1989 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	01648003
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) 小林常利慶応義塾大学, 医学部, 教授 (30109798) 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) 伊東しょう徳島文理大学, 薬学部, 教授 (00004242)
キーワード	フェナレニル / 両性炭化水素 / [2,2]メタシクロファン / アントラセンジキノン / ペンタフルベン / チエノアセン / ジチアペリレン / CT錯体
研究概要	1.電気化学的に高い両性をもつ炭化水素としてsーインダセノジフェナレン(IDPL)を設計し、このジイソプロピル誘導体を合成した。ジイソプロピルーIDPLは予想通り高い両性を示す事を見い出すと共に、そのジアニオンが大きなジアトロピズムを示すのに反して、ジカチオンではパラトロピズムを示すことが明らかとなった(村田)。2.syn[2.2]メタシクロファンにおけるsyn antiの反転速度から二つのベンゼン環の間のCT相互作用を評価すべく、ドナー・アクセプター置換基をもつシクロファンの合成を検討した。またNADーNADHモデルとしてのシクロファン合成を試みた(伊東)。3.高い電子受容体として1、4、5、8ーアントラセンジキノン類の合成法を開発すると共に、アセプライアジエン縮環ベンゾキノンの合成に成功しそれらの物性を検討した。またペンタフルベン類の電子移動を利用する方法により新しπ電子系化合物の合成を研究した(小田)。4.新規な電子供与体として4個および5個のチオフェン環がリニヤーに縮合したエアノアセン類の合成を行い、固体状態でのイオン化エネルギーを著しく低くすることに成功した。このようなhydrogenーpoor分子の設計によって固相での電子授受能を高めることが可能となった(小林啓二)。5.分子機能発現を軌道レベルで制御するための一般原理を探るべく、種々の分子の光電子スペクトルを検討した。これによりイオン化エネルギー値を制御する問題に答える上での有用な手法を明かにした。(小林常利)。6.ペリレン基本骨格とするドナーとして3、10ー、1、7ーおよび3、9ージチアペレリンの合成を達成し、何れも低い酸化電位をもつ二段階レドックス系として挙動する事を明らかにした。またこれらのドナーのCT錯体の合成を行い、比較的高電導性を示す物資の開発を行った(中筋)。

研究成果
(30件)

すべてその他

すべて文献書誌 (30件)

[文献書誌] Yoshikazu Sugihara: "An Unusual Thermal Behaviour of Tricyclo[4.1.0.0^<2,7>]heptー4ー3ーone(Tropovalene)" J.Chem Soc.,Chem.Commun. 537-539 (1989)
[文献書誌] Kenichi Imaeda: "Electronic Properties of New Organic Conductors Based on 2,7ーBisー(methylthio)ー1,6ーdithiapyrene(MTDTPY)with TCNQ and pーBenzoquinone" Bull.Chem.Soc.Jpn.62. 372-379 (1989)
[文献書誌] Nobuyuki Harada: "Interchromophoric Homoconjugation Effect and Intramolecular Charge Transfer Transition of the Triptycene System Containing a Tetracyanoquinodimethane Chromophore" J.Chem.Soc.Perkin II. 1449-1453 (1989)
[文献書誌] Yoshikazu Sugihara: "lーPhenalenol:Isolation and Disproportionation Reaction" Angew.Chem.,Int.ED.Engl. 28. 1268-1269 (1989)
[文献書誌] Kimiaki Yamamura: "Cyclohepta[1]phenanthrenylium Ion Derivatives:Intramolecular cyclization of 1ーPhrny1ー2ーtropy1benzenes" Chem.Lett.1511-1514 (1989)
[文献書誌] Kazuhiro Nakasuji: "Synthesis and Properties of 1,7ーDithiaperylene:A New Pericondensed Weitz Type Donor" J.Chem.Soc.,Chem.Commun. 1553-1554 (1989)
[文献書誌] Ichiro Murata: "Some New Aspect of Thiepine and Thiazepine Chemistry" Phosphorus,Sulfur and Silica. 43. 243-259 (1989)
[文献書誌] Kazuhiro Nakasuji: "Synthesis and Characterization of Phenalenyl Cations,Radicals,and,Anions Having Donor and Acceptor Substituents" J.Am.Chem.Soc. 111. 9265-9267 (1989)
[文献書誌] Masahiro Hirama: "Asymmetric Dihydroxylation of Alkenes with Osmium Tetroxide;Chiral N.N^1ーDialkylー2,2^1ーbipyrrolidine Commplex" J.Chem.Soc.,Chem.Commun. 665-666 (1989)
[文献書誌] T.Kawase: "Reductive Coupling of 6ーDimethylaminofulvenes Furnising 6,6^1ーBifulvenyls" J.Chem.Soc.,Chem.Commun. 1989. 1145-1146 (1989)
[文献書誌] T.Kawase: "6ーDimethylaminoー6ーLithiofulvene,A Novel 6ーFulvenyl Anion of Potential Synthetic Utility" Tetrahedron Letters. 37. 545-548 (1990)
[文献書誌] T.Kawase: "Synthesis of synーSubstituted Triptycenes via Heteroatom Directed Mettallation." J.Chem.Soc.,Chem.Commun.
[文献書誌] T.Kawase: "A Novel Synthesis 1,4,5,8ーAnthradiquinones,Potentially Highly Electron Accepting Quinones" Bull.Chem.Soc.Jpn.
[文献書誌] K.Kanoda: "EPR Studies of a New Family of Orgnic Conductors:The Dimethyl(ethylenedithio)diselenadithiafulvalene Compounds" Phys.Rev.B,. 39. 3996-4003 (1989)
[文献書誌] K.Kanoda: "Anomalous Spin Dynamics of Conduction Electrons in the Organic Conductor,[dimethyl(ethylenedithio)diselena dithiafulvalene]_2AuBr_2[(DMET)_2AuBr_2]" Solid State Commun. 69. 415-418 (1989)
[文献書誌] K.Saito: "First Unsymmetrical Donor Which Gives Organic Superconductors:DMET" Acta.Cryst.C45. 1403-1406 (1989)
[文献書誌] K.Saito: "Phase Transition of(DMET)_2Au(CN)_2 at 180K" J.Phys.:Condens.Matter.1. 8823-8828 (1989)
[文献書誌] Y.Mazaki: "Structure and Intramolecular Dynamics of Bis(diisobutyl selenocarbamoyl)Triselenide as Identified in Solution by the ^<77>SeーNMR Spectroscopy" Tetrahedron Lett. 30. 2813-2816 (1989)
[文献書誌] Y.Ishikawa: "Structure of the Organic Superconductor(DMET)_2AuI_2" Acta.Cryst. C45. 572-575 (1989)
[文献書誌] K.Saito: "Thermoelectric Power and an OrderーParameter Associated with the Phase Transition at 180 K of the Organic Metal,(DMET)_2Au(CN)_2" J.Phys.Soc.Jpn.58. 4093-4097 (1989)
[文献書誌] M.R.Bryce,: "Synthesis of Tetrathiafulvalene(TTF)Derivatives Substituted with Two and Four Hydrophyobic Alkyl Chains" Synthetic Metals. 31. 379-387 (1989)
[文献書誌] Y.Mazaki: "Synthesis of Tetraーthienoacene and Pentaーthienoacene;UVーspectral Trend in a Homologous Series of Thienoーacenes" Tetrahedron Lett.30. 3315-3318 (1989)
[文献書誌] K.Kobayashi: "Solfur Heterocycles for Organic Conductors and Superconductors" Phosphorous,Sulfer and Sillica. 43. 187-208 (1989)
[文献書誌] I.Ikemoto,: "Tetramized Structure of(DMET)_2ReO_4 and Its Apparent Metallic Behavior in Resistivity." Bull.Chem,Soc.Jpn.
[文献書誌] K.Murata: "Organic Superconductors,(DMET)_2X" Mol.Cryst.Liq.Cryst.
[文献書誌] Kazuhiro Nakasuji: "Synthesis and Properties of 1,7ーDithiaperylene:a New Periーcondensed Weitzーtype Donor" J.Chem.Soc,Chem.Commun.1553-1554 (1989)
[文献書誌] Nobuyuki Harada: "Interchromophoric Homoconjugation Effect and Intramolecular Chargetrandfer Transition of the Triptycene System Containing a Tetracyanoquinodimethane Chromophore" J.Chem.Soc.,Perkin Trans.II. 1449-1453 (1989)
[文献書誌] Kazuhiro Nakasuji: "Synthesis and Characterization of Phenalenyl Cations,Radicals,and Anions Having Donor and Acceptor Substituents:Three Redox States of Modified Odd Alternant Systems" J.Am.Chem.Soc.111. 9265-9269 (1989)
[文献書誌] Kazuhiro Nakasuji: "New Multiーstage Redox Systems and New Organic Molecular Metals" Pure Appl.Chem.,.
[文献書誌] Kazuhiro Nakasuji: "Synthesis and Properties of 3,9ーDithiaperylene:A Third Isomer of Peri-Condensed WeitzーType Donors Based on the Perylene Skeleton" J.Chem.Soc.,Chem.Commun.

1989 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] Yoshikazu Sugihara: "An Unusual Thermal Behaviour of Tricyclo[4.1.0.0^<2,7>]heptー4ー3ーone(Tropovalene)" J.Chem Soc.,Chem.Commun. 537-539 (1989)

[文献書誌] Kenichi Imaeda: "Electronic Properties of New Organic Conductors Based on 2,7ーBisー(methylthio)ー1,6ーdithiapyrene(MTDTPY)with TCNQ and pーBenzoquinone" Bull.Chem.Soc.Jpn.62. 372-379 (1989)

[文献書誌] Nobuyuki Harada: "Interchromophoric Homoconjugation Effect and Intramolecular Charge Transfer Transition of the Triptycene System Containing a Tetracyanoquinodimethane Chromophore" J.Chem.Soc.Perkin II. 1449-1453 (1989)

[文献書誌] Yoshikazu Sugihara: "lーPhenalenol:Isolation and Disproportionation Reaction" Angew.Chem.,Int.ED.Engl. 28. 1268-1269 (1989)

[文献書誌] Kimiaki Yamamura: "Cyclohepta[1]phenanthrenylium Ion Derivatives:Intramolecular cyclization of 1ーPhrny1ー2ーtropy1benzenes" Chem.Lett.1511-1514 (1989)

[文献書誌] Kazuhiro Nakasuji: "Synthesis and Properties of 1,7ーDithiaperylene:A New Pericondensed Weitz Type Donor" J.Chem.Soc.,Chem.Commun. 1553-1554 (1989)

[文献書誌] Ichiro Murata: "Some New Aspect of Thiepine and Thiazepine Chemistry" Phosphorus,Sulfur and Silica. 43. 243-259 (1989)

[文献書誌] Kazuhiro Nakasuji: "Synthesis and Characterization of Phenalenyl Cations,Radicals,and,Anions Having Donor and Acceptor Substituents" J.Am.Chem.Soc. 111. 9265-9267 (1989)

[文献書誌] Masahiro Hirama: "Asymmetric Dihydroxylation of Alkenes with Osmium Tetroxide;Chiral N.N^1ーDialkylー2,2^1ーbipyrrolidine Commplex" J.Chem.Soc.,Chem.Commun. 665-666 (1989)

[文献書誌] T.Kawase: "Reductive Coupling of 6ーDimethylaminofulvenes Furnising 6,6^1ーBifulvenyls" J.Chem.Soc.,Chem.Commun. 1989. 1145-1146 (1989)

[文献書誌] T.Kawase: "6ーDimethylaminoー6ーLithiofulvene,A Novel 6ーFulvenyl Anion of Potential Synthetic Utility" Tetrahedron Letters. 37. 545-548 (1990)

[文献書誌] T.Kawase: "Synthesis of synーSubstituted Triptycenes via Heteroatom Directed Mettallation." J.Chem.Soc.,Chem.Commun.

[文献書誌] T.Kawase: "A Novel Synthesis 1,4,5,8ーAnthradiquinones,Potentially Highly Electron Accepting Quinones" Bull.Chem.Soc.Jpn.

[文献書誌] K.Kanoda: "EPR Studies of a New Family of Orgnic Conductors:The Dimethyl(ethylenedithio)diselenadithiafulvalene Compounds" Phys.Rev.B,. 39. 3996-4003 (1989)

[文献書誌] K.Kanoda: "Anomalous Spin Dynamics of Conduction Electrons in the Organic Conductor,[dimethyl(ethylenedithio)diselena dithiafulvalene]_2AuBr_2[(DMET)_2AuBr_2]" Solid State Commun. 69. 415-418 (1989)

[文献書誌] K.Saito: "First Unsymmetrical Donor Which Gives Organic Superconductors:DMET" Acta.Cryst.C45. 1403-1406 (1989)

[文献書誌] K.Saito: "Phase Transition of(DMET)_2Au(CN)_2 at 180K" J.Phys.:Condens.Matter.1. 8823-8828 (1989)

[文献書誌] Y.Mazaki: "Structure and Intramolecular Dynamics of Bis(diisobutyl selenocarbamoyl)Triselenide as Identified in Solution by the ^<77>SeーNMR Spectroscopy" Tetrahedron Lett. 30. 2813-2816 (1989)

[文献書誌] Y.Ishikawa: "Structure of the Organic Superconductor(DMET)_2AuI_2" Acta.Cryst. C45. 572-575 (1989)

[文献書誌] K.Saito: "Thermoelectric Power and an OrderーParameter Associated with the Phase Transition at 180 K of the Organic Metal,(DMET)_2Au(CN)_2" J.Phys.Soc.Jpn.58. 4093-4097 (1989)

[文献書誌] M.R.Bryce,: "Synthesis of Tetrathiafulvalene(TTF)Derivatives Substituted with Two and Four Hydrophyobic Alkyl Chains" Synthetic Metals. 31. 379-387 (1989)

[文献書誌] Y.Mazaki: "Synthesis of Tetraーthienoacene and Pentaーthienoacene;UVーspectral Trend in a Homologous Series of Thienoーacenes" Tetrahedron Lett.30. 3315-3318 (1989)

[文献書誌] K.Kobayashi: "Solfur Heterocycles for Organic Conductors and Superconductors" Phosphorous,Sulfer and Sillica. 43. 187-208 (1989)

[文献書誌] I.Ikemoto,: "Tetramized Structure of(DMET)_2ReO_4 and Its Apparent Metallic Behavior in Resistivity." Bull.Chem,Soc.Jpn.

[文献書誌] K.Murata: "Organic Superconductors,(DMET)_2X" Mol.Cryst.Liq.Cryst.

[文献書誌] Kazuhiro Nakasuji: "Synthesis and Properties of 1,7ーDithiaperylene:a New Periーcondensed Weitzーtype Donor" J.Chem.Soc,Chem.Commun.1553-1554 (1989)

[文献書誌] Nobuyuki Harada: "Interchromophoric Homoconjugation Effect and Intramolecular Chargetrandfer Transition of the Triptycene System Containing a Tetracyanoquinodimethane Chromophore" J.Chem.Soc.,Perkin Trans.II. 1449-1453 (1989)

[文献書誌] Kazuhiro Nakasuji: "Synthesis and Characterization of Phenalenyl Cations,Radicals,and Anions Having Donor and Acceptor Substituents:Three Redox States of Modified Odd Alternant Systems" J.Am.Chem.Soc.111. 9265-9269 (1989)

[文献書誌] Kazuhiro Nakasuji: "New Multiーstage Redox Systems and New Organic Molecular Metals" Pure Appl.Chem.,.

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

1989 年度実績報告書

村田一郎大阪大学, 理学部, 教授 (90028077)