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特異なスピン共役系の関係と展開

Research Project

Project/Area Number 10146101
Research Category

Grant-in-Aid for Scientific Research on Priority Areas (A)

Allocation TypeSingle-year Grants
Research InstitutionThe 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) 石黒 勝也  名古屋大学, 大学院・工学研究科, 助教授 (40202981)
井上 克己 (井上 克也)  分子科学研究所, 相関領域系, 助教授 (40265731)
岡田 恵次  大阪市立大学, 理学部, 教授 (50152301)
阿波賀 邦夫  東京大学, 大学院・総合文化研究科, 助教授 (10202772)
鈴木 孝紀  北海道大学, 大学院・理学研究科, 助教授 (70202132)
富岡 秀雄  三重大学, 工学部, 教授 (20024599)
Project Period (FY) 1998 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥143,500,000 (Direct Cost: ¥143,500,000)
Fiscal Year 2000: ¥35,000,000 (Direct Cost: ¥35,000,000)
Fiscal Year 1999: ¥35,000,000 (Direct Cost: ¥35,000,000)
Fiscal Year 1998: ¥73,500,000 (Direct Cost: ¥73,500,000)
Keywords分子磁性 / 安定ラジカル / 安定カルベン / 磁気双安定性 / 不斉分子磁石 / スピン発生 / 開殻分子種 / 磁気的相互作用 / 反磁性 / 強磁性 / 常磁性 / イオンラジカル / 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 / ビラジカル / 有機強磁性 / 電子移動
Research Abstract

主な研究実績は以下の三つに大別することができる。
新しい安定スピン共役電子系の開発:立体保護により、半減期が室温で10分近くに及ぶ非常に安定な三重項カルベンを開発した。安定なラジカル種により構成される単一成分分子性金属が見い出された。また、キラルな構造を有する不斉ラジカル種の開発に成功し、不斉分子磁石の構築への指針が提示された。
集合体としてのスピン共役電子系の設計と性質:窒素二座型配位子を中心に、スピン共役電子系を配位子とする自己集積型金属錯体による高スピン種の開発が行われ、配位子におけるスピン伝達の様式が解析できた。また、室温をまたいで磁気的双安定性を示すラジカル集合体結晶が発見され、室温での磁気的性質のスイッチング現象を実現させた。
外部応答を示す動的なスピン共役電子系の研究:プロトン濃度に依存して双極イオン構造とビラジカル構造との平衡が成立する分子開発した。酸性度を磁性をプローブとして計測する方法論の基礎が検討された。電気化学的反応系でも、このようなイオン反応が絡む電子構造スイッチング反応が見い出された。電荷移動を固体摩砕により誘起できることが分かった。固相中に開殻分子種を発生させる手法へと展開が計られ、さらに固相反応の触媒的役割が明らかになった。

Report

(3 results)
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • Research Products

    (72 results)

All Other

All Publications (72 results)

  • [Publications] K.Takahashi: "Furane-fused TCNQ and DCNQ ; Synthesis and Properties."J.Org.Chem.. 65. 2577 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Sekiya: "Intramolecular Migration of Bulky Substituents in the Solid State ; Vinylogous Pinacol Rearrangements"J.Am.Chem.Soc.. 122. 10282 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Tanaka: "Solid State Solvolysis of Thiophene-Substituted Trityl-Type Alcohols"J.Org.Chem.. 66. 803 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] N.Tanifuji: "Pseudo-Polymorphs Arising from Weak and Strong -OH- N≡C- Hydrogen Bonding in Inclusion Crystals"Cryst En Comm.. 3. (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.Kumagai: "Synthesis and magnetic properties of a new complex made up of Mn (hfac)2 and the radical with a triplet ground state"New J.Chem.. 7. 537 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Suzuki: "Single-Component Organic Semiconductors Based on Novel Radicals that Exhibit Electrochemical Amphotericity :"J.Org.Chem.. 66. 216 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Kamiyama: "Benzoic Acid and Phenol Derivatives of Nitronyl Nitroxide Biradical as Building Blocks of Organic Molecule-Based Ferrimagnets,"Appl.Mag.Reson.. 19. 45 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] W.Fujita: "Magnetic molecular bistability in the crystals of heterocyclic thiazyl radicals"Mol.Cryst.Liq.Cryst.. 345. 485 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] W.Fujita: "Magnetic properties of layered copper hydroxides under high pressure"Mol.Cryst.Liq.Cryst.. 341. 1193 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Y.Fujii: "Nuclear magnetic relaxation of H-1 in the organic radical salts"J.Phys.Soc.Japan. 69. 1294 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] P.Rabu: "Exchange Coupling Parameters and Energy Levels for Cyclic Metal-Radical Complexes"Europ.J.Inorg.Chem.. 211 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Katoh: "Singlet ground states in an organic S=1/2 spin ladder and a novel double spin chain of ferromagnetic dimers"J.Phys.Soc.Japan. 69. 1008 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Suzuki: "Generation and Amphoteric Redox Properties of Novel Neutral Radicals with the TTF-TCNQ Hybrid Structure,"Heterocycles. 54. 387 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Suzuki: "Preparation, Structure, and Unique Redox Reactions of Novel 2,2'-(2,2-Dimethylpropane-1,3-diylidene)bis(1,3-benzodithiole)-type"J.Chem.Soc.,Perkin Trans.1. 3417 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Suzuki: "Preparation, Structure, and Redox Reactions of Nine-Membered Cyclic Peroxides : A Novel Electrochromic System"Angeur.Chem.Int.Ed.. 39. 1804 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Ohkita: "Syntheses of Acetylenic Oligophenylene Macrocycles based on a Novel Dewar Benzene Building Block Approach,"J.Org.Chem.. 65. 4385 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.Kawai: "Kinetic Stabilization of [1.1] Paracyclophane System."Chem.Eur.J.. 6. 4177 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Ohkita: "First Dewar Benene Approach to Acetylenic Oligophenylene Macrocycles : Synthesis and Structure"Chem.Commun.. 83 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Y. Pontillon: "Experimental and Theoretical Spin Density in a Ferromagnetic Molecular Complex Presenting Interheteromolecular Hydrogen Bonds"J. Am. Chem. Soc.. 41. 10126-10133 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Kuruma: "Guest-Exchange and Guest-Release via Gas-Solid Contact in Clathrate Crystals Based on 2,5-Bis(9-hydroxyfluoren-9-yl)thieno[3.2-b]thiophene"Bull. Chem. Soc. Jpn.. 72. 1395-1401 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Takahashi: "Preparation and Redox Properties of Longitudinally Twinned TCNQ : Hexacyanostilbenequinodimethane Dianion"Tetrahedron Lett.. 40. 5349-5352 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y. Pontillon: "Experimental and Theoretical Spin Density in a Ferromagnetic Molecular Complex"Mol. Cryst., Liq. Cryst.. 334. 211-220 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H. Ohnuki: "Preparation of a New Conducting Langmuir-Blodgett Films Based on Oxygen Substituted TTF Derivative"Synth. Metals. 102. 1699-1700 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H. Yokoi: "The Photochemical Doping of TCNQ by the Photoinduced Electron-Transfer and C-C Cleavage Reaction"Chem Lett.. 545-546 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H. Kumagai: "A chiral molecule-based metamagnet made by chiral organic radical and manganese ion"Angew. Chem. Int. Ed.. 38. 1601-1603 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y. Hosokoshi: "Pressure effect on Mn complexes of bisaminoxyl radicals"Mol. Cryst., Liq. Cryst.. 334. 511-520 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y. Hosokoshi: "Pressure effects on organic rqadicals with ferromagnetic and antiferromagnetic interactions"Synth. Metals. 103. 2323-2324 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M. Mito: "Pressure-induced crossover from alternating to uniform interaction in a S = 1/2 one-dimensional Heisenberg antiferromagnet"Solid State Commun.. 111. 607-611 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A. Sato: "Coexistence of antiferromagnetically ordered Fe3+ spins and metal p-electrons in 1-BETS2FeCl4[BETS = bis(ethylenedithio)tetraselenafulvalene]"Adv. Mater.. 11. 1192-1194 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A. S. Morkosyan: "Magnetic behavior of the ferrimagnetic (1/2, 5/2, 1/2) linear trimer in complex of Mn(hfac)2 with bis- and trisnitroxide radicals"Mol. Cryst., Liq. Cryst.. 334. 549-568 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] F. Iwahori: "Mn(II)-induced formation and structural elucidation of a [3+3] benzene-dimer derivative from m-phenylenebis(N-tert-butylaminoxyl)"J. Am. Chem. Soc.. 121. 7264-7265 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] S. Hayami: "Structure and magnetic property of the organic triradical with triazine skeleton ; 2,4,6-tris{p-(N-oxy-N-tert-butylamino)phenyl}triazine"Chem. Lett.. 545-546 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Hirai: "Laser Flash Photolysis of 3-Noradamantyl(phenyl)diazomethane. Generation, Detection and Kinetics of 2-Phenyladamantene."J. Phys. Org. Chem.. 12. 165-169 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H. Tomioka: "Spectroscopic Studies on Effects of Triptycyl Goup on Structures and Reactivities of Triplet Arylcarbenes"Can. J. Chem.. 77. 1066-1076 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A. Nicolaides: "Effect of Angle Strain in Conjugated Cycloalkenylidenes. Singlet-Triplet Splitting of Cyclobutenylidene and its Ground State Intramolecular"J. Org. Chem.. 54. 3299-3305 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Hirai: "A Tripret Carbene That Can Be Almost Bottled"J. Am. Chem. Soc.. 121. 10213-10214 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A. Nicolaides: "Of Ortho-Conjugatively Linked Reactive Intermediates : The Cases of Ortho-Phenylene-(Bis)Nitrene, -Carbenonitrene and -(Bis)Carbene"J. Am. Chem. Soc.. 121. 10563-10572 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T. Aoki: "Photoinduced Electron-Transfer Cope Rearrangements of 3,6-Diaryl-2,6-octadienes and 2,5-Diaryl-3,4-dimethyl-1,5-hexadiens"J. Org. Chem.. 64-5. 1640-1649 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M. Ohkita: "Synthesis and reaction of 1,4-acetal-bridged 2,3,5,6-tetramethylidenebicyclo[2.2.0]hexane"Chem. Commun.. 19. 1999-2000 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T. Fukushima: "First Stable Tetracyanodiphenoquinodimethane with a Completely Planar Geometry"Tetrahedron Lett.. 40-6. 1175-1178 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T. Otsuka: "Impurity Doping to Molecular Spin ladders : Magnetic Properties of EPYNN^+・[Ni(dmit)_2]^-_<1-x>[Au(dmit)_2]^-_<x->"Synth. Metals. 103. 2292-2293 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M. Yamashita: "Pressure Effect on Halden Gap System"Synth. Metals. 103. 2162-2163 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H. Imai: "M(dmit)_2 Salts with Nitronyl Nitroxide Radical Cations (M = Ni and Au, dmit = 1,3-Dithiol-2-thione-4,5-dithiolate)"J. Am. Chem. Soc.. 121. 8098-8103 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] W. Fujita: "Room-Temperature Magnetic Bistability in Organic Radical Crystals"Science. 286. 261-262 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Awaga: "Magnetic Properties of Molecular Compounds of Mn_<12>Ph"Mol. Cryst., Liq. Cryst.. 335. 1185-1194 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M. A. Girtu: "Magnetic Order and Disorder in a Family of Layered Organic/Inorganic Nanocomposites"Mol. Cryst., Liq. Cryst.. 334. 703-712 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] W. Fujita: "Solvent-Mediated Magnetic Change in Copper-Hydroxy Intercalation Compounds"Mol. Cryst., Liq. Cryst.. 334. 597-604 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T. Suzuki: "Supramolecular Aggregation of m-Nitrobenzoic Acid"J. Org. Chem.. 64. 7107-7113 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 林直人: "Guest-Incorporation in Temary Clathrate Formation is Random but Shows Site-Selectivity" J.Am.Chem.Soc.120. 3799-3800 (1998)

    • Related Report
      1998 Annual Research Report
  • [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)

    • Related Report
      1998 Annual Research Report
  • [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)

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

    • Related Report
      1998 Annual Research Report
  • [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)

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

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

    • Related Report
      1998 Annual Research Report
  • [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)

    • Related Report
      1998 Annual Research Report
  • [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.

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Yokoi: "The Photochemical Doping of TCNQ by the Photoinduced Electron-Transfer and C-C Cleavage Reaction." Chem.Lett.(印刷中).

    • Related Report
      1998 Annual Research Report
  • [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)

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

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

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

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

    • Related Report
      1998 Annual Research Report
  • [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)

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

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

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

    • Related Report
      1998 Annual Research Report
  • [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)

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

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

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

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

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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