton, and the three same substituents bonded in the same direction of the benzene rings of the triptycene skeleton are aligned in the same direction.
  • the film according to (81), wherein the film is a film that is collected in a concentrated manner.
  • the film forms a layer structure composed of a portion where benzene rings arranged in a three-ply shape of a triptycene skeleton are nested and a portion where the substituent —XR 3 in the general formula [II] is accumulated.
  • the film according to (81) or (82). The film according to any one of (81) to (83), wherein the film is a multilayer film.
  • the Janus-type triptycene derivative according to any of (67) to (80) above is dissolved in a solvent, and the solution is applied to the surface of the solid substrate, or the solid substrate is immersed in the solution, and then dried.
  • a method for producing a Janus type triptycene derivative film (94) The method according to (93), further comprising annealing the dried film.
  • the polar solvent is dimethylformamide (DMF) or tetrahydrofuran (THF).
  • (97) A step of evaporating the Janus type triptycene derivative represented by the general formula [II] according to any one of (67) to (80) above its melting point, and the evaporated Janus type triptycene
  • (98) The production method according to (97), further comprising a step of annealing the produced film.
  • (99) The production method according to the above (98), wherein the annealing is a heat treatment at a temperature from 100 ° C. to a melting point for 5 to 50 minutes.
  • the film forms a layer structure composed of a portion where benzene rings arranged in a three-blade shape of a triptycene skeleton are nested and a portion where the substituent —X—R 3 in the general formula [II] is accumulated
  • the Janus type triptycene derivative according to any one of (67) to (80) is dissolved in a solvent, and the solution is applied to the surface of the solid substrate, or the solid substrate is immersed in the solution and then dried.
  • a method for producing a structure in which a film of a Janus triptycene derivative represented by the general formula [II] is formed on the surface of a solid substrate. (111) The method according to (110), further comprising annealing the dried film.
  • the polar solvent is dimethylformamide (DMF) or tetrahydrofuran (THF).
  • the film forms a layer structure composed of a portion where benzene rings arranged in a triple-blade shape of a triptycene skeleton are nested and a portion where the substituent —X—R 3 in the general formula [II] is accumulated.
  • a 1,8,13 comprising dissolving a trihydroxytriptycene mixture in a solvent to form a solution, crystallizing 1,8,13-trihydroxytriptycene from the solution and separating it.
  • a process for producing trihydroxytriptycene (128) The method according to (127), wherein the mixture of trihydroxytriptycene is a mixture of 1,8,13-trihydroxytriptycene and 1,8,16-trihydroxytriptycene.
  • the solvent is dimethylformamide (DMF).
  • (130) The method according to any one of (127) to (129), wherein the trihydroxytriptycene mixture is produced by hydrolyzing a trialkoxytriptycene mixture.
  • a trialkoxytriptycene mixture is produced by reacting 1,8-dialkoxyanthracene with 1-alkoxy-6-trialkylsilyl-phenol or a derivative thereof in the presence of a condensing agent. The method according to (130) above.
  • (132) The method according to (131) above, wherein the 1-alkoxy-6-trialkylsilyl-phenol has a phenolic hydroxyl group as a leaving group.
  • the leaving group is a triflate group.
  • the present invention provides a novel film-forming material for forming a self-assembled film, particularly a self-assembled monolayer.
  • the film forming material is integrated by being bonded or adsorbed on the surface of the substrate, and it is necessary to be bonded or adsorbed on the surface of the substrate. It has an accumulation capability in itself and does not necessarily have a functional group for binding or adsorbing to the surface of the substrate.
  • triptycene itself has a rigid structure and has a regular arrangement in which triple benzene rings arranged in a triptycene skeleton are accumulated in a nested manner.
  • the groups are regularly arranged with respect to the triptycene skeleton, and a regular and rigid film can be formed regardless of the chemical and / or physical conditions of the substrate surface.
  • the interaction with the solid substrate surface can be strengthened or the interaction can be weakened.
  • the group Z together or a group R 2 together may be a film of a bilayer formation, similar to the biological membrane.
  • the film formed using the novel film forming material of the present invention can have extremely unique characteristics different from those of conventional self-assembled films, and can be used for electronic devices such as thin film transistors. It is possible to provide a nano-unit thin film having a very wide application range as a protective film, a biological membrane-like film, and the like.
  • the triptycene derivative of the present invention has two surfaces, a group —X—R 1 —Z in the general formula [I] and an R 2 surface in the general formula [I] above and below the rigid triptycene skeleton. Therefore, various functions can be added simultaneously with the film forming ability. For example, by introducing an appropriate hydrophilic group or hydrophobic group into R 2 in the general formula [I], it becomes possible to appropriately adjust the hydrophilicity or hydrophobicity of one surface of the membrane. In addition, by introducing a group such as an electron acceptor into R 2 in the general formula [I], it is possible to give a semiconductor-like property to one surface of the film.
  • the present invention provides a novel triptycene derivative for a novel film-forming material and a novel intermediate for producing the same.
  • the triptycene derivative of the present invention is characterized by having the group —X—R 1 —Z in the general formula [I] only on one surface of a rigid triptycene skeleton. Further, the group —X—R 1 —Z consists of three parts having respective functions, and the group R 1 is a long-chain group for obtaining an interaction necessary for film formation, It is the hydrophobic group of the chain and characterizes the properties of the film formed.
  • the group X is a linker group for linking the R 1 group and the triptycene skeleton
  • the group Z is a terminal group of the chain portion
  • the group Z is a functional group that requires interaction with a substrate or the like. It is a group that can also function as a group. Therefore, the triptycene derivative of the present invention can not only form a regular and stable thin film, but also can be easily modified according to the purpose of the thin film, and provide a film forming material with a wide range of applications. it can.
  • FIG. 1 schematically shows a state in which the Janus triptycene derivative of the present invention is accumulated.
  • FIG. 2 schematically shows the crystal structure of 1,8,13-trimethoxytriptycene according to the present invention. The oxygen atom of the methoxy group is shown in red.
  • FIG. 3 schematically shows a single layer structure (left side of FIG. 3) of Compound 1 of the present invention and a bilayer structure (right side of FIG. 3) of Compounds 18 and 20.
  • FIG. 4 is a diagram schematically showing the bilayer structure of the compound 18 in more detail.
  • FIG. 5 shows the results of AFM measurement of a film produced on a glass substrate using Compound 1 of the present invention.
  • FIG. 6 shows the results of AFM measurement of a film produced on a mica substrate using Compound 1 of the present invention.
  • FIG. 7 shows the results of AFM measurement of a film produced on a mica substrate using Compound 1 of the present invention.
  • Triptycene itself is a known compound, which is a compound having benzene rings arranged in a unique three-blade shape.
  • the position number of triptycene is as follows according to the CAS nomenclature.
  • the “Janus type triptycene derivative” in the present invention has two different planes, ie, the 1,8,13 position plane and the 4,5,16 position plane of triptycene, and the respective planes have different characteristics. It is a triptycene derivative having Janus is the name of a god that appears in Roman mythology with different faces before and after the head. The triptycene derivative of the present invention is based on the name of the Roman mythology because it has two different faces on the 1,8,13 position plane and the 4,5,16 position faces of triptycene. It is named “Janus type”.
  • the Janus-type triptycene derivative of the present invention is a triptycene derivative having different characteristics on two faces of triptycene.
  • the Janus-type triptycene derivative of the present invention is characterized by having two surfaces, a surface on which a film is formed and a surface on which no film is formed. More specifically, the Janus-type triptycene derivative of the present invention is characterized in that it has the same substituent for forming a film on only one of the planes, for example, the planes at positions 1, 8, and 13. It is a triptycene derivative.
  • FIG. 1 the Janus triptycene derivative of the present invention in which X is —O—, R 1 is a C 11 alkylene group, Z is a —COOMe group, and all R 2 are hydrogen atoms ( Hereinafter, it is referred to as Compound 1).
  • the three benzene rings arranged in the form of three feathers of the triptycene skeleton accumulated in a nested manner means that the three benzene rings of the triptycene skeleton each form a face angle of 120 °. This is a state in which the benzene rings of adjacent triptycene are nested, and such a state is schematically shown in FIG. 1 when viewed from above.
  • the benzene rings of the adjacent triptycene skeleton enter between each of the three benzene rings arranged in the form of three triptycene skeletons, and are regularly accumulated.
  • the distance between the triptycene bridgehead and the adjacent triptycene bridgehead was about 0.81 nm.
  • “three identical substituents bonded in the same direction of the benzene ring of the triptycene skeleton are aligned and accumulated in the same direction” means that Janus type triptycene represented by the general formula [I] of the present invention Three substituents —X—R 1 —Z present on one side of the derivative extend in the same direction of the triptycene skeleton aggregate in which the benzene rings are nested, and It shows the state of being aligned and accumulated. If the state which the compound 1 illustrated above accumulate
  • the upper triptycene layer shows a triptycene skeleton aggregate in which the benzene rings are nested. Then, in the case of FIG. 3, in the case of FIG. 3, three identical substituents are aligned and accumulated in the same direction to form an alkyl layer and an ester layer.
  • the triptycene skeleton is accumulated, if the same three substituents are randomly arranged in different directions, they do not form an orderly film as shown in FIG.
  • the present inventors are the first to show that when the Janus-type triptycene derivative of the present invention is integrated, these substituents are not random, but are orderly integrated in the same direction to form a stable film.
  • FIG. 3 schematically shows a case where the terminal Z group has a bilayer structure of a compound of —COOH (compound 18) and —CH 2 NH 2 (compound 20).
  • FIG. 4 is a diagram for explaining the bilayer structure of the compound 18 in more detail.
  • the “film” in the present invention refers to a film formed by accumulating the Janus type triptycene derivative of the present invention in the state described above.
  • the film formed in this way becomes a monomolecular film and can be said to be a SAM film.
  • the film thickness can be adjusted by the number of carbon atoms in the alkylene chain, and can be determined according to the general rule of about 0.2 nm per carbon atom.
  • such layers can be overlapped to form a multilayer film. In this case, there are a case where they overlap in the same direction and a case where they overlap in opposite directions.
  • a film formed by applying a solution (1 mg / 200 mL, approximately 5.3 ⁇ M) of Compound 1 exemplified above in THF on a glass substrate and drying the film has a single-layer structure, a two-layer structure, or a three-layer structure. It can be a structure.
  • the film thickness in the case of the single layer structure was about 2.46 nm.
  • the film thickness in the case of the two-layer structure was about 5.4 nm.
  • the film thickness in the case of the three-layer structure was about 7.84 nm.
  • a film formed by applying the same solution to a mica substrate and drying can have a single-layer structure or a two-layer structure, and the film thickness in the case of the single-layer structure is about 3.27 nm.
  • the film thickness in the case of the structure was about 6.45 nm.
  • the film formed by applying the same solution to a mica substrate and drying, and then annealing at 180 ° C. had a single layer structure, and the film thickness was about 2.04 nm.
  • the “functional film” in the present invention refers to a film in which functional groups having various functions are bonded to the above-described film of the present invention.
  • a film such as a SAM film has a portion for binding or adsorbing to the surface of a solid substrate, a portion for obtaining van der Waals force between alkyl chains such as an alkyl chain for forming a stable film, and Divided into three parts, the terminal part of the molecule.
  • various functions can be imparted to the formed film by introducing a functional group having any of electrochemical, optical, and biological functions into the terminal portion of the molecule.
  • various functions can be imparted to the membrane of the present invention by using the terminal portion of the molecule.
  • the Janus-type triptycene derivative of the present invention has two surfaces, “a surface of the group —X—R 1 —Z in the general formula [I]” and “an R 2 surface in the general formula [I]”. It is possible to introduce functional groups having various functions on the surface of R 2 in the same manner as the conventional membrane. Moreover, in the conventional film, it was essential to have a portion for binding or adsorbing to the surface of the solid substrate.
  • an inter-alkyl chain such as an alkyl chain is between Since not only the van der Waals force but also the toptycene skeleton portion has a film forming ability, a portion for binding or adsorbing on the solid surface is not necessarily required. Therefore, functional groups having various functions can be introduced into the group Z moiety of the Janus-type triptycene derivative represented by the general formula [I] of the present invention.
  • a film formed by introducing a functional group having it is referred to as a “functional film”.
  • solid substrate in the present invention refers to glass, quartz, sapphire, nonmetal such as silicon and germanium, nonmetal oxide such as silicon oxide, gold, and platinum, which have been conventionally used as a solid substrate such as a SAM film.
  • Metals such as silver and copper; metal oxides such as indium oxide and ITO (Indium Tin Oxide); GaAs; solid substrates such as CdS; organic polymer materials such as polyolefin, polyacryl, polyethersulfone, polyimide, and polyethylene terephthalate Organic substrates; not only solid substrates such as biological materials derived from animals and plants derived from collagen, starch, cellulose, etc., but also solids that are difficult to bind to and adsorb to solid substrates can be used as substrates. All solids in which the membrane of the present invention described above can exist stably can be included. Further, the solid shape is not particularly limited, and may be a thin film.
  • the film using the Janus-type triptycene derivative of the present invention has a film-forming ability not only in the van der Waals force due to an alkyl chain but also in the triptycene skeleton portion, and therefore is necessarily bound or adsorbed on the surface of the solid substrate. This part is not essential. Therefore, it is not necessary to consider the binding property and adsorption capacity with the solid substrate, and the solid substrate is not particularly limited. However, in order to ensure the positional stability of the formed film, it is preferable to select a Janus-type triptycene derivative containing a moiety that can be bound and / or adsorbed to a solid substrate.
  • the “saturated or unsaturated divalent hydrocarbon group having 2 to 60 carbon atoms” in the present invention is a saturated or unsaturated chain having 2 to 60 carbon atoms, preferably 2 to 30, more preferably 5 to 30 carbon atoms. Or cyclic, linear or branched divalent hydrocarbon groups, and these saturated and unsaturated carbon atoms, chain carbon atoms and carbon atoms forming the ring are regular or irregular. May be arranged. Examples of the “saturated or unsaturated divalent hydrocarbon group having 2 to 60 carbon atoms” in the present invention include, for example, a straight chain having 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms, more preferably 5 to 20 carbon atoms.
  • a branched alkylene group a linear or branched alkenylene group having 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms; 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms, more preferably A linear or branched alkynylene group having 2 to 20 carbon atoms; containing a monocyclic, polycyclic or condensed cyclic aryl ring having 6 to 30, preferably 6 to 20, more preferably 6 to 12 carbon atoms A divalent arylene group having a total carbon number of 6 to 60, preferably 6 to 30 (the arylene group is an alkylene group, an alkenylene group, or an alkynyl group between or at the ends of the aryl ring.
  • a carbon-carbon double bond for forming an alkenylene group, a carbon-carbon triple bond for forming an alkynylene group, or an aryl ring for forming an arylene group is in a saturated alkylene group (including the terminal). Alternatively, they may be regularly or irregularly arranged before and after the unsaturated carbon-carbon bond.
  • C 6 , C 7 , C 8 , C 9 , C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , or C 17 linear or Branched, preferably straight-chain alkylene groups, one, two or three carbon-carbon double bonds are regularly or irregularly arranged in the alkylene groups (including the ends)
  • An alkylene group in which one, two, or three carbon-carbon triple bonds (including terminals) are regularly or irregularly arranged,-(-Ph-CH CH-) m-Ph- (
  • Ph represents a p-phenylene group
  • m represents an integer of 1, 2, 3, or 4.
  • the “saturated or unsaturated divalent hydrocarbon group having 2 to 60 carbon atoms” in the present invention may have a substituent, and as the “substituent”, a halogen atom; a hydroxyl group; An alkyl group having 1 to 5 carbon atoms; an alkyl group having 1 to 5 carbon atoms substituted with 1 to 5, preferably 1 to 3 halogen atoms; 1 to 5, preferably Is from the group consisting of an alkoxy group having 1 to 5 carbon atoms substituted with 1 to 3 halogen atoms; an amino group; and an amino group substituted with 1 or 2 alkyl groups having 1 to 5 carbon atoms
  • substituent are as follows.
  • the “saturated or unsaturated divalent hydrocarbon group having 2 to 60 carbon atoms” in the present invention means that “one or more carbon atoms in the hydrocarbon group are oxygen atoms, sulfur atoms, silicon atoms” Or may be substituted with —NR 5 — (wherein R 5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms) ”
  • One or more carbon atoms in the chain of carbon atoms of —C—C—C— are replaced by other atoms, eg, —C—O—C—, —C—S—C—, —C—SiH 2 —C—
  • the hydrogen atom bonded to the silicon atom in the formula may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. ), —C—NR 5 —C— and the like
  • alkyl group having 1 to 10 carbon atoms in the present invention is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms.
  • alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, An octyl group, and the like.
  • the “optionally substituted alkyl group having 1 to 5 carbon atoms” in the present invention is a straight chain having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. Or a branched alkyl group is mentioned. Examples of such alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, and the like. It is done.
  • alkenyl group having 2 to 10 carbon atoms in the present invention is a group having one or more carbon-carbon double bonds, and has a total carbon number of 2 to 10, preferably 2 to 8 carbon atoms.
  • a straight chain or branched alkenyl group having 2 to 6 carbon atoms in total is used.
  • alkenyl groups include vinyl, 1-methyl-vinyl, 2-methyl-vinyl, n-2-propenyl, 1,2-dimethyl-vinyl, 1-methyl-propenyl, Examples include 2-methyl-propenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group and the like.
  • alkynyl group having 2 to 10 carbon atoms in the present invention is a group having one or more carbon-carbon triple bonds, and has 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably Includes a straight-chain or branched alkynyl group having 2 to 6 carbon atoms in total.
  • alkynyl groups include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, n-3-butynyl group and the like. It is done.
  • the “aryl group having 6 to 30 carbon atoms” in the present invention is a monocyclic, polycyclic or condensed ring having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. And an aryl group of the formula.
  • carbocyclic aromatic groups include a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthryl group.
  • the “5- to 8-membered heteroaryl group having 1 to 5 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom and having 2 to 10 carbon atoms” in the present invention is 1
  • Monocyclic, polycyclic, or fused-ring heteroaryl groups having Examples of such a heterocyclic group include a 2-furyl group, a 2-thienyl group, a 2-pyrrolyl group, a 2-pyridyl group, a 2-indole group, and a benzoimidazolyl group.
  • alkoxy group having 1 to 10 carbon atoms a group in which an oxygen atom is bonded to the aforementioned alkyl group having 1 to 10 carbon atoms can be mentioned.
  • alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentyloxy and the like.
  • alkylthio group having 1 to 10 carbon atoms examples include a group having a sulfur atom bonded to the alkyl group having 1 to 10 carbon atoms.
  • alkylthio group examples include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, a butylthio group, and a pentylthio group.
  • the sulfur atom in these alkylthio groups may be sulfinyl (—SO—) or sulfonyl (—SO 2 —).
  • alkylcarbonyl group having 1 to 10 carbon atoms examples include those in which a carbonyl group (—CO— group) is bonded to the aforementioned alkyl group having 1 to 10 carbon atoms.
  • Examples of such an alkylcarbonyl group include a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an isopropylcarbonyl group, and the like.
  • alkoxycarbonyl group having 1 to 10 carbon atoms there may be mentioned those in which an oxycarbonyl group (—O—CO— group) is bonded to the aforementioned alkyl group having 1 to 10 carbon atoms.
  • alkoxycarbonyl group examples include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, and an isopropoxycarbonyl group.
  • alkylcarbonyloxy group having 1 to 10 carbon atoms examples include those in which a carbonyloxy group (—CO—O— group) is bonded to the aforementioned alkyl group having 1 to 10 carbon atoms.
  • Examples of such an alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, and the like.
  • the “substituent” in the various groups in the present invention is not particularly limited.
  • a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted amino group an alkylsilyl group, a carbon number 1-10 alkyl group, alkenyl group having 2-10 carbon atoms, alicyclic hydrocarbon group having 3-10 carbon atoms, aryl group having 6-30 carbon atoms, arylalkyl group having 7-30 carbon atoms, heteroaryl Group, an alkylcarbonyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon-carbonyl group having 3 to 16 carbon atoms, an arylcarbonyl group having 6 to 30 carbon atoms, an arylalkylcarbonyl group having 7 to 30 carbon atoms, a carbon number
  • the “monoalkyl-substituted amino group” in the present invention is an amino group in which one hydrogen atom in the amino group (—NH 2 ) is substituted with the aforementioned alkyl group having 1 to 10 carbon atoms. Examples thereof include a methylamino group and an ethylamino group.
  • the “dialkyl-substituted amino group” in the present invention is an amino group in which two hydrogen atoms in the amino group (—NH 2 ) are each substituted with the above-described alkyl group having 1 to 10 carbon atoms. Examples thereof include a dimethylamino group, a diethylamino group, and a methylethylamino group.
  • the “formyl group” in the present invention is an aldehyde group (—CHO).
  • Examples of the “halogen atom” in the present invention include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • the “trialkylsilyl group” in the present invention is a silyl group in which three alkyl groups having 1 to 5 carbon atoms are substituted, and each alkyl group may be the same or different.
  • Examples of such a trialkylsilyl group include a triethylsilyl group, an ethyldimethylsilyl group, a tert-butyldimethylsilyl group, and a tert-butyldiethylsilyl group.
  • linker group composed of a divalent atomic group composed of atoms means an atom other than 1 to 5 hydrogen atoms selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a carbon atom, and a silicon atom, and It is a group composed of a divalent atomic group composed of hydrogen atoms, and is a group that links a triptycene skeleton and a divalent hydrocarbon group R 1 group, and its structure is not particularly limited.
  • Preferred groups X include, for example, —O—; —S—; —SO—; —SO 2 —; —NR 6 — (wherein R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). represents); -.
  • —NR 62 CO— (wherein R 62 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms) and the like, and particularly preferred X is —O—; —NR 6 — (wherein R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms); —CH 2 —; —CO— and the like.
  • the “group capable of binding or adsorbing to the surface of a solid substrate” in the terminal group Z of the general formula [I] of the present invention means a functional group capable of binding or adsorbing to the substrate surface such as glass, metal, metal oxide, etc. Examples thereof include trimethoxysilyl groups and trichlorosilyl groups for glass substrates, and groups containing sulfur atoms such as mercapto groups and disulfide groups for gold and the like.
  • terminal group consisting of a monovalent atomic group composed of is a monovalent group that is a terminal of the divalent hydrocarbon group R 1 group in the general formula [I] of the present invention, and includes 1 to 15 There is no particular limitation as long as it is a monovalent atomic group composed of preferably 1 to 10, more preferably 1 to 6 atoms and hydrogen atoms.
  • Preferred examples of the group Z include, for example, an alkyl group having 1 to 10 carbon atoms; a linear or branched alkenyl group having 2 to 15, preferably 2 to 10, more preferably 2 to 6 carbon atoms; A linear or branched alkynyl group of 15, preferably 2 to 10, more preferably 2 to 6; monocyclic, polycyclic, 6 to 15, preferably 6 to 12, more preferably 6 to 10 carbon atoms; Or a divalent aryl group having a total carbon number of 6 to 15, preferably 6 to 12, containing a condensed cyclic aryl ring (the aryl group is an alkylene group or an alkenylene between or at the end of the aryl rings) Or an alkynylene group.); A haloalkyl having 1 to 10 carbon atoms in which any position of the alkyl group having 1 to 10 carbon atoms is substituted with 1 to 7 halogen atoms ; (Wherein, R 11 represents a hydrogen atom, or an al
  • COO-R 13 (wherein, R 13 is a hydrogen atom, an alkyl group, or an aryl group having a carbon number of 6 12 1 to 10 carbon atoms the expressed); -.
  • OCOO-R 14 (wherein, R 14 represents an alkyl group, or an aryl group having 6 to 12 carbon atoms of 1 to 10 carbons); -.
  • each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms); —NR 13 CO—R 13 (where R 13 represents Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.); —N (R 13 ) CON (R 13 ) 2 (where R 13 represents Each independently a hydrogen atom, carbon An alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms is represented.
  • SiR 9 R 10 -N (R 13) 2 where , R 9 and R 10 may each independently be substituted with a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.
  • R 13 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms); —NH—SiR 9 R 10 —O—R 13 (wherein R 9 and R 10 are each independently an amino group optionally substituted with a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. represents a group, R 13 is a hydrogen atom, a carbon 1 to 10 alkyl group, or a C 6 represents the 12 aryl group); -.
  • R 15 are each independently a hydrogen atom, a carbon number of 1 to 10 Represents an alkyl group or an aryl group having 6 to 12 carbon atoms; and —P ( ⁇ O) (OR 15 ) 2 (wherein R 15 each independently represents a hydrogen atom, a carbon atom having 1 to 10 carbon atoms). Represents an alkyl group or an aryl group having 6 to 12 carbon atoms.);
  • the “janus type triptycene derivative” of the general formula [I] of the present invention has two different planes of the 1,8,13 position and the 4,5,16 position of the triptycene, These are triptycene derivatives having different characteristics.
  • Non-Patent Document 3 a triptycene derivative is produced using a Diels-Alder reaction using benzoquinone as a key reaction. In this method, the same substituent (—OH) is present at the 13-position and the 16-position. It is difficult to produce the “Janus type triptycene derivative” of the present invention introduced at the same time.
  • the inventors condense a compound in which the phenolic hydroxyl group of 1-alkoxy-6-trialkylsilyl-phenol is a leaving group such as a triflate group and 1,8-dialkoxyanthracene in the presence of a condensing agent.
  • a trisubstituted triptycene derivative was successfully produced.
  • a specific example of this reaction is shown in Example 1 described later. By this method, a 3-substituted triptycene derivative was able to be produced.
  • triptycene derivative was a 1,8,13-3 substituted triptycene derivative (Janus type) and a 1,8,16-3 substituted Although it was a mixture of triptycene derivatives (non-Janus type) and it was difficult to separate them, 1,8,13-trimethoxytriptycene was separated and purified by recrystallization and purification. Succeeded. See Example 1 below.
  • 1,8,13-Trimethoxytriptycene could be separated and purified as a crystal having a unique packing structure in which benzene rings arranged in triplicate at the triptycene site were nested.
  • the crystal structure of 1,8,13-trimethoxytriptycene is shown in FIG. In FIG. 2, the oxygen atom of the methoxy group is shown in red.
  • This crystal structure is an integrated structure in which dipoles are offset by a layer of triptycene molecules with the methoxy group facing the back side of the paper and a layer of molecules facing the front side of the paper. Surprisingly, such a nested crystal structure is not seen in unsubstituted triptycene.
  • the 1,8,13-trimethoxytriptycene thus separated and purified can be hydrolyzed to 1,8,13-trihydroxytriptycene by a conventional method. For example, it can be hydrolyzed in the presence of boron halide in a solvent such as dichloromethane. Then, 1,8,13-trimethoxytriptycene and 1,8,13-trihydroxytriptycene obtained by hydrolysis thereof are used as key intermediates by various known synthetic means, and the present invention.
  • the "Janus type triptycene derivative" and its intermediate compound can be produced. For example, a trialkoxy derivative can be obtained by alkylating with an alkylating agent.
  • 1,8,13-tricyanotriptycene can be obtained by changing the hydroxyl group to triflate (Tf: trifluoromethanesulfonate) and then cyanating with dicyanozinc.
  • the cyano group can be hydrolyzed to formyl group or carboxyl group by an ordinary method. Further, by reducing the cyano group by a usual method, it can be converted to an aminomethyl group, and the amino group can be substituted with various substituents by a usual method.
  • the obtained formyl group can be used as various reaction raw materials as a carbonyl compound. For example, the formyl group can be reacted with a Wittig reagent to form a —CH ⁇ C— bond. This can be converted to a carbon-carbon triple bond by dehydrogenation by an ordinary method.
  • 1,5,16-tribromo-1,8,13-trihydroxytriptycene is obtained by brominating 1,8,13-trihydroxytriptycene using NBS (N-bromosuccinimide).
  • NBS N-bromosuccinimide
  • This compound is a compound having different substituents, ie, three hydroxy groups on one side and three bromo groups on the other side with respect to one symmetry plane in the triptycene molecule, and different with respect to one symmetry plane.
  • This compound is a key intermediate of the “Janus type triptycene derivative” of the present invention having a functional group.
  • This bromo compound can be directly converted into various aryl groups and heteroaryl groups such as phenyl and thienyl groups by various coupling reactions using boron compounds and silicon compounds.
  • a functional group serving as an electron acceptor is to be introduced on the side where the bromo group is substituted, the functional group can be introduced directly or stepwise by such a coupling reaction.
  • a triphenylamine unit which is an electron donor fluorescent dye, was introduced into triptycene via a phenylene vinylene moiety as a photo / electronic functional unit.
  • DMF Specifically, a t BuOK as base, by mixing the Janus type triptycene 2 and phosphonate 3 having a formyl group to give compound 4 which dye moiety was introduced 3 groups with 11% yield. This chemical reaction formula is shown below.
  • Compound 4 showed an absorption band having a maximum at 385 nm in dichloromethane. When fluorescence spectrum measurement was performed using this as an excitation wavelength, strong emission was observed at 486 nm. In Compound 4, it was shown that the absorption / fluorescence characteristics of the dye portion were not impaired even though the dye was integrated at a high density. As described above, a functional group having optical characteristics and electronic characteristics can be introduced into one surface of the Janus-type triptycene derivative of the present invention by ordinary synthesis means.
  • the compound represented by the general formula [I] of the present invention has different substituents on the two planes of the 1,8,13 position and the 4,5,16 position of triptycene. And having three identical substituents on at least one of the surfaces.
  • a unique film structure can be formed by forming a unique packing structure in which such specific triptycene derivatives are formed by nesting benzene rings arranged in triplicate at the triptycene site. Is.
  • we succeeded in separating and purifying the triptycene derivative having such a specific structure by being able to crystallize 1,8,13-trimethoxytriptycene, and using it as a key intermediate It has been found that it can be manufactured.
  • Z can be a cyano group compound, and the resulting product can be hydrolyzed to a carboxyl group.
  • Z is an ester group
  • the ester may be reacted as it is, or may be esterified after being converted to a carboxyl group.
  • the protecting group and deprotection are well known to those skilled in the art, but if necessary, refer to Protective Group in Organic Synthesis (John Wiley and Sons, 1991) by TW Green.
  • the triptycene substituent is a compound having a carbonyl group such as a formyl group
  • the general formula in which the group X is —C ⁇ C— can be obtained by using the Wittig reagent described above [ I].
  • 1,8,13-trihydroxytriptycene is used as a raw material, and methyl 12-bromododecanoate (a chloro, iodo, or a pseudohalide such as tosylate instead of bromo)
  • methyl 12-bromododecanoate a chloro, iodo, or a pseudohalide such as tosylate instead of bromo
  • Compound 1 having the above-mentioned ester group as a terminal group can be produced by reacting with a compound in the presence of a base.
  • a solvent can be used as necessary.
  • solvents include ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as diethyl ether and THF, aprotic polar solvents such as DMF, DMA and DMSO, alcohol solvents such as ethanol, toluene, Aromatic hydrocarbon solvents such as xylene, halogen solvents such as dichloromethane and chlorobenzene, and the like are exemplified, but not limited thereto.
  • the reaction can be performed in the presence of various reagents as necessary.
  • Such a reagent is preferably a base, and examples of the base include alkali metal carbonates such as potassium carbonate, sodium carbonate and cesium carbonate, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. It is not limited to these.
  • An organic base such as trialkylamine can be used as the base, but an inorganic base is preferred.
  • the reaction temperature can be arbitrarily set as long as the reaction proceeds appropriately. Usually, the range from room temperature to the boiling point of the solvent is preferable.
  • the target product As a method for isolating and purifying the target product from the reaction mixture, it may be carried out by usual isolation / purification means such as solvent extraction, recrystallization, reprecipitation, silica gel column chromatography, gel filtration chromatography, etc. Can do.
  • isolation / purification means such as solvent extraction, recrystallization, reprecipitation, silica gel column chromatography, gel filtration chromatography, etc. Can do.
  • the product when it has optical activity, it can be optically resolved as required.
  • the benzene rings arranged in triplicate in the form of three nesting rings accumulate in a nested manner, and this characteristic integration behavior is utilized.
  • a two-dimensional molecular assembly with controlled dimensionality can be reasonably constructed and a film can be formed.
  • a spin coating method, a dipping method, a casting method, an ink jet method, an ultrasonic method, a gas phase method, a vapor deposition method and the like can be arbitrarily selected.
  • the spin coating method is a method in which a thin film having a uniform film thickness is formed by dropping a solution on a substrate that rotates at high speed.
  • the dipping method is a method of forming a film by dipping a substrate in a solution.
  • the cast method (including the drop cast method) is a method in which a solution is dropped on a substrate and then the solvent is dried to form a film, but the film thickness is not necessarily uniform.
  • the ink jet method is a method of forming a film by dropping a minute solution at an arbitrary position.
  • the film of the present invention exhibits a specific integration behavior, it depends on the liquid / liquid interface. It can also be performed by a film forming method. For example, a solution obtained by dissolving the compound of the present invention in an organic solvent insoluble in water can be brought into contact with water to form a water / organic solvent interface, and a film can be produced at the interface. Further, some of the compounds represented by the general formula [I] of the present invention can form a film by a vapor deposition method, preferably a vacuum vapor deposition method. In particular, a compound having a relatively low melting point and a high decomposition temperature is preferred.
  • the vapor deposition method in this invention can be performed by the normal vapor deposition method.
  • the compound is preferably heated to a melting point or higher to evaporate, or when the compound is sublimable, it is preferably sublimated and carried out under a reduced pressure of 10 ⁇ 5 Pa to 10 ⁇ 3 Pa.
  • the temperature of the substrate may be around room temperature, but is preferably about 50 ° C. to 100 ° C.
  • the compound of the present invention suitable for forming a film by a vapor deposition method in general formula [I], X is —CH 2 —, Z is a hydrogen atom, and R 1 is an alkylene group having 8 to 15 carbon atoms, preferably Is a compound having an alkylene group of 9 to 12 carbon atoms.
  • the above-described solid substrate of the present invention can be used. Furthermore, these solid substrates have been subjected to cleaning treatment with ultraviolet rays (UV), ozone, etc .; on these solid substrates, there are other connection terminals such as wiring and electrodes, insulation layers, conductive layers, etc. A laminate in which these layers are stacked can also be used as a solid substrate.
  • a glass substrate or an organic substrate is preferable, and a substrate subjected to a cleaning treatment is particularly preferable.
  • a step of dissolving a Janus type triptycene derivative represented by the general formula [I] of the present invention in an organic solvent to form a solution and then applying or spinning the solution.
  • the method include a step of immersing a solid substrate in a coating or the solution, and a step of drying the solution on the solid substrate.
  • a Janus type triptycene derivative represented by the general formula [I] of the present invention is dissolved in an organic solvent that does not intersect with a second solvent such as water to obtain a solution.
  • the film thickness of the film of the present invention produced by such a method is not particularly limited, but the average thickness in the case of a monomolecular film is 0.1 nm to 5 nm, preferably 1 nm to 3 nm. Is preferred. In the case of a multilayer film, the average thickness is 2 nm to 50 nm or less, preferably 3 nm to 30 nm. Further, when the film is manufactured at the liquid / liquid interface, a film having a larger film thickness can be manufactured, and the film thickness can be 30 nm to 1000 nm, preferably 50 nm to 500 nm.
  • the organic solvent for producing the film is not particularly limited as long as it can dissolve the Janus type triptycene derivative represented by the general formula [I] of the present invention.
  • a lactone such as ⁇ -butyrolactone is used.
  • Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone; monohydric alcohols such as methanol, ethanol, isopropanol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc.
  • glycol esters such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate; Monoether or monoether esters of polyhydric alcohols or the above-mentioned esters such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate Esters such as methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether, ethyl benzene, diethyl benzen
  • organic solvents may be used independently and may be used as 2 or more types of mixed solvents.
  • Preferred organic solvents include amides such as dimethylformamide (DMF) and dimethylacetamide (DMA), cyclic ethers such as dioxane and THF, and sulfur-containing solvents such as dimethylsulfoxide (DMSO).
  • Particularly preferred solvents include polar solvents such as dimethylformamide (DMF) and tetrahydrofuran (THF).
  • the Janus type triptycene derivative represented by the general formula [I] of the present invention in 100 mL of an organic solvent is 0.01 mg to 1000 mg, more preferably 0.1 mg to 100 mg, still more preferably 0.1 mg. It can be 10 mg.
  • the temperature at which the membrane of the present invention is produced can be usually room temperature, but depending on the type of solvent and production conditions, it can be carried out under heating or cooling.
  • Drying in the production of the membrane of the present invention is sufficient by natural drying, but it can be dried by a method such as blowing dry air or nitrogen, or by heating if necessary.
  • the film manufactured using an organic solvent such as methanol or chloroform, purified water, or the like may be washed, but it is not particularly necessary to wash the film.
  • the film of the present invention is produced at the interface, the film produced at the interface can be transferred to a substrate such as a glass substrate and separated. The separated membrane can be dried by the method described above.
  • the film of the present invention thus produced can be further annealed.
  • the annealing treatment is performed at a temperature almost the same as the melting point of the Janus type triptycene derivative represented by the general formula [I] of the present invention, preferably It is carried out by heating to about 100 ° C. to 230 ° C., more preferably about 130 ° C. to 230 ° C., and further preferably 150 ° C. to 200 ° C.
  • the film produced by the vapor deposition method is performed by heating to about 100 ° C. to 200 ° C., preferably about 110 ° C. to 150 ° C.
  • the annealing treatment can be usually performed in the atmosphere, but may be performed in an inert air flow such as a nitrogen air flow.
  • the annealing time is not particularly limited, but usually 5 to 50 minutes, preferably 10 to 30 minutes is sufficient. Although the details of the mechanism by the annealing treatment are unknown, it is considered that the film once formed by the annealing is reconstructed to obtain a more uniform film thickness.
  • the film of the present invention can have a single layer structure or a bilayer structure in which the end groups Z face each other depending on the type of the end groups Z in the general formula [I]. Also, the thickness of the film can be adjusted by the manufacturing method, and it is suitable for a wide range of applications as a thin film suitable for a wide range of applications as an electronic material, an optical material, a surface treatment material, or a structure integrated with a solid substrate. A structure can be provided.
  • Trimethoxytriptycene was produced according to the following reaction formula.
  • Acetonitrile 750 mL was added to 1,8-dimethoxyanthracene (22.3 g, 93.7 mmol) and cesium fluoride (CsF) (85.3 mg, 561.0 mmol) to form a suspension and heated to 80 ° C.
  • CsF cesium fluoride
  • 2-methoxy-6-trimethylsilyloxy-trifluoromethylsulfonate (61.5 g, 188 mmol) was added dropwise and heated to reflux for 5 hours.
  • trimethoxytriptycene was composed of 2,8,13-trimethoxytriptycene (compound 5a) and 1,8,16-trimethoxytriptycene (compound 5b). 1 mixture.
  • the trimethoxytriptycene mixture (10.0 mg) prepared in Example 1 was dissolved in chloroform and crystallized by standing to give the title 1,8,13-trimethoxytriptycene (2 0.0 mg) was obtained.
  • this crystal is orthorhombic (system), and the values of a, b, and c of the unit cell are each in angstrom units, 15.608, 13.388, and 8.041.
  • the value of V was 1680 cubic angstroms.
  • the structure of the obtained crystal is shown as a schematic diagram in FIG.
  • 1,8,13-Tris (methoxymethoxy) -4,5,16-tribromotriptycene (Compound 8) (10.0 mg, 0.015 mmol) prepared in Example 5 was added to 2.0 mL of THF and water 1 Dissolved in 0.0 mL, to which (2 ′, 6′-dimethoxy-1,1′-biphenylyl) dicyclohexylphosphine (SPos) (6.49 mg, 0.016 mmol) and palladium acetate (Pd (OAc) 2 ) (20 0.7 mg, 0.098 mmol) was added, and the mixture was stirred at 60 ° C.
  • SPos (2 ′, 6′-dimethoxy-1,1′-biphenylyl) dicyclohexylphosphine
  • SPos (2 ′, 6′-dimethoxy-1,1′-biphenylyl) dicyclohexylphosphine
  • thienyl boric acid (thienyl B (OH) 2 ) (11.5 mg, 0.090 mmol) was gradually added dropwise thereto, and the mixture was reacted at 60 ° C. for 14 hours.
  • 30 mL of chloroform was added to the reaction mixture, and after washing with water, the organic layer was dried over magnesium sulfate and filtered, and then distilled off under reduced pressure.
  • the residue was subjected to silica gel column chromatography using chloroform as a solvent to obtain the title 1,8,13-tris (methoxymethoxy) -4,5,16-trithienyltriptycene (compound 16) ( Yield 5.2 mg, 51% yield).
  • the title compound 17 was produced in the same manner as in Example 14 using tertenylboric acid instead of thienylboric acid in Example 14 (yield 12%).
  • the powder of Compound 1 was annealed at 240 ° C. and cooled to 25 ° C. to produce an aggregate structure of Compound 1.
  • the produced aggregate structure of Compound 1 is formed by a powder X-ray diffraction measurement to form a lamellar accumulation structure composed of a layer in which three benzene rings are nested and a layer of a long-chain alkyl group. (See FIG. 3).
  • An interlayer distance of about 2.4 nm is observed by powder X-ray diffraction measurement, which is consistent with the long-axis direction distance of molecule 1.
  • the above results show that functional groups and functional groups can be integrated in a layered manner at high density by using the assembly behavior of the present Janus molecule.
  • Example 30 the compound 21 produced in Example 20 was vacuum deposited on a quartz substrate, a mica substrate, a polyimide substrate, and a PET substrate, respectively. Each film pressure obtained was 50 nm. The molecular orientation in each of the obtained films was measured by GIXD in the same manner as in Example 30, and as a result, it was found that the films were regularly oriented molecular films having a d110 interval of about 0.41 nm.
  • Example 30 In the same manner as in Example 30, compound 21 produced in Example 20, compound 22 produced in Example 21, compound 23 produced in Example 22 and compound 24 produced in Example 23 were applied to a sapphire substrate. Each was vacuum deposited. The film thicknesses obtained were 50 nm each. When the vapor deposition film produced using Compound 23 was measured by attenuated total reflection infrared absorption spectrum (ATR-IR), the characteristic absorption of the carbon-carbon triple bond could be confirmed.
  • ATR-IR attenuated total reflection infrared absorption spectrum
  • a toluene solution of compound 21 (200 ⁇ M, 50 ⁇ L) was spin-coated on a silicon substrate at 2300 rpm.
  • the monomolecular film was formed by setting the coating amount to an amount conceivable for the formation of the monomolecular film. This was naturally dried, and the resulting film was measured with an atomic force microscope (AFM). As a result, the film thickness was about 1.9 nm. When this was annealed at 150 ° C. for 1 hour, a very flat film could be obtained. Similar results were obtained when annealing was performed with toluene vapor at 80 ° C. for 1 hour.
  • a transistor using a film produced using Compound 1 was produced.
  • An Al 2 O 3 / Al gate electrode was manufactured by patterning with aluminum on a silicon wafer and oxidizing the surface with plasma.
  • a solution of the compound 1 of the present invention was drop-cast and annealed at 200 ° C. to produce a monomolecular film (SAM).
  • DNTT Diinaphthothienothiophene
  • the obtained transistor has a capacitance (capacitance) of 644 nF / cm 2 , an electron mobility (mobility) of 0.387 cm 2 / Vs, an on / off ratio of 7.32 ⁇ 10 6 , and a threshold voltage of It was ⁇ 0.487 V, and the leakage current was 9.44 ⁇ 10 ⁇ 11 A.
  • the present invention can have extremely unique characteristics different from those of conventional self-assembled films, and can be applied not only as a thin film for electronic devices such as thin film transistors but also as a protective film or a biological film-like film.
  • the present invention provides a nano-unit thin film having a wide range, a triptycene derivative useful as a novel film-forming material for forming the film, and an intermediate compound for producing the derivative. Therefore, the present invention is useful in the industrial field using thin films such as thin film transistors, and has industrial applicability not only in the chemical industry but also in the electronic device industry.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Thin Film Transistor (AREA)
  • Indole Compounds (AREA)

Abstract

La présente invention concerne : un dérivé de triptycène de type Janus représenté par la formule générale [I] et qui est utilisé comme matériau pour un film monomoléculaire auto-assemblé; un dérivé de triptycène de type Janus qui est représenté par la formule générale [II] et qui peut être utilisé comme matière première dans la production du dérivé susmentionné, ainsi que des procédés respectifs pour produire les dérivés. La présente invention concerne également un matériau filmogène contenant un dérivé de triptycène de type Janus, un film auto-assemblé produit à l'aide du matériau, un substrat solide sur la surface duquel est formé le film, et un procédé de production du film. (Dans les formules, X représente un groupe de liaison comme un atome d'oxygène; R1 représente un groupe à chaîne longue; Z représente un atome d'hydrogène ou l'un des divers groupes fonctionnels situés à l'extrémité; et R2 représente un atome d'hydrogène ou l'un de divers substituants.)
PCT/JP2013/004952 2013-01-16 2013-08-21 Dérivé de triptycène utilisé comme matériau pour former un film auto-assemblé, procédé de production dudit dérivé, film produit à l'aide dudit dérivé et procédé de production dudit film WO2014111980A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014557181A JP6219314B2 (ja) 2013-01-16 2013-08-21 自己組織化膜形成材料として有用なトリプチセン誘導体、その製造方法、それを用いた膜、及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-005126 2013-01-16
JP2013005126 2013-01-16

Publications (1)

Publication Number Publication Date
WO2014111980A1 true WO2014111980A1 (fr) 2014-07-24

Family

ID=51209112

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/004952 WO2014111980A1 (fr) 2013-01-16 2013-08-21 Dérivé de triptycène utilisé comme matériau pour former un film auto-assemblé, procédé de production dudit dérivé, film produit à l'aide dudit dérivé et procédé de production dudit film

Country Status (2)

Country Link
JP (1) JP6219314B2 (fr)
WO (1) WO2014111980A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104529716A (zh) * 2014-12-23 2015-04-22 重庆大学 1,1’,1”-三羟基三蝶烯及其合成方法
WO2016010061A1 (fr) * 2014-07-15 2016-01-21 国立研究開発法人科学技術振興機構 Dérivé de triptycène utile en tant que matériau pour la formation d'un film autoassemblé, procédé de préparation dudit dérivé de triptycène, film l'utilisant, procédé de production dudit film et dispositif électronique utilisant ledit procédé
EP2958148A4 (fr) * 2013-02-12 2016-09-07 Japan Science & Tech Agency Dispositif électronique mettant en uvre un film mince organique, et appareil électronique comprenant celui-ci
JP2018046279A (ja) * 2016-09-13 2018-03-22 東京エレクトロン株式会社 セルフアセンブル単層表面前処理を用いた選択的金属酸化物堆積
CN109929117A (zh) * 2019-01-15 2019-06-25 浙江大学宁波理工学院 一种磷氮型刚性骨架多孔阻燃剂及其制备方法和应用
WO2019167704A1 (fr) * 2018-02-28 2019-09-06 Jsr株式会社 Méthode de modification de surface de substrat, composition et polymère
JP2020188047A (ja) * 2019-05-10 2020-11-19 コニカミノルタ株式会社 バリアー膜、バリアー膜の作製方法、バリアー膜積層体及び電子デバイス
JP2020186281A (ja) * 2019-05-10 2020-11-19 コニカミノルタ株式会社 塗膜、塗膜積層体、塗膜積層体の作製方法及び電子デバイス
WO2021060042A1 (fr) * 2019-09-25 2021-04-01 富士フイルム株式会社 Composé, composition, film, corps structural et dispositif électronique
CN113881004A (zh) * 2021-09-30 2022-01-04 浙江工业大学 具有stp拓扑网络结构的三维金属卟啉基共价有机框架材料及其制备方法与应用
WO2023210378A1 (fr) * 2022-04-28 2023-11-02 Ａｇｃ株式会社 Composé, composition, agent de traitement de surface, procédé de fabrication d'article et article
CN117069919A (zh) * 2023-08-17 2023-11-17 湖北大学 基于五蝶烯醌的血液净化用有机多孔吸附材料及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117597768A (zh) 2021-07-09 2024-02-23 东京毅力科创株式会社 图案形成方法和等离子体处理方法

Non-Patent Citations (17)

* Cited by examiner, † Cited by third party
Title
ADAM J. WOLPAW ET AL.: "Synthesis of self- orienting triptycene adsorbates for STM investigations", TETRAHEDRON LETTERS, vol. 44, no. 41, 2003, pages 7613 - 7615 *
AKITO NISHINAKA ET AL.: "Janus-gata Triptycene o Platform to suru Denshi Oyobi Hikari Kassei Kinodan no Ko Mitsudo Shusekika", DAI 23 KAI SYMPOSIUM ON PHYSICAL ORGANIC CHEMISTRY POSTER BUNSHO, 19 September 2012 (2012-09-19) *
AKITO NISHINAKA ET AL.: "Janus-gata Triptycene o Platform to suru Denshi Oyobi Hikari Kassei Kinodan no Ko Mitsudo Shusekika", DAI 23 KAI SYMPOSIUM ON PHYSICAL ORGANIC CHEMISTRY YOSHISHU, 5 September 2012 (2012-09-05), pages 216 *
DANIEL ORRIN HUTCHINS ET AL.: "Effects of self- assembled monolayer structural order, surface homogeneity and surface energy on pentacene morphology and thin film transistor device performance", JOURNAL OF MATERIALS CHEMISTRY C: MATERIALS FOR OPTICAL AND ELECTRONIC DEVICES, vol. 1, no. 1, 2013, pages 101 - 113 *
GLEN A. RUSSE LL ET AL.: "Radical Anions of Triptycene Bis- and Tris (quinones)", J. AM. CHEM. SOC., vol. 103, no. 6, 1981, pages 1560 - 1561 *
HELMUT QUAST ET AL.: "ESR-spektroskopischer Nachweis intramolekularer Wechselwirkungen in Radikalkationen von Poly(a-methoxy)triptycenen", CHEMISCHE BERICHTE, vol. 119, no. 3, 1986, pages 1016 - 1038 *
JINXUAN LIU ET AL.: "Deposition of Metal-Organic Frameworks by Liquid-Phase Epitaxy: The Influence of Substrate Functional Group Density on Film Orientation", MATERIALS, vol. 5, 2012, pages 1581 - 1592 *
MARKETA RYBACKOVA ET AL.: "Synthesis of Highly Symmetrical Triptycene Tetra- and Hexacarboxylates", SYNTHESIS, vol. 10, 2007, pages 1554 - 1558 *
MIRIAM E. ROGERS ET AL.: "Symmetrically Trisubstituted Triptycenes", J. ORG. CHEM., vol. 51, no. 17, 1986, pages 3308 - 3314 *
NORIYA SHIMIZU ET AL.: "Nijigen Bunshi Shusekitai no Kochiku e Muketa Janus-gata Triptycene Yudotai no Design", DAI 23 KAI SYMPOSIUM ON PHYSICAL ORGANIC CHEMISTRY POSTER BUNSHO, 19 September 2012 (2012-09-19) *
NORIYA SHIMIZU ET AL.: "Nijigen Bunshi Shusekitai no Kochiku e Muketa Janus-gata Triptycene Yudotai no Design", DAI 23 KAI SYMPOSIUM ON PHYSICAL ORGANIC CHEMISTRY YOSHISHU, 5 September 2012 (2012-09-05) *
NORIYA SHIMIZU ET AL.: "Nijigen Bunshi Shusekitai no Kochiku e Muketa Janus-gata Triptycene Yudotai no Kaihatsu", CSJ: THE CHEMICAL SOCIETY OF JAPAN SHUKI JIGYO, DAI 2 KAI CSJ KAGAKU FESTA 2012 POSTER BUNSHO, 16 October 2012 (2012-10-16) *
NORIYA SHIMIZU ET AL.: "Nijigen Bunshi Shusekitai no Kochiku e Muketa Janus-gata Triptycene Yudotai no Kaihatsu", CSJ: THE CHEMICAL SOCIETY OF JAPAN SHUKI JIGYO, DAI 2 KAI CSJ KAGAKU FESTA 2012 PROGRAM · KOEN YOKOSHU, 26 September 2012 (2012-09-26), pages 266 *
TAKANORI FUKUSHIMA ET AL.: "Nijigen Shusekikano o Yusuru Bunshi Building Block no Kaihatsu", FUCHI KENKYUSHO-KAN ALLIANCE 'JISEDAI ELECTRONICS' GROUP (G1) BUNKAKAI (YAMAGATA UNIVERSITY JOINT SYMOPSIUM, 5 August 2013 (2013-08-05), pages 32 *
YOSHIAKI SHOJI ET AL.: "Janus-gata Triptycene: Kinodan no Seimitsu katsu Ko Mitsudo Shusekika o Kano ni suru Han'yosei Bunshi Platform no Kaihatsu", DAI 23 KAI SYMPOSIUM ON PHYSICAL ORGANIC CHEMISTRY KOTO HAPPYO BUNSHO, 19 September 2012 (2012-09-19) *
YOSHIAKI SHOJI ET AL.: "Janus-gata Triptycene: Kinodan no Seimitsu katsu Ko Mitsudo Shusekika o Kano ni suru Han'yosei Bunshi Platform no Kaihatsu", DAI 23 KAI SYMPOSIUM ON PHYSICAL ORGANIC CHEMISTRY YOSHISHU, 5 September 2012 (2012-09-05), pages 30 - 31 *
YOSHIAKI SHOJI ET AL.: "Nijigen Shusekika ni yoru Centimeter Scale no Tankesshojo Bunshi Usumaku no Keisei", FUCHI KENKYUSHO-KAN ALLIANCE 'JISEDAI ELECTRONICS' GROUP (G1) BUNKAKAI (YAMAGATA UNIVERSITY JOINT SYMPOSIUM, 5 August 2013 (2013-08-05), pages 78 *

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2014125527A1 (ja) * 2013-02-12 2017-02-02 国立研究開発法人科学技術振興機構 有機薄膜を用いた電子デバイス、及びそれを含有してなる電子機器
US9825232B2 (en) 2013-02-12 2017-11-21 Japan Science And Technology Agency Electronic device using organic thin film, and electronic apparatus containing the same
EP2958148A4 (fr) * 2013-02-12 2016-09-07 Japan Science & Tech Agency Dispositif électronique mettant en uvre un film mince organique, et appareil électronique comprenant celui-ci
US10305052B2 (en) 2014-07-15 2019-05-28 Japan Science And Technology Agency Triptycene derivative useful as material for forming self-assembled film, method for manufacturing said triptycene derivative, film using same, method for manufacturing said film, and electronic device using said method
WO2016010061A1 (fr) * 2014-07-15 2016-01-21 国立研究開発法人科学技術振興機構 Dérivé de triptycène utile en tant que matériau pour la formation d'un film autoassemblé, procédé de préparation dudit dérivé de triptycène, film l'utilisant, procédé de production dudit film et dispositif électronique utilisant ledit procédé
CN104529716A (zh) * 2014-12-23 2015-04-22 重庆大学 1,1’,1”-三羟基三蝶烯及其合成方法
JP2018046279A (ja) * 2016-09-13 2018-03-22 東京エレクトロン株式会社 セルフアセンブル単層表面前処理を用いた選択的金属酸化物堆積
WO2019167704A1 (fr) * 2018-02-28 2019-09-06 Jsr株式会社 Méthode de modification de surface de substrat, composition et polymère
JP7136182B2 (ja) 2018-02-28 2022-09-13 Jsr株式会社 基材表面の修飾方法、組成物及び重合体
JPWO2019167704A1 (ja) * 2018-02-28 2021-03-04 Jsr株式会社 基材表面の修飾方法、組成物及び重合体
US11426761B2 (en) 2018-02-28 2022-08-30 Jsr Corporation Modification method of surface of base, composition, and polymer
CN109929117B (zh) * 2019-01-15 2021-04-30 浙江大学宁波理工学院 一种磷氮型刚性骨架多孔阻燃剂及其制备方法和应用
CN109929117A (zh) * 2019-01-15 2019-06-25 浙江大学宁波理工学院 一种磷氮型刚性骨架多孔阻燃剂及其制备方法和应用
JP2020186281A (ja) * 2019-05-10 2020-11-19 コニカミノルタ株式会社 塗膜、塗膜積層体、塗膜積層体の作製方法及び電子デバイス
JP2020188047A (ja) * 2019-05-10 2020-11-19 コニカミノルタ株式会社 バリアー膜、バリアー膜の作製方法、バリアー膜積層体及び電子デバイス
JP7230675B2 (ja) 2019-05-10 2023-03-01 コニカミノルタ株式会社 バリアー膜、バリアー膜の作製方法、バリアー膜積層体及び電子デバイス
JPWO2021060042A1 (fr) * 2019-09-25 2021-04-01
WO2021060042A1 (fr) * 2019-09-25 2021-04-01 富士フイルム株式会社 Composé, composition, film, corps structural et dispositif électronique
JP7316365B2 (ja) 2019-09-25 2023-07-27 富士フイルム株式会社 化合物、組成物、膜、構造体及び電子デバイス
CN113881004A (zh) * 2021-09-30 2022-01-04 浙江工业大学 具有stp拓扑网络结构的三维金属卟啉基共价有机框架材料及其制备方法与应用
WO2023210378A1 (fr) * 2022-04-28 2023-11-02 Ａｇｃ株式会社 Composé, composition, agent de traitement de surface, procédé de fabrication d'article et article
CN117069919A (zh) * 2023-08-17 2023-11-17 湖北大学 基于五蝶烯醌的血液净化用有机多孔吸附材料及其制备方法
CN117069919B (zh) * 2023-08-17 2024-02-09 湖北大学 基于五蝶烯醌的血液净化用有机多孔吸附材料及其制备方法

Also Published As

Publication number Publication date
JPWO2014111980A1 (ja) 2017-01-19
JP6219314B2 (ja) 2017-10-25

Similar Documents

Publication Publication Date Title
JP6219314B2 (ja) 自己組織化膜形成材料として有用なトリプチセン誘導体、その製造方法、それを用いた膜、及びその製造方法
JP6272242B2 (ja) 有機薄膜を用いた電子デバイス、及びそれを含有してなる電子機器
JP6793946B2 (ja) 自己組織化膜形成材料として有用なトリプチセン誘導体、その製造方法、それを用いた膜、当該膜の製造方法、及びそれを用いた電子デバイス
JP6080870B2 (ja) 溶液プロセス用有機半導体材料及び有機半導体デバイス
KR101410150B1 (ko) 전계 효과 트랜지스터
EP2109162B1 (fr) Composite semi-conducteur organique, materiau de transistor organique et transistor a effet de champ organique
JP5283635B2 (ja) 有機トランジスタおよびその製造方法
JP5502923B2 (ja) 二価結合を有する小分子チオフェン化合物を備える装置
TW201341375A (zh) 含硫族元素有機化合物與其製造方法、有機半導體材料、有機半導體膜及有機場效應電晶體
TWI549327B (zh) 有機場效電晶體及有機半導體材料
TW200306027A (en) Surface modified organic thin film transistors
JP5948772B2 (ja) ジチエノベンゾジチオフェン誘導体組成物及びこれを用いた有機薄膜トランジスタ
JP2006013483A (ja) 小分子チオフェン化合物を備える装置
JP5655301B2 (ja) 有機半導体材料
JP4752269B2 (ja) ポルフィリン化合物及びその製造方法、有機半導体膜、並びに半導体装置
WO2010055898A1 (fr) Semi-conducteur de type n composé d’un composé du fullerène
JP5637985B2 (ja) ジアザボロール化合物、およびそれを含有した電界効果トランジスタ
Kim et al. Soluble terthiophene-labeled cruciform molecule as a semiconductor for organic field-effect transistor
JP2009049056A (ja) ヘキサベンゾコロネンナノチューブを用いた電界効果トランジスタ
JP2021125476A (ja) ペリレン誘導体化合物、該化合物を用いた有機半導体用組成物、該有機半導体用組成物を用いた有機薄膜トランジスタ
JP4365357B2 (ja) 側鎖含有型有機シラン化合物、有機薄膜トランジスタ及びそれらの製造方法
KR100755482B1 (ko) 펜타센 전구체, 펜타센, 이들의 제조방법 및 이들을 이용한유기 박막 트랜지스터
TW202348609A (zh) 光電用墨水組合物、化合物、光電膜、及光電元件
JP2007250784A (ja) 有機薄膜及びその製造方法
JP2013170126A (ja) 含フッ素芳香族化合物およびその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13871714

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014557181

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13871714

Country of ref document: EP

Kind code of ref document: A1