1990 年度実績報告書

分子機能制御のための電子授受の設計

研究課題

研究課題/領域番号	02230103
研究機関	大阪大学
研究代表者	村田一郎大阪大学, 理学部, 教授 (90028077)
研究分担者	中筋一弘分子科学研究所, 教授 (60028230) 杉本豊成京都大学, 工学部, 助教授 (30093256) 小林啓二東京大学, 教養学部, 教授 (50012456) 小田雅司大阪大学, 理学部, 教授 (60004438) 伊東〓徳島文理大, 薬学部, 教授 (00004242)
キーワード	チエピン / NADーNADHモデル / プライアデンキノン / ペンタフルベン / チエノアセン / ジセレナピレン / 含硫黄トリメチレンメタン / CTー錯体
研究概要	1.熱的に極めて不安定な母体チエピンを鉄カルボニル錯体として安定な黄色結晶として単離する事が出来た。この合成にはチエピンスルホン錯体を一電子還元剤であるSn12での還元が含まれており、この還元はスルホンからスルフィドへの一般的な変換方法となり得るものである(村田)。2.NADーNADHモデルとしてニコチン酸アミド部分を組み込んだ15,18ージメトキシー9ーメチルー9ーアザ[3.3]メタシクロファンー5ーカルボアミドを合成し、完全にシン型として存在する事を明らかにした。現在その還元力を検討中である(伊東)。4.チエノアセンを構造修飾した電子授受系を合成した。この中でチエノアセンを利用した新しいアクセプタ-のヨウ化銅錯体は、これ迄に例のない新しいタイプの高電導性錯体である事が明らかとなった。また剛直部分構造を持つチエノアセンは優れたホマト分子となる事が判った(小林)。3.新しいキノンとしてプライアデンー8,11ーキノンの合成に成功し、ベンゾキノンに匹敵する電子受容能をもつ事を明らかにし、そのテトラシアノキノジメタン類縁体の合成を行った。またペンタフルベンオリゴマ-の合成とその有機電導体としての展開を図った(小田)。5.CT錯体に基づく有機磁性体の構成分子として1,3ージチオ-ル[3]ラジアレンと同じC3対称をもつ含硫黄トリメチレンメタンのジカチオンを安定な塩として単離した。このジカチオンの二電子還元で生成するトリメチレンメタンのスピン状態を調べた(杉本)。6.有機分子性金属開発の一環として新しいドナ-である1,6ージセレナピレンを合成し、その各種電荷移動錯体の物性を検討した。また水素結合の特性を利用した電荷移動錯体の開発として拡張共役キンヒドロンの設計・合成を行った(中筋)。

研究成果

(47件)

すべてその他

すべて文献書誌 (47件)

[文献書誌] Tomoo Nakazawa: "Synthesis and Properties of 3ーSubstituted 8Hー3ーAzaheptalenー8ーones" Chem.Lett.91-92 (1990)
[文献書誌] Kazuhiro Nakasuji: "Synthesis and Properties of 3,9ーDithiaperylene.A Third Isomer of PeriーCondensed Weitz Type Donors based on the perylene Skeleton" J.Chem.Soc.,Chem.Commun.366-367 (1990)
[文献書誌] Hideaki Hori: "Ein monocyclisches Selenepin: Synthese und Charakerisierung von 2,7ーDiーtertーbutylー4,5ーselenepindicarbonsaurediethylester" Angew.Chem.102. 450-451 (1990)
[文献書誌] Shigeharu Wakabayashi: "Novel Products in the Reaction of 6ーCyanotricyclo[5.5.0.0^<2,5>]dodeca 3,6,9,12ーtetraene with 2,3ーDichloroー5,6ーdicyanoー1,4ーbenzoquinone" J.Chem.Soc.Perkin I. 1489-1490 (1990)
[文献書誌] Toshikazu Kitagawa: "Amphoteric Redox Nature of pーBenzoquinones with Donor and Acceptor Substituents" Chem.Lett.897-900 (1999)
[文献書誌] William E.Acree,Jr,: "Polycyclic Aromatic Hydrocarbons and Polycyclic Aromatic Sulfur Heterocycles: Examination of Molecular StructureーFluorescense Probe Character Correlations" Appl.Spectrosc.44. 951-957 (1990)
[文献書誌] Satoshi Inagaki: "Conformational Adaptation: A New Aspect of Substituent Effects" Bull.Chem.Soc.Jpn.63. 2099-2100 (1990)
[文献書誌] Atsushi Kawamoto: "Crystal and Electronic Structures of Radical Salts of 2,7ーBisー(methylthio)ー1,6ーdithiapyrene (MTDTPY) and 2,7ーBis(methylseleno)ーー1,6ーdithiapyrene (MSDTPY)" Bull.Chem.Soc.Jpn.63. 2137-2145 (1990)
[文献書誌] Atsushi Kawamoto: "Electronic Structures of 2,7ーBis(methylthio)ー1,6ーdithiapyrene (MTDTPY) ChargeーTransfer Complexes" Bull.Chem.Soc.Jpn.63. 2146-2149 (1990)
[文献書誌] Yuriko Aoki: "Molecular Orbital Study on the Electron Donating and Accepting Abilities of NonーAlternant Polycyclic Conjugated Hydrocarbons" Tetrahedron. 46. 6659-6672 (1990)
[文献書誌] Keitaro Nishino: "Synthesis and Thermal Stability of 2ーMethylー1ーbenzothiepine" Chem.Express. 5. 853-856 (1990)
[文献書誌] Shigeru Sasaki: "Synthesis of a Highly Amphoteric 8,16ーDiisopropylーsーindaceno [1,2,3ーcd;5,6,7ーc'd']diphenalene: Switching Between Diatropism and Paratropism Accompanied by its Oxidation levels" Angew.Chem.103. (1991)
[文献書誌] Y.Nakasato,H.Hioki,S.Ito: "Synー[2.2]metacyclophaneー5,13ーdicarbaldhydes.Synthesis,spectra and thermal stability." Tetrahedron letters.
[文献書誌] S.Ito,C.Hashimoto and H.Hioki: "15,18ーDimethoxyー9ーmethylー9ーaza[3.3]metacyclophane,a NAD model." Tetrahedron Letters.
[文献書誌] Takeshi Kawase: "Synthesis of synーSubstituted Triptycenes viaーHeteroatomーdirected Metallation" J.Chem.Soc.,Chemical Communications. 339-340 (1990)
[文献書誌] Takeshi Kawase: "6ーDimethylaminoー6ーlithofulvene,a Novel 6ーFulvenyl Anion of Potential Synthetic Utility" Tetrahedron Letters,. 31. 545-548 (1990)
[文献書誌] Masahiko Iyoda: "NickelーCatalyzed cyclodimerization of Hexapentaenes: 4 Radialenes and 5 Radialenones with Cumulated Double Bonds" Angew.Chem.Int.Ed.Engl.29. 1062-1064 (1990)
[文献書誌] Takeshi Kawase: "Generation,Characterization,and Reactions of Fulvene Dianions" Chemistry Letters. 1683-1686 (1990)
[文献書誌] Masahiko Iyoda: "Thermal and Nickelーcatalyzed Dimerization of Hexapentaene.Synthesis of Two 4 Radialenes with Planar,Stable Cyclobutadieneーlike Geometry" Chemistry Letters. 2149-2152 (1990)
[文献書誌] Shigeru Murata: "Reaction of Bicyclo 6.3.0 undecaー2,4,6,8,11ーpentaenー10ーylidene in OxygenーDoped Matrices: Characterization of the First Carbonyl Oxide with a ーDonating Ring System" J.Org.Chem.55. 4502-4504 (1990)
[文献書誌] Masaji Oda: "Novel Thermal Decarbonylative Dimerization of 1,2,3,4,5,6ーHexahydrobenzo 1,2;4,5 dicyclobuteneー3,6ーdione" Tetrahedron Letters. 31. 7341-7342 (1990)
[文献書誌] Keiji Okada: "A Simple and Convenient Photodecarboxylation Method of Intact Carboxylic Acids in the Presence of Aza Aromatic Compounds" J.Photobiol.A.
[文献書誌] Takashi Kumagai: "Preparative Derivatization of endoーDicyclopentadiene via Metallation" Bull.Chem.Soc.Jpn.
[文献書誌] Takeshi Kawase: "8,11ーDihydropleiadeneー8,11ーdione.A New Pleiadenequinone having Considerable Electron Affinity"
[文献書誌] Takeshi Kawase: "Synthesis of 2ーCyclopentadienylideneー2Hーthiapyran by Novel Reductive Rearrangement of a 6ーThienylfulvene"
[文献書誌] Takeshi Kawase: "A New Synthesis of 1,4,5,8ーAnthradiquinones"
[文献書誌] K.Saito: "Tetramerized Structure of (DMET)_2ReO_4 and Its Apparent Metallic Behavior in Resistivity." Bull.Chem.Soc.Jpn.63. 1865-1870 (1990)
[文献書誌] K.Murata: "Physical Properties and Crystal Structures of DMET Superconductors and Conductors." “The Physics and Chemistry of Organic Superconductors" ed.by G.Saito and S.Kagoshima,SpringerーVerlag,Berlin. 230-233 (1990)
[文献書誌] K.Murata: "Superconductivity and Spin Density Waves in (DMET)_2Au(CN)_2" “The Physics and Chemistry of Organic Superconductors" ed.by G.Saito and S.Kagoshima,SpringerーVerlag,Berlin. 234-237 (1990)
[文献書誌] K.Saito: "Phase Transition of the Organic Metal (DMET)_2Au(CN)_2" “The Physics and Chemistry of Organic Superconductors" ed.by G.Saito and S.Kagoshima,SpringerーVerlag,Berlin. 238-241 (1990)
[文献書誌] K.Kanoda: "Antiferromagnetic Transitions in (DMET)_2X and (DMPT) and (DMPT)_2X." “The Physics and Chemistry of Organic Superconductors" ed.by G.Saito and S.Kagoshima,SpringerーVerlag,Berlin. 242-245 (1990)
[文献書誌] I.Ikemoto: "Organic Superconductors,(DMET)_2X." Mol.Cryst.Liq.Cryst.181. 185-195 (1990)
[文献書誌] Y.Ishikawa: "Structure of the Organic Superconductor (DMET)_2AuCl_2." Acta Cryst.C46. 1652-1655 (1990)
[文献書誌] Y.Ishikawa: "Crystal Structure of the Organic Metal (DMET)_2BF_4." Bull.Chem.Soc.Jpn.64. 212-215 (1991)
[文献書誌] Y.Harada: "Characterization of Organic UltraーThin Films by Penning Ionization Electron Spectroscopy During Layerーbyーlayer Preparation." Surf.Sci.
[文献書誌] K.Kobayashi: "Linearly Condensed Polythiophenes; Characteristic Molecular Aggregation." J.Am.Chem.Soc.
[文献書誌] Y.Mazaki: "A New Host Series for HostーGuest Inclusion Complexes." J.Chem.Soc.,Chem.Commun.
[文献書誌] Y.Mazaki: "Thermal and Photochemical formation of Quinonoid Derivatives of Linearly Condensed Polythiophenes." Tetrahedron Lett.
[文献書誌] Z.Yoshida,T.Sugimoto,and Y.Misaki: "Electronーdonating Radialenes.Potential Donors for (Super)Conductors and Ferromagnets" Materials Research Society Symposium Proceedings. 173. 3-14 (1990)
[文献書誌] T.Sugimoto,K.Ikeda,and J.Yamauchi: "Tris(ethylenedithio)ー and Tris(1,2ーbenzodithio)ーsubstituted Trimethylenemethanes" Chemistry Letters. 29-32 (1991)
[文献書誌] T.Sugimoto,A.Kawachi,K.Ikeda,and J.Yamauchi: "Synthesis of Tetrakis(1,2ーbenzodithio)tetramethyleneethane Dication Salt and Its Twoーelectron Reduction" Chemistry Letters. (1991)
[文献書誌] T.Kitagawa: "Amphoteric Pedox Nature of pーBenzoquinones with Donorー and AcceptorーSubstituents" Chem.Lett.897-900 (1990)
[文献書誌] K.Nakasuji: "Synthesis and Properties of 3,9ーDithiaperylene: A Third Isomer of PeriーCondensed WeitzーType Donors Based on the Perylene Skeleton" J.Chem.Soc.,Chem.Commun.366-367 (1990)
[文献書誌] S.Inagaki: "Conformational Adaptation: A New Aspect of Substituent Effects" Bull.Chem.Soc.Jpn.63. 2099-2100 (1990)
[文献書誌] A.Kawamoto: "Crystal Structure and Electronic Structure of Radical Salts of 2,7ーBis(methylthio)ー1,6ーdithiapyrene (MTDTPY) and 2,7ーBis(methylseleno)ー1,6ーdithiapyrene (MSDTPY)" Bull.Chem.Soc.Jpn.63. 2137-2145 (1990)
[文献書誌] A.Kawamoto: "Electronoic Structure of 2,7ーBis(methylthio)ー1,6ーdithiapyrene (MTDTPY) Charge Transfer Complexes" Bull.Chem.Soc.Jpn.63. 2146-2149 (1990)
[文献書誌] W.E.Acree: "Polycyclic Aromatic Hydrocarbons and Polycyclic Aromatic Sulfur Heterocycles: Examination of Molecular StructureーFluorescence Probe Character Correlations" Appl.Spectrosc.44. 951-957 (1990)

1990 年度 実績報告書

分子機能制御のための電子授受の設計

研究代表者

村田 一郎 大阪大学, 理学部, 教授 (90028077)

研究成果

[文献書誌] Tomoo Nakazawa: "Synthesis and Properties of 3ーSubstituted 8Hー3ーAzaheptalenー8ーones" Chem.Lett.91-92 (1990)

[文献書誌] Kazuhiro Nakasuji: "Synthesis and Properties of 3,9ーDithiaperylene.A Third Isomer of PeriーCondensed Weitz Type Donors based on the perylene Skeleton" J.Chem.Soc.,Chem.Commun.366-367 (1990)

[文献書誌] Hideaki Hori: "Ein monocyclisches Selenepin: Synthese und Charakerisierung von 2,7ーDiーtertーbutylー4,5ーselenepindicarbonsaurediethylester" Angew.Chem.102. 450-451 (1990)

[文献書誌] Shigeharu Wakabayashi: "Novel Products in the Reaction of 6ーCyanotricyclo[5.5.0.0^<2,5>]dodeca 3,6,9,12ーtetraene with 2,3ーDichloroー5,6ーdicyanoー1,4ーbenzoquinone" J.Chem.Soc.Perkin I. 1489-1490 (1990)

[文献書誌] Toshikazu Kitagawa: "Amphoteric Redox Nature of pーBenzoquinones with Donor and Acceptor Substituents" Chem.Lett.897-900 (1999)

[文献書誌] William E.Acree,Jr,: "Polycyclic Aromatic Hydrocarbons and Polycyclic Aromatic Sulfur Heterocycles: Examination of Molecular StructureーFluorescense Probe Character Correlations" Appl.Spectrosc.44. 951-957 (1990)

[文献書誌] Satoshi Inagaki: "Conformational Adaptation: A New Aspect of Substituent Effects" Bull.Chem.Soc.Jpn.63. 2099-2100 (1990)

[文献書誌] Atsushi Kawamoto: "Crystal and Electronic Structures of Radical Salts of 2,7ーBisー(methylthio)ー1,6ーdithiapyrene (MTDTPY) and 2,7ーBis(methylseleno)ーー1,6ーdithiapyrene (MSDTPY)" Bull.Chem.Soc.Jpn.63. 2137-2145 (1990)

[文献書誌] Atsushi Kawamoto: "Electronic Structures of 2,7ーBis(methylthio)ー1,6ーdithiapyrene (MTDTPY) ChargeーTransfer Complexes" Bull.Chem.Soc.Jpn.63. 2146-2149 (1990)

[文献書誌] Yuriko Aoki: "Molecular Orbital Study on the Electron Donating and Accepting Abilities of NonーAlternant Polycyclic Conjugated Hydrocarbons" Tetrahedron. 46. 6659-6672 (1990)

[文献書誌] Keitaro Nishino: "Synthesis and Thermal Stability of 2ーMethylー1ーbenzothiepine" Chem.Express. 5. 853-856 (1990)

[文献書誌] Shigeru Sasaki: "Synthesis of a Highly Amphoteric 8,16ーDiisopropylーsーindaceno [1,2,3ーcd;5,6,7ーc'd']diphenalene: Switching Between Diatropism and Paratropism Accompanied by its Oxidation levels" Angew.Chem.103. (1991)

[文献書誌] Y.Nakasato,H.Hioki,S.Ito: "Synー[2.2]metacyclophaneー5,13ーdicarbaldhydes.Synthesis,spectra and thermal stability." Tetrahedron letters.

[文献書誌] S.Ito,C.Hashimoto and H.Hioki: "15,18ーDimethoxyー9ーmethylー9ーaza[3.3]metacyclophane,a NAD model." Tetrahedron Letters.

[文献書誌] Takeshi Kawase: "Synthesis of synーSubstituted Triptycenes viaーHeteroatomーdirected Metallation" J.Chem.Soc.,Chemical Communications. 339-340 (1990)

[文献書誌] Takeshi Kawase: "6ーDimethylaminoー6ーlithofulvene,a Novel 6ーFulvenyl Anion of Potential Synthetic Utility" Tetrahedron Letters,. 31. 545-548 (1990)

[文献書誌] Masahiko Iyoda: "NickelーCatalyzed cyclodimerization of Hexapentaenes: 4 Radialenes and 5 Radialenones with Cumulated Double Bonds" Angew.Chem.Int.Ed.Engl.29. 1062-1064 (1990)

[文献書誌] Takeshi Kawase: "Generation,Characterization,and Reactions of Fulvene Dianions" Chemistry Letters. 1683-1686 (1990)

[文献書誌] Masahiko Iyoda: "Thermal and Nickelーcatalyzed Dimerization of Hexapentaene.Synthesis of Two 4 Radialenes with Planar,Stable Cyclobutadieneーlike Geometry" Chemistry Letters. 2149-2152 (1990)

[文献書誌] Shigeru Murata: "Reaction of Bicyclo 6.3.0 undecaー2,4,6,8,11ーpentaenー10ーylidene in OxygenーDoped Matrices: Characterization of the First Carbonyl Oxide with a ーDonating Ring System" J.Org.Chem.55. 4502-4504 (1990)

[文献書誌] Masaji Oda: "Novel Thermal Decarbonylative Dimerization of 1,2,3,4,5,6ーHexahydrobenzo 1,2;4,5 dicyclobuteneー3,6ーdione" Tetrahedron Letters. 31. 7341-7342 (1990)

[文献書誌] Keiji Okada: "A Simple and Convenient Photodecarboxylation Method of Intact Carboxylic Acids in the Presence of Aza Aromatic Compounds" J.Photobiol.A.

[文献書誌] Takashi Kumagai: "Preparative Derivatization of endoーDicyclopentadiene via Metallation" Bull.Chem.Soc.Jpn.

[文献書誌] Takeshi Kawase: "8,11ーDihydropleiadeneー8,11ーdione.A New Pleiadenequinone having Considerable Electron Affinity"

[文献書誌] Takeshi Kawase: "Synthesis of 2ーCyclopentadienylideneー2Hーthiapyran by Novel Reductive Rearrangement of a 6ーThienylfulvene"

[文献書誌] Takeshi Kawase: "A New Synthesis of 1,4,5,8ーAnthradiquinones"

[文献書誌] K.Saito: "Tetramerized Structure of (DMET)_2ReO_4 and Its Apparent Metallic Behavior in Resistivity." Bull.Chem.Soc.Jpn.63. 1865-1870 (1990)

[文献書誌] K.Murata: "Physical Properties and Crystal Structures of DMET Superconductors and Conductors." “The Physics and Chemistry of Organic Superconductors" ed.by G.Saito and S.Kagoshima,SpringerーVerlag,Berlin. 230-233 (1990)

[文献書誌] K.Murata: "Superconductivity and Spin Density Waves in (DMET)_2Au(CN)_2" “The Physics and Chemistry of Organic Superconductors" ed.by G.Saito and S.Kagoshima,SpringerーVerlag,Berlin. 234-237 (1990)

[文献書誌] K.Saito: "Phase Transition of the Organic Metal (DMET)_2Au(CN)_2" “The Physics and Chemistry of Organic Superconductors" ed.by G.Saito and S.Kagoshima,SpringerーVerlag,Berlin. 238-241 (1990)

[文献書誌] K.Kanoda: "Antiferromagnetic Transitions in (DMET)_2X and (DMPT) and (DMPT)_2X." “The Physics and Chemistry of Organic Superconductors" ed.by G.Saito and S.Kagoshima,SpringerーVerlag,Berlin. 242-245 (1990)

[文献書誌] I.Ikemoto: "Organic Superconductors,(DMET)_2X." Mol.Cryst.Liq.Cryst.181. 185-195 (1990)

[文献書誌] Y.Ishikawa: "Structure of the Organic Superconductor (DMET)_2AuCl_2." Acta Cryst.C46. 1652-1655 (1990)

[文献書誌] Y.Ishikawa: "Crystal Structure of the Organic Metal (DMET)_2BF_4." Bull.Chem.Soc.Jpn.64. 212-215 (1991)

[文献書誌] Y.Harada: "Characterization of Organic UltraーThin Films by Penning Ionization Electron Spectroscopy During Layerーbyーlayer Preparation." Surf.Sci.

[文献書誌] K.Kobayashi: "Linearly Condensed Polythiophenes; Characteristic Molecular Aggregation." J.Am.Chem.Soc.

[文献書誌] Y.Mazaki: "A New Host Series for HostーGuest Inclusion Complexes." J.Chem.Soc.,Chem.Commun.

[文献書誌] Y.Mazaki: "Thermal and Photochemical formation of Quinonoid Derivatives of Linearly Condensed Polythiophenes." Tetrahedron Lett.

[文献書誌] Z.Yoshida,T.Sugimoto,and Y.Misaki: "Electronーdonating Radialenes.Potential Donors for (Super)Conductors and Ferromagnets" Materials Research Society Symposium Proceedings. 173. 3-14 (1990)

[文献書誌] T.Sugimoto,K.Ikeda,and J.Yamauchi: "Tris(ethylenedithio)ー and Tris(1,2ーbenzodithio)ーsubstituted Trimethylenemethanes" Chemistry Letters. 29-32 (1991)

[文献書誌] T.Sugimoto,A.Kawachi,K.Ikeda,and J.Yamauchi: "Synthesis of Tetrakis(1,2ーbenzodithio)tetramethyleneethane Dication Salt and Its Twoーelectron Reduction" Chemistry Letters. (1991)

[文献書誌] T.Kitagawa: "Amphoteric Pedox Nature of pーBenzoquinones with Donorー and AcceptorーSubstituents" Chem.Lett.897-900 (1990)

[文献書誌] K.Nakasuji: "Synthesis and Properties of 3,9ーDithiaperylene: A Third Isomer of PeriーCondensed WeitzーType Donors Based on the Perylene Skeleton" J.Chem.Soc.,Chem.Commun.366-367 (1990)

[文献書誌] S.Inagaki: "Conformational Adaptation: A New Aspect of Substituent Effects" Bull.Chem.Soc.Jpn.63. 2099-2100 (1990)

[文献書誌] A.Kawamoto: "Crystal Structure and Electronic Structure of Radical Salts of 2,7ーBis(methylthio)ー1,6ーdithiapyrene (MTDTPY) and 2,7ーBis(methylseleno)ー1,6ーdithiapyrene (MSDTPY)" Bull.Chem.Soc.Jpn.63. 2137-2145 (1990)

[文献書誌] A.Kawamoto: "Electronoic Structure of 2,7ーBis(methylthio)ー1,6ーdithiapyrene (MTDTPY) Charge Transfer Complexes" Bull.Chem.Soc.Jpn.63. 2146-2149 (1990)

[文献書誌] W.E.Acree: "Polycyclic Aromatic Hydrocarbons and Polycyclic Aromatic Sulfur Heterocycles: Examination of Molecular StructureーFluorescence Probe Character Correlations" Appl.Spectrosc.44. 951-957 (1990)

1990 年度実績報告書

村田一郎大阪大学, 理学部, 教授 (90028077)