1999 年度実績報告書

特異なスピン共役系の開発と展開

研究課題

研究課題/領域番号	10146101
研究機関	東京大学
研究代表者	小林啓二東京大学, 大学院・総合文化研究科, 教授 (50012456)
研究分担者	井上克也分子科学研究所, 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) 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, 院・理学, 助教授 (70202132) 石黒勝也名古屋大学, 院・工学, 助教授 (40202981)
キーワード	安定ラジカル / 磁気的相互作用 / 反磁性 / 強磁性 / 常磁性 / イオンラジカル
研究概要	新しい開殻構造をもつ分子種が数多く開発され、それらの磁気的な性質が明らかにされた。その中で、安定ラジカル1,3,5-trithia-2,4,6-triazopentalenylの結晶が、室温をまたいで常磁性と反磁性との磁気的双安定性を示すことが見い出されたのは特筆に値する。このほか、酸性度により分子内の磁気的相互作用が規則的に変化するビラジカル種、光照射にたいしてphotochromismを示すビラジカル種などが設計、合成された。これらはいずれも磁気的性質を外部刺激によりスイッチングすることができる新しいスピン共役系である。反応中間体と知られる開殻分子種を安定化する試みも多くの成功を修めた。例えば、三重項カルベンを立体保護により安定化しその寿命を著しく延ばすことができた。ケイ素、鉛、ゲルマニウムなどのヘテロカルベン種が補足され、これら化学種の存在を証明した。開殻分子の発生という点でも、新しい反応が開拓された。カチオン種が還元されやすい共役系が設計されelectrochromismへ展開がはかられた。また、固相での混合摺り合わせによりアモルファスな固体中での電荷移動が確認され、その発展として、固相求核置換反応が実現された。

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] Y. Pontillon: "Experimental and Theoretical Spin Density in a Ferromagnetic Molecular Complex Presenting Interheteromolecular Hydrogen Bonds"J. Am. Chem. Soc.. 41. 10126-10133 (1999)
[文献書誌] 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)
[文献書誌] K. Takahashi: "Preparation and Redox Properties of Longitudinally Twinned TCNQ : Hexacyanostilbenequinodimethane Dianion"Tetrahedron Lett.. 40. 5349-5352 (1999)
[文献書誌] Y. Pontillon: "Experimental and Theoretical Spin Density in a Ferromagnetic Molecular Complex"Mol. Cryst., Liq. Cryst.. 334. 211-220 (1999)
[文献書誌] H. Ohnuki: "Preparation of a New Conducting Langmuir-Blodgett Films Based on Oxygen Substituted TTF Derivative"Synth. Metals. 102. 1699-1700 (1999)
[文献書誌] H. Yokoi: "The Photochemical Doping of TCNQ by the Photoinduced Electron-Transfer and C-C Cleavage Reaction"Chem Lett.. 545-546 (1999)
[文献書誌] H. Kumagai: "A chiral molecule-based metamagnet made by chiral organic radical and manganese ion"Angew. Chem. Int. Ed.. 38. 1601-1603 (1999)
[文献書誌] Y. Hosokoshi: "Pressure effect on Mn complexes of bisaminoxyl radicals"Mol. Cryst., Liq. Cryst.. 334. 511-520 (1999)
[文献書誌] Y. Hosokoshi: "Pressure effects on organic rqadicals with ferromagnetic and antiferromagnetic interactions"Synth. Metals. 103. 2323-2324 (1999)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] H. Tomioka: "Spectroscopic Studies on Effects of Triptycyl Goup on Structures and Reactivities of Triplet Arylcarbenes"Can. J. Chem.. 77. 1066-1076 (1999)
[文献書誌] 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)
[文献書誌] K. Hirai: "A Tripret Carbene That Can Be Almost Bottled"J. Am. Chem. Soc.. 121. 10213-10214 (1999)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] T. Fukushima: "First Stable Tetracyanodiphenoquinodimethane with a Completely Planar Geometry"Tetrahedron Lett.. 40-6. 1175-1178 (1999)
[文献書誌] 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)
[文献書誌] M. Yamashita: "Pressure Effect on Halden Gap System"Synth. Metals. 103. 2162-2163 (1999)
[文献書誌] 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)
[文献書誌] W. Fujita: "Room-Temperature Magnetic Bistability in Organic Radical Crystals"Science. 286. 261-262 (1999)
[文献書誌] K. Awaga: "Magnetic Properties of Molecular Compounds of Mn_<12>Ph"Mol. Cryst., Liq. Cryst.. 335. 1185-1194 (1999)
[文献書誌] M. A. Girtu: "Magnetic Order and Disorder in a Family of Layered Organic/Inorganic Nanocomposites"Mol. Cryst., Liq. Cryst.. 334. 703-712 (1999)
[文献書誌] W. Fujita: "Solvent-Mediated Magnetic Change in Copper-Hydroxy Intercalation Compounds"Mol. Cryst., Liq. Cryst.. 334. 597-604 (1999)
[文献書誌] T. Suzuki: "Supramolecular Aggregation of m-Nitrobenzoic Acid"J. Org. Chem.. 64. 7107-7113 (1999)

1999 年度 実績報告書

特異なスピン共役系の開発と展開

研究代表者

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

研究成果

[文献書誌] Y. Pontillon: "Experimental and Theoretical Spin Density in a Ferromagnetic Molecular Complex Presenting Interheteromolecular Hydrogen Bonds"J. Am. Chem. Soc.. 41. 10126-10133 (1999)

[文献書誌] 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)

[文献書誌] K. Takahashi: "Preparation and Redox Properties of Longitudinally Twinned TCNQ : Hexacyanostilbenequinodimethane Dianion"Tetrahedron Lett.. 40. 5349-5352 (1999)

[文献書誌] Y. Pontillon: "Experimental and Theoretical Spin Density in a Ferromagnetic Molecular Complex"Mol. Cryst., Liq. Cryst.. 334. 211-220 (1999)

[文献書誌] H. Ohnuki: "Preparation of a New Conducting Langmuir-Blodgett Films Based on Oxygen Substituted TTF Derivative"Synth. Metals. 102. 1699-1700 (1999)

[文献書誌] H. Yokoi: "The Photochemical Doping of TCNQ by the Photoinduced Electron-Transfer and C-C Cleavage Reaction"Chem Lett.. 545-546 (1999)

[文献書誌] H. Kumagai: "A chiral molecule-based metamagnet made by chiral organic radical and manganese ion"Angew. Chem. Int. Ed.. 38. 1601-1603 (1999)

[文献書誌] Y. Hosokoshi: "Pressure effect on Mn complexes of bisaminoxyl radicals"Mol. Cryst., Liq. Cryst.. 334. 511-520 (1999)

[文献書誌] Y. Hosokoshi: "Pressure effects on organic rqadicals with ferromagnetic and antiferromagnetic interactions"Synth. Metals. 103. 2323-2324 (1999)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] H. Tomioka: "Spectroscopic Studies on Effects of Triptycyl Goup on Structures and Reactivities of Triplet Arylcarbenes"Can. J. Chem.. 77. 1066-1076 (1999)

[文献書誌] 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)

[文献書誌] K. Hirai: "A Tripret Carbene That Can Be Almost Bottled"J. Am. Chem. Soc.. 121. 10213-10214 (1999)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] T. Fukushima: "First Stable Tetracyanodiphenoquinodimethane with a Completely Planar Geometry"Tetrahedron Lett.. 40-6. 1175-1178 (1999)

[文献書誌] 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)

[文献書誌] M. Yamashita: "Pressure Effect on Halden Gap System"Synth. Metals. 103. 2162-2163 (1999)

[文献書誌] 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)

[文献書誌] W. Fujita: "Room-Temperature Magnetic Bistability in Organic Radical Crystals"Science. 286. 261-262 (1999)

[文献書誌] K. Awaga: "Magnetic Properties of Molecular Compounds of Mn_<12>Ph"Mol. Cryst., Liq. Cryst.. 335. 1185-1194 (1999)

[文献書誌] M. A. Girtu: "Magnetic Order and Disorder in a Family of Layered Organic/Inorganic Nanocomposites"Mol. Cryst., Liq. Cryst.. 334. 703-712 (1999)

[文献書誌] W. Fujita: "Solvent-Mediated Magnetic Change in Copper-Hydroxy Intercalation Compounds"Mol. Cryst., Liq. Cryst.. 334. 597-604 (1999)

[文献書誌] T. Suzuki: "Supramolecular Aggregation of m-Nitrobenzoic Acid"J. Org. Chem.. 64. 7107-7113 (1999)

1999 年度実績報告書

小林啓二東京大学, 大学院・総合文化研究科, 教授 (50012456)