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WO2003055853A1 - Composes accepteurs d'electrons pouvant former des monocouches autoassemblees - Google Patents

Composes accepteurs d'electrons pouvant former des monocouches autoassemblees Download PDF

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Publication number
WO2003055853A1
WO2003055853A1 PCT/JP2002/013590 JP0213590W WO03055853A1 WO 2003055853 A1 WO2003055853 A1 WO 2003055853A1 JP 0213590 W JP0213590 W JP 0213590W WO 03055853 A1 WO03055853 A1 WO 03055853A1
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group
compound
formula
electron
bond
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PCT/JP2002/013590
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English (en)
Japanese (ja)
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Haruo Saso
Toshiaki Satoh
Toshiaki Takahashi
Satoshi Ogawa
Noriyuki Yoshimoto
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Nippon Soda Co., Ltd.
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Priority to AU2002357515A priority Critical patent/AU2002357515A1/en
Priority to JP2003556385A priority patent/JP4272068B2/ja
Publication of WO2003055853A1 publication Critical patent/WO2003055853A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • Electron-accepting compounds that form self-assembled monolayers are Electron-accepting compounds that form self-assembled monolayers
  • the present invention relates to a compound suitable for forming a self-assembled monolayer that exhibits a charge separation function, a photoresponsive function, a complex formation function, and the like of an electron accepting molecule on a substrate.
  • J. Chem. Soc, Faraday Trans., 92, 3813, (1996) states that 2- (11-mercaptodecyl) hydroquinone is self-assembled on its surface to form a monomolecular film on a gold electrode. It is described that quinone is produced by an electrochemical oxidation reaction.
  • Japanese Patent Application Laid-Open No. 2000-26016 describes a photocharge separation material composed of a compound containing a carbon molecule on a spherical shell as an acceptor. Describes a substrate in which a compound in which an electron donor and a photosensitizer are three-dimensionally arranged forms a self-assembled monolayer.
  • Japanese Unexamined Patent Publication No. 2001-2583883 discloses that a mercapto group or an acetylthio group is bonded to a imidazolylporphyrin skeleton via a divalent linking group containing at least one of an arylene group and an alkylene group. And a mercapto-substituted imidazolyl porphyrin metal complex monomer having a mercapto group, and a polymer formed by the monomer interacting with an imidazole group and a porphyrin central metal to form a mercapto group or the like. To the electrode surface It is described that a device can be constructed that connects between them and transfers energy in nanometer units.
  • Japanese Patent Application Laid-Open No. 2001-303022 discloses that a metal formed on a substrate surface or a semiconductor surface has a general formula (a) ELB in.
  • L is an atomic group having a long chain of (CH 2 ) N — or an atomic group in which the main chain of the atomic group is separated by 0, S or N. —, 10—, or 1—CO—, and B in.
  • B in. Is a group that provides a binding group that binds compound (a) to the metal or semiconductor surface by a covalent bond or a coordinate bond.
  • the present invention has a simple structure, is easy to manufacture, has an electron-accepting function, forms a monomolecular film by self-assembly, and undergoes structural transformation to improve the denseness and orientation of the film. It is an object of the present invention to provide a compound that is easier and may have the desired performance.
  • the present inventors have conducted intensive studies on the above problems, and found that diaminomaleonitrile or a cyano group that can be synthesized using a compound having a similar diamine structure as a raw material.
  • the above problem was solved by performing various molecular conversions so that aromatic heterocycles such as virazine and imidazole, which have a substituent as a substituent, have an electron accepting function and can form a monomolecular film by self-assembly.
  • aromatic hydrocarbon ring as a magnetic anisotropic unit capable of forming a strong stacking structure in the electron-accepting partial structure, orientation control by self-organization can be expected.
  • the present inventors have found a compound that is easy to produce and has a novel structure that does not impair the electron accepting function, and has completed the present invention.
  • A is at least one selected from the group consisting of (i) a cyano group, a C1-C6 alkoxycarbonyl group, and a CI-C11 acyl group, which are bonded on a ring or via a conjugated system.
  • a group in which an aromatic heterocyclic group is bonded to an atomic group represented by Sp on a ring or via a conjugated system, or (ii) an electron acceptor fused with at least one aromatic hydrocarbon ring Represents a divalent linking group containing at least one of an arylene group and an alkylene group, and X represents a covalent bond or a coordinate bond with a metal surface, a metal oxide surface, or a semiconductor surface. Represents a linking group that forms a bond.
  • the aromatic heterocyclic group is pyrazine, imidazole or a condensed ring thereof with another aromatic hydrocarbon or an aromatic heterocycle.
  • T to T 4 may each independently have a cyano group, may have a substituent, or may have a C 6 alkoxycarbonyl group, or may have a substituent
  • Sp represents a nitrogen atom, an oxygen atom, a sulfur atom, an amide bond, an ester bond, or a siloxane bond which may have a substituent in the main chain.
  • X represents a mercapto group, an optionally substituted C1-C6 alkylthio group, a C1-1C11 acylthio group, a C1-1C6 alkoxysilyl group
  • a substrate characterized in that a self-assembled monolayer containing the compound according to any one of (1) to (6) is formed on the surface.
  • one of A is selected from the group consisting of a cyano group, a 1-alkoxycarbonyl group, and a C 1 -C 11 acyl group. At least one selected is an aromatic heterocyclic group bonded on a ring or via a conjugated system, and an atomic group represented by Sp and a functional group bonded on the ring or via a conjugated system. Represent. Specifically, it represents a group of compounds represented by the following formulas A1-A155.
  • a cyano group is described as a representative, but any cyano group may be substituted with a C 1 -C 6 alkoxycarbonyl. Or a C 1 -C 11 acyl group.
  • an electron-withdrawing group is preferable in order to reduce the electron density on the aromatic heterocyclic ring.
  • a nitro group such as a fluorine atom, a trifluoromethyl group, a sulfenyl group , A sulfonyl group, a sulfonic acid group, a phosphonyl group, a phosphoryl group, a phosphinyl group, a C1-C7 acyloxy group and the like.
  • a halogen atom such as a fluorine atom, a trifluoromethyl group, a sulfenyl group , A sulfonyl group, a sulfonic acid group, a phosphonyl group, a phosphoryl group, a phosphinyl group, a C1-C7 acyloxy group and the like.
  • Each substituent may further have an appropriate substituent at any position.
  • the present invention is that the formula (I), 1 type of A is an electron acceptor functional group with at least one or more aromatic hydrocarbon rings are fused, represented by S P Represents a functional group that is bonded to an atomic group directly through a ring or through a hetero atom. Specifically, it represents a group of conjugated compounds represented by the following formulas A161 to A172.
  • a cyano group is described as a representative, but any cyano group may have a substituent. 6 al It may be substituted with a carbonyl group or a C 1 -C 6 alkylsulfonyl group which may have a substituent.
  • a halogen atom such as a 1-107-acyl group, a nitro group, a fluorine atom, a sulfenyl group, a sulfonyl group Sulfonic acid group, phosphonyl group, phosphoryl group, phosphinyl group, C 11 -C 7 acyloxy group, trifluoromethyl group and the like.
  • a substituent represented by the following formula can be exemplified.
  • CI-C6 alkoxycarbonyl group examples include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxy group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, and a t-butoxycarbonyl group.
  • Examples of the C 1 -C 11 acyl group include a formyl group, an acetyl group, and a propanol group.
  • a conjugated system refers to a bonding state that can form a resonance structure with a 7- or higher-orbital electron or higher electron on the aromatic heterocyclic ring, and specifically, a carbon-carbon double bond and a carbon-carbon triple bond.
  • Bond, a carbon-nitrogen double bond, etc. including the case where a plurality of aromatic hydrocarbons and aromatic heterocycles are condensed, and further via the sp 2 carbon of a carbonyl group, an imino group, and a methylidene group. And the case where it is bonded to another aromatic hydrocarbon or an aromatic heterocycle.
  • substituent bonded on the ring in the aromatic heterocyclic group or via a conjugated system may be bonded to another position of the aromatic complex ring to form a ring.
  • a heterocyclic group having a virazine skeleton or an imidazole skeleton is preferably exemplified in consideration of the ease of the production method described later and the availability of raw materials. Can be.
  • C 1 -C 6 alkoxycarbonyl group for 1 to 4 in the formula (II) include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxy group, and an n-butoxycarbonyl group.
  • Examples of the C 6 alkylsulfonyl group include a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an isopropylsulfonyl group, a trifluoromethanesulfonyl group, and a pentafluoroethanesulfonyl group.
  • the groups include formyl, acetyl, propanoinole, bivaloyl, trifluoroacetyl, and It can be exemplified Zoiru group.
  • Sp represents a divalent linking group containing at least one of an arylene group and an alkylene group. Further, the linking group may include the following functional groups as other structural units.
  • R 1 to R 5 each independently represent a hydrogen atom or a C 1 to C 20 hydrocarbon group which may have a substituent. Further, these functional groups may simultaneously contain two or more kinds in one linking group. Further, the linking group may have a cyclic structure, and the cyclic structure may be formed with an aromatic heterocyclic group of A and a bonding group of X.
  • a group or a C1-C20, preferably C6-C20 alkylene group can be preferably exemplified.
  • a linking group represented by the following formula can be exemplified.
  • n and m each independently represent 0 or an integer of 1 or more.
  • X represents a bonding group that forms a bond with a metal surface, a metal oxide surface, or a semiconductor surface by a covalent bond or a coordinate bond.
  • Specific examples include a mercapto group, an optionally substituted C1-C6 alkylthio group, and a C1-C11 acylthio group.
  • L and K represent the numbers of the corresponding aromatic heterocyclic group and bonding group, respectively.
  • the compounds represented by the formula (I) of the present invention are all novel compounds, and specific examples thereof include the compounds shown in the following table.
  • the compound of the present invention represented by the formula (I) can be produced, for example, as follows.
  • the electron-accepting moiety of A in the formula (I) can be obtained from a diaminomaleonitrile or a compound having a similar diamine structure, for example, by the method described in Advances in Heterocyclic Chemistry, vol. 41, pp. 1-39, It can be produced as various nitrogen-containing heterocycles.
  • Y represents a halogen atom or a functional group that can be derived into a halogen atom in a later step, and represents, for example, an ester group, a hydroxyl group to which a protecting group is applied, and the like.
  • lithium, magnesium, zinc, or the like can be used as a metal used for forming the organometallic body.
  • a metal complex such as nickel and palladium can be used as a metal used for forming the organometallic body.
  • the intermediate thus obtained is reduced to a 7j acid group, and when the protected hydroxyl group is deprotected, the intermediate is deprotected to obtain a hydroxyl group. It can be halogenated to lead to a terminal halogen intermediate.
  • the reducing agent L i A 1 H 4, N a BH 4, or the like can Rukoto used.
  • reaction for converting the 7] c acid group into a halogen may be a reaction with a halogenating reagent such as thionyl halide, oxyphosphorus chloride, phosphorus trihalide, or the like, or a conversion to a sulfonic ester, followed by a metal halide salt Can be obtained by an exchange reaction with
  • hydroxyl-protecting group examples include a C 1 -C 6 alkoxymethyl group, a triflatinylmethyl group, a 2-tetrahydrovinylyl group, a C 1 -C 6 trialkylsilyl group, and the like.
  • the halide thus produced can be reacted with an appropriate sulfurizing reagent to introduce a sulfur atom.
  • an appropriate sulfurizing reagent for example, thiourea can be reacted in the presence of a suitable base and then acidified to introduce a mercapto group, or an alkali metal salt of thiocarboxylic acid can be reacted to introduce an acylthio group.
  • the obtained mercapto group can be alkylated in the presence of a suitable base to obtain a desired sulfide compound. (See formula (IV) below) Formula (IV)
  • Examples of the base used for the alkylation and the like include alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates such as lithium carbonate, and tertiary amines such as triethylamine. can do.
  • the dimer disulfide can be obtained by reacting the above mercapto form with iodine or bromine, or hydrogen peroxide or a salt thereof in the presence of a base.
  • oxidizing agent used in the above oxidation reaction examples include nitric acid, cerium nitrate (IV) diammonium salt, silver oxide (II), thallium (III) trifluoroacetate, and the like.
  • a quinodimethane compound can be obtained by reacting the above quinone compound with an active methylene compound in the presence of a suitable catalyst.
  • Active methylene compounds include malononitrile, malonic acid diester, 2-cyanoacetic acid ester, cyanomethanesulfonic acid ester And the like.
  • the catalyst to be used include secondary amines such as dibutylamine, pyrrolidine, piperidine and morpholin, and Ti (IV) compounds such as tetrasalt ⁇ titanium and tetra (isopropoxy) titanium.
  • a method for producing a compound in which X is a silyl group can be obtained by reacting an intermediate having an olefinic terminal with hydrosilane in the presence of a catalyst.
  • a catalyst chloride salts such as platinum, rhodium and ruthenium, complexes and the like can be used. (See formula (VI) below) Formula (VI)
  • A-Sp'-CH CH 2 + H-Si (0R) 3 ⁇ A-Sp'-CH 2 CH 2 Si (OR) 3
  • Sp ' is a heteroatom such as oxygen, nitrogen, sulfur, etc.
  • the compound in which X is a phosphate group can be used to convert the intermediate having a hydroxyl group into a desired compound by a condensation reaction or hydrolysis reaction with diphosphorus pentoxide, a phosphoryl halide, or an activated monophosphate ester. Obtainable.
  • cyclic imid compounds For the production of cyclic imid compounds, the corresponding acid anhydrides and dicarboxylic acid derivatives are reacted directly with primary amines having a functional group such as halogen at the terminal, or with primary amines having a hydroxyl group at the terminal. After the reaction, an intermediate having a functional group such as halogen at the terminal can be obtained by reacting with the halogenating reagent. Alternatively, a similar intermediate can be obtained by reacting the cyclic imide NH with an ⁇ , ⁇ -dihaloalkane in the presence of a base.
  • the terminal functional group of the compound thus obtained can be converted into a functional group containing a sulfur, a gayne, or a phosphoric acid moiety in the same manner as in the formula (IV), the formula (V), and the above method. (See formula (VII) below) Formula (VII)
  • Q represents a 7-acid group and a halogen atom
  • L represents a leaving group such as a halogen atom
  • Sp and X have the same meanings as in formula (I).
  • Sp having an amide bond can be produced as follows.
  • a desired compound can be obtained by reacting an amino group and a carboxylic acid in the presence of a suitable condensing agent.
  • a suitable condensing agent carbonylbis-1H-imidazole, carposimid, cyanophosphate, N-hydroxysuccinic acid, N-hydroxybenzotriazole, and the like can be used.
  • a catalytic amount or an equivalent or more of a base may be present.
  • tertiary amines such as triethylamine, 4-dimethylaminopyridine, alkali metal carbonate, and the like can be used.
  • those containing oxygen, sulfur, and nitrogen atoms as Sp can be produced by, for example, the following method.
  • a cyano-substituted virazine having a suitable leaving group such as a cyano group or a halogen atom with an alcohol, a thiol or an amine at a temperature between -20 ° C and 100 ° C, the desired A compound can be obtained.
  • a catalytic amount or an equivalent or more of a base may be present.
  • tertiary amines such as triethylamine, 4-dimethylaminopyridine, alkali metal carbonate, and the like can be used.
  • C0 2 ff ′ represents a Sp-X moiety
  • L represents a hydroxyl group, a halogen atom, or a C 1 -C 6 alkoxy group.
  • a desired compound can be obtained by reacting a carboxylic acid, a carboxylic acid halide, or a carboxylic acid ester with an alcohol in the presence of a suitable condensing agent or catalyst.
  • a suitable condensing agent or catalyst include tertiary amines such as carbonylbis-1H-imidazole, carposimide, cyanophosphate, N-hydroxysuccinic acid, N-hydroxybenzotriazole, tetraalkoxytitanium, and triethylamine, and hydrochloric acid.
  • Mineral acids such as can be used.
  • the method of formula (IX) can be combined to obtain a compound of formula (I) via both an oxygen, sulfur and nitrogen atom and an ester bond.
  • those having a sulfur atom as X can be obtained by protecting the SH group first and then producing the compound by the production method of formulas (VIII) to (X).
  • the protecting group for protecting the SH group include an acyl group, a C 1 -C 6 alkoxyalkyl group, a 2-cyanoethyl group, a triphenylmethylinole group, a t-butyl group, and the like.
  • the desired mercapto compound can be obtained by reacting an acyl group or a 2-cyanoethyl group with an alkali metal salt such as sodium hydroxide or cesium carbonate.
  • an alkali metal salt such as sodium hydroxide or cesium carbonate.
  • 1 to 6 alkyloxy and 1 to 6 alkyl groups and triphenylmethyl groups can be obtained in the same manner by reacting with mineral acids such as hydrochloric acid and hydrobromic acid, or in the presence of mercury acetate and silver acetate. be able to.
  • a sulfur atom can be introduced by using a compound having a hydroxyl group or a halogen atom at the terminal end as an intermediate, which can be obtained by the production methods of formulas (VIII) to (X).
  • the above production method can be carried out in an organic solvent such as THF, DMF, toluene, chloroform, acetone, acetonitrile, alcohol, etc., or in a two-phase water-organic solvent system at 180 ° C. To 150 ° C.
  • organic solvent such as THF, DMF, toluene, chloroform, acetone, acetonitrile, alcohol, etc.
  • the compound represented by the formula (I) of the present invention obtained as described above has, for example, a layer of a metal such as gold or a metal oxide in a solution of an organic solvent in which they are dissolved. By simply immersing the substrate, it is possible to self-assemble on the substrate and form a monomolecular film.
  • FIG. 1 shows a surface photograph of the substrate prepared in Example 16 using a scanning tunneling microscope.
  • FIG. 2 shows a CV curve of the substrate prepared in Example 16.
  • FIG. 3 shows a CV curve in a solution state of the compound 1.
  • FIG. 4 shows the element distribution state of the substrate prepared in Example 16 by XPS measurement.
  • FIG. 5 shows a CV curve of the electrode immersed in the solution of compound 211. in Example 17.
  • FIG. 6 shows a CV curve measured in Example 17 using a non-immersed electrode in an electrolyte solution of compound 211.
  • the reaction was carried out in the same manner as in Example 1 using 0.52 g of thiooctanoic acid. After extraction into ethyl acetate, the mixture was washed successively with water, 1M hydrochloric acid, saturated saline, aqueous sodium bicarbonate and saturated saline, and dried over anhydrous magnesium sulfate. The mixture was concentrated under reduced pressure, and ethyl acetate (20 mL), activated carbon (1 g) was added and the mixture was stirred at room temperature for 1 hour. After filtration, the filtrate was concentrated under reduced pressure to obtain 0.76 g of the desired compound as a boxy solid.
  • Example 6 (Synthesis of Compound 53.) To a solution of 0.3 g of compound C prepared from ninhydrin according to the above formula, 1.0 g of HO (CH 2 ) 1X S CH 2 CH 2 CN and 20 mL of THF, add 0.03 g of tetraisopropoxytitanium and reflux for 3 days did. The reaction mixture was dissolved in chloroform, washed successively with dilute hydrochloric acid, saturated saline, aqueous sodium bicarbonate, and saturated saline, dried over anhydrous magnesium sulfate, and concentrated, and the concentrated residue was purified by silica gel gel column chromatography. did. It was not possible to determine if the ester group was in the ⁇ -position. Yield 10%
  • compound 174 could be confirmed by 1 H-NMR by mixing the solution of compound 175. with an aqueous alkaline solution, and thus the compound 174. After that, it was found that it was formed.
  • Example 12 (Synthesis of Compound 208.) A solution of 20 g of compound DO. Produced from ninhydrin according to the above formula and 0.33 g of disulfide of compound E in 5 mL of dioxane was stirred at room temperature for 15 hours, concentrated under reduced pressure, and purified by column chromatography. 0.23 g (yield 67-0, yielding yellow crystals) of 208.
  • a gold (111) surface substrate (10 10 mm) deposited on a My substrate was immersed in a 1 mM dichloromethane solution of the compound 1 for 24 hours, and then the substrate was taken out and thoroughly washed with dichloromethane. Then, it was dried for 1 hour under an argon atmosphere to obtain an organic molecular thin film substrate.
  • the substrate was prepared as described above was fixed to a cyclic Porta emissions cytometry (CV) cells open hole, as the electrolyte, 0. 1 M n- B u 4 N ⁇ C 1 0 4 Asetonitoriru solution, a reference electrode to a g / a g N 0 3 electrodes, platinum electrodes as a counter electrode, as a working electrode, using a fixed substrate to measure the CV.
  • CV cyclic Porta emissions cytometry
  • FIG. 3 shows the results in a solution using the gold electrode and the same conditions in which the conjugate 1 was dissolved in the above electrolyte solution (1 OmM :). Observing a reduction potential of 0.996 V, which is very close to 0.89 V observed in the solution state, it is clear that Compound 1. forms an electron-accepting thin film on the substrate. found.
  • Figure 4 shows the results of analyzing the substrate obtained as described above by the angle-resolved X-ray electron spectroscopy (XPS) method. At the depth of 2 nm in the depth direction, carbon atoms were more abundant than gold atoms, so it was verified that a thin film was formed by compound 1.
  • XPS angle-resolved X-ray electron spectroscopy
  • Cyclic voltammetry (CV) measurement of a self-assembled monolayer using compound 211 A gold electrode (1.6 mm0) for CV measurement was attached to the 0.1% mM ethanol solution was immersed for 24 hours, ethanol, washed sequentially with Asetonitoriru, as an electrolyte, 0. 1 M ⁇ - ⁇ ⁇ ⁇ C10 4 Asetonitoriru solution, Ag / AgNO 3 electrode as the reference electrode, a platinum electrode as a counter electrode, CV was measured using the above immersion electrode as a working electrode. The measurement results are shown by the curve SAM in FIG. As an example of the control data, FIG.
  • the compound of the present invention is a novel compound that can be easily produced, and can easily form a monomolecular film by self-organization.
  • compounds in which an aromatic hydrocarbon ring is condensed are compounds which are not condensed due to their planarity, intermolecular interaction based on a unique 7-electron, and the like. Compared with, higher orientation and denseness can be exhibited in the self-assembly process. And its manufacture Also in the above, the effect of the condensed aromatic hydrocarbon ring has an advantage that the desired product can be easily obtained as compared with other cases. For example, in the quinone production process by an oxidation reaction, when there is no condensation structure, dimerization easily occurs and it is difficult to obtain the target product, whereas when there is a condensation structure, The desired quinone can be easily obtained with high efficiency.
  • the compound of the present invention can easily form a monomolecular film by self-assembly, and furthermore, since it exhibits an electron accepting ability, it can be used as a raw material for a molecular device having a new function. It can be said that it is high.

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Abstract

L'invention concerne des composés possédant une structure simple, faciles à préparer, acceptant un électron et s'autoassemblant facilement en formant des monocouches. Ces composés sont représentés par la formule générale (I): dans laquelle A représente (I) un groupe hétérocyclique aromatique portant au moins un groupe sélectionné parmi l'ensemble comprenant un groupe cyano, C1-6alkoxycarbonyle, et C1-11acyle soit sur le cycle soit lié au cycle par l'intermédiaire d'un système conjugué, ou (ii) un groupe fonctionnel accepteur d'électron auquel est fusionné au moins un cycle hydrocarboné aromatique, Sp représente un groupe de liaison divalent contenant un groupe arylène et/ou un groupe alkylène, et X représente un groupe de liaison pouvant réaliser une liaison avec une surface métallique, une surface d'oxyde métallique ou une surface semi-conductrice par une liaison covalente ou de coordination.
PCT/JP2002/013590 2001-12-26 2002-12-26 Composes accepteurs d'electrons pouvant former des monocouches autoassemblees WO2003055853A1 (fr)

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JP2010240829A (ja) * 2009-03-17 2010-10-28 Toshiba Corp 粒子および近接場光導波路
US7928067B2 (en) 2009-05-14 2011-04-19 Ischemix Llc Compositions and methods for treating ischemia and ischemia-reperfusion injury
JP2012126703A (ja) * 2010-03-04 2012-07-05 Sumitomo Chemical Co Ltd 含窒素縮合環化合物、含窒素縮合環重合体、有機薄膜及び有機薄膜素子
WO2014125527A1 (fr) 2013-02-12 2014-08-21 独立行政法人科学技術振興機構 Dispositif électronique mettant en œuvre un film mince organique, et appareil électronique comprenant celui-ci
US8815937B2 (en) 2010-11-18 2014-08-26 Ischemix Llc Lipoyl compounds and their use for treating ischemic injury
CN106062982A (zh) * 2014-02-19 2016-10-26 默克专利股份有限公司 环胺表面改性剂和包含这样的环胺表面改性剂的有机电子器件
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
US10744115B2 (en) 2017-04-25 2020-08-18 Ischemix Llc Compositions and methods for treating traumatic brain injury

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