1998 Fiscal Year Annual Research Report

特異なスピン共役系の開発と展開

Research Project

Project/Area Number	10146101
Research Institution	The University of Tokyo
Principal Investigator	小林啓二東京大学, 大学院・総合文化研究科, 教授 (50012456)
Co-Investigator(Kenkyū-buntansha)	鈴木孝紀北海道大学, 理学部, 助教授 (70202132) 石黒勝也名古屋大学, 工学部, 助教授 (40202981) 井上克也東京大学, 分子科学研究所, 助教授 (40265731) 岡田恵次大阪市立大学, 理学部, 教授 (50152301) 富岡秀雄三重大学, 工学部, 教授 (20024599)
Keywords	カルベン / スピンラダー / スピンクロスオーバー / ラジカルイオン / 分子磁性 / ビラジカル / 有機強磁性 / 電子移動
Research Abstract	年度始めの研究計画に述べた以下の三つのアプローチにおいて、それぞれ研究成果が得られた。 1。安定スピン共役系:低温マトリクス中に発生したジアントリニルカルベンの挙動を明らかにし、200K付近でビラジカル種に変換する現象を見出した。このビラジカル種の三量体を単離し、結晶構造解析に成功した。ラジカル中心を嵩高い置換基で立体的に保護し、分子のもう一方に機能性官能基をもたせたスピンシールド型の安定ラジカルを各種合成し、それらの磁性を明らかにした。共役により安定化された新しいラジカル種を各種合成し、酸化還元挙動を検討した。また、電子移動によりビラジカル種を生成するパイ共役系を開発した。これらは、エレクトロミズム系としても興味深く、その色調変化などを詳細に検討した。 2。集合系:ラジカルがニッケルに配位した錯体を使ってスピンラダー系の構築に成功した。磁気測定の結果、940Kのスピンギャップをもつことが明らかになった。キラルな安定ラジカル種を合成し、その集合化した結晶により不斉分子磁石の構築に成功した。 3。外部応答系:プロトン授受によりビラジカルの発生と消滅をスイッチングできるような分子を設計・合成して、酸化還元電位、酸性度依存性、熱力学パラメーターなどの検討を行った。これは、新しいタイプのスピン・クロスオーバー系の構築に一歩近づくた成果である。電子供与性の基質と電子受容体を固体状態で直接に摺り混ぜることにより、局所的に電荷移動が達成されてアモルファスの電荷移動固体が得られることが分かった。ここで固体中に生じたラジカルカチオンにアルコールの蒸気に曝すことにより求電子置換反応を固相で実現することができた。

Research Products

(24 results)

All Other

All Publications (24 results)

[Publications] 林直人: "Guest-Incorporation in Temary Clathrate Formation is Random but Shows Site-Selectivity" J.Am.Chem.Soc.120. 3799-3800 (1998)
[Publications] 田中素子: "Solid-State Solvolysis Induced via Charge-Transfer Complexation by Solid-State Grinding Followed by Contact with Solvent Vapor" Chem.Commun.1965-1966 (1998)
[Publications] 小林啓二: "ESIPT-Induced Photocyclization of N,N'-diphenyl-1,5-dihydroxy-9,10-anthra-quinone diimine" Chem.Comm.763-764 (1998)
[Publications] 今久保達郎: "A Tailor-made Hexagonal System in a Molecular Conductor" Chem.Commun.2021-2022 (1998)
[Publications] 小林啓二: "Photocyclization of N,N'-diphenyl-1-hydroxy-9,10-anthraquinone diimines via excited-state intramolecular proton transfer(ESIPT)" J.Chem.Soc.,Perkin Trans.1993-1998 (1998)
[Publications] 山形武広: "Intramolecular Spin Interactions through Cumulative Double Bonds" Chem.Letters. 129-130 (1998)
[Publications] H.Kawai: "A New Type of Tricolor Electrochromic System Based on the Dynamic Redox Properties of Hexaarylethyane Derivatives" Chem.Commun.2193-2194 (1998)
[Publications] 鈴木孝紀: "A Kinetically Stabilized 〔1.1〕Parecyclophane:Isolation and X-RayStructural Analysis" Angew.Chem.Int.Ed.Engl.37. 817-819 (1998)
[Publications] H.Yokoi: "Formation of sigma- and pi-Type Dimer Radical Cations by the Photochemical One-Electron Oxidation of Aromatic Sulfides." J.Am.Chem.Soc.
[Publications] H.Yokoi: "The Photochemical Doping of TCNQ by the Photoinduced Electron-Transfer and C-C Cleavage Reaction." Chem.Lett.(印刷中).
[Publications] Koji Nakatsuji: "4,4-(Trimethylene)bis(2,6-t-butylphenoxy)Diradical:An Application of the sequential Redox-Solid State Photolysis(SRSSP)Method" Chem Lett.845-846 (1998)
[Publications] Masatoshi Koizaki: "Preparation and Characterization of Novel DPPH-based Diradicals" Tetrahedron Lett.39. 5979-5982 (1998)
[Publications] 村田滋: "Large Deuterium Isotope Effects for Intramolecular CH Insertion Reaction of 2-Alkylphenylnitrenes" Chem.Lett.549-550 (1998)
[Publications] 富岡秀雄: "Persistent High-Spin Polycarbene" J.Am.Chem.Soc.120. 1106-1107 (1998)
[Publications] M.Terazima: "Translational Diffusion of Chemically Active Species;Carbenes and Carbonyl Oxides" Chem.Phys.Lett.289. 253-260 (1998)
[Publications] 村田滋: "Photochemistry of 2,4-Bis(diazo)-1,2,3,4-tetrahydronaphthalene-1,3-dione" J.Am.Chem.Soc.120. 9088-9089 (1998)
[Publications] A.Nicolaides: "Direct Observation and Identification of p-Phenylenebis(nitrene).A Labile Quinoidal Diradical" J.Am.Chem.Soc.120. 11530-11531 (1998)
[Publications] 鈴木孝紀: "Biphenyl-type Eectron Acceptors Exhibiting Dynamic Redox Properties" Chem.Commun.1331-1332 (1998)
[Publications] Kouzou Matsumoto: "Exchange Interaction of Bispyridinyl Diradicals Linked by s-Frames" Tetrahedron Lett.39. 6307-6310 (1998)
[Publications] Hiroki Mori: "A New Photochemical Approach to Benzylic Polyradicals through C-N Bond Cleavage of a Pyridinyl Radical" Tetrahedron Lett.39. 6315-6316 (1998)
[Publications] T.Sekine: "Observation of Spontaneous Magnetization in the Layered Perovskite Ferromagnet," Inorg.Chem.37. 2129-2133 (1998)
[Publications] T.Otsuka: "Crystal Structures and Magnetic Properties of Acid-Base Molecular Compounds" J.Mater.Chem.8. 1157-1164 (1998)
[Publications] W.Fujita: "Photoisomerism of Azobenzene Derivatives in Layered Magnetic Materials" Mol.Cryst.Liq.Cryst.315. 29-34 (1998)
[Publications] K.Awaga: "High-Pressure Effects on a Manganese Hexacyanomanganate Ferrimagnet" Chem.Phys.Lett.293. 352-356 (1998)

1998 Fiscal Year Annual Research Report

特異なスピン共役系の開発と展開

Principal Investigator

小林 啓二 東京大学, 大学院・総合文化研究科, 教授 (50012456)

Research Products

[Publications] 林直人: "Guest-Incorporation in Temary Clathrate Formation is Random but Shows Site-Selectivity" J.Am.Chem.Soc.120. 3799-3800 (1998)

[Publications] 田中素子: "Solid-State Solvolysis Induced via Charge-Transfer Complexation by Solid-State Grinding Followed by Contact with Solvent Vapor" Chem.Commun.1965-1966 (1998)

[Publications] 小林啓二: "ESIPT-Induced Photocyclization of N,N'-diphenyl-1,5-dihydroxy-9,10-anthra-quinone diimine" Chem.Comm.763-764 (1998)

[Publications] 今久保達郎: "A Tailor-made Hexagonal System in a Molecular Conductor" Chem.Commun.2021-2022 (1998)

[Publications] 小林啓二: "Photocyclization of N,N'-diphenyl-1-hydroxy-9,10-anthraquinone diimines via excited-state intramolecular proton transfer(ESIPT)" J.Chem.Soc.,Perkin Trans.1993-1998 (1998)

[Publications] 山形武広: "Intramolecular Spin Interactions through Cumulative Double Bonds" Chem.Letters. 129-130 (1998)

[Publications] H.Kawai: "A New Type of Tricolor Electrochromic System Based on the Dynamic Redox Properties of Hexaarylethyane Derivatives" Chem.Commun.2193-2194 (1998)

[Publications] 鈴木孝紀: "A Kinetically Stabilized 〔1.1〕Parecyclophane:Isolation and X-RayStructural Analysis" Angew.Chem.Int.Ed.Engl.37. 817-819 (1998)

[Publications] H.Yokoi: "Formation of sigma- and pi-Type Dimer Radical Cations by the Photochemical One-Electron Oxidation of Aromatic Sulfides." J.Am.Chem.Soc.

[Publications] H.Yokoi: "The Photochemical Doping of TCNQ by the Photoinduced Electron-Transfer and C-C Cleavage Reaction." Chem.Lett.(印刷中).

[Publications] Koji Nakatsuji: "4,4-(Trimethylene)bis(2,6-t-butylphenoxy)Diradical:An Application of the sequential Redox-Solid State Photolysis(SRSSP)Method" Chem Lett.845-846 (1998)

[Publications] Masatoshi Koizaki: "Preparation and Characterization of Novel DPPH-based Diradicals" Tetrahedron Lett.39. 5979-5982 (1998)

[Publications] 村田滋: "Large Deuterium Isotope Effects for Intramolecular CH Insertion Reaction of 2-Alkylphenylnitrenes" Chem.Lett.549-550 (1998)

[Publications] 富岡秀雄: "Persistent High-Spin Polycarbene" J.Am.Chem.Soc.120. 1106-1107 (1998)

[Publications] M.Terazima: "Translational Diffusion of Chemically Active Species;Carbenes and Carbonyl Oxides" Chem.Phys.Lett.289. 253-260 (1998)

[Publications] 村田滋: "Photochemistry of 2,4-Bis(diazo)-1,2,3,4-tetrahydronaphthalene-1,3-dione" J.Am.Chem.Soc.120. 9088-9089 (1998)

[Publications] A.Nicolaides: "Direct Observation and Identification of p-Phenylenebis(nitrene).A Labile Quinoidal Diradical" J.Am.Chem.Soc.120. 11530-11531 (1998)

[Publications] 鈴木孝紀: "Biphenyl-type Eectron Acceptors Exhibiting Dynamic Redox Properties" Chem.Commun.1331-1332 (1998)

[Publications] Kouzou Matsumoto: "Exchange Interaction of Bispyridinyl Diradicals Linked by s-Frames" Tetrahedron Lett.39. 6307-6310 (1998)

[Publications] Hiroki Mori: "A New Photochemical Approach to Benzylic Polyradicals through C-N Bond Cleavage of a Pyridinyl Radical" Tetrahedron Lett.39. 6315-6316 (1998)

[Publications] T.Sekine: "Observation of Spontaneous Magnetization in the Layered Perovskite Ferromagnet," Inorg.Chem.37. 2129-2133 (1998)

[Publications] T.Otsuka: "Crystal Structures and Magnetic Properties of Acid-Base Molecular Compounds" J.Mater.Chem.8. 1157-1164 (1998)

[Publications] W.Fujita: "Photoisomerism of Azobenzene Derivatives in Layered Magnetic Materials" Mol.Cryst.Liq.Cryst.315. 29-34 (1998)

[Publications] K.Awaga: "High-Pressure Effects on a Manganese Hexacyanomanganate Ferrimagnet" Chem.Phys.Lett.293. 352-356 (1998)

小林啓二東京大学, 大学院・総合文化研究科, 教授 (50012456)