核酸を分子組織化の場とする有機磁性体の開拓

• 研究課題/領域番号: 19350072
• 研究種目: 基盤研究(B)
• 配分区分: 補助金
• 応募区分: 一般
• 研究分野: 機能物質化学
• 研究機関: 大阪市立大学
• 研究代表者: 塩見 大輔 大阪市立大学, 大学院・理学研究科, 准教授 (40260799)
• 研究期間 (年度): 2007 – 2009
• 研究課題ステータス: 完了 (2009年度)
• 配分額: 13,780千円 (直接経費: 10,600千円、間接経費: 3,180千円); 2009年度: 2,600千円 (直接経費: 2,000千円、間接経費: 600千円); 2008年度: 2,860千円 (直接経費: 2,200千円、間接経費: 660千円); 2007年度: 8,320千円 (直接経費: 6,400千円、間接経費: 1,920千円)
• キーワード: 電気 / 磁気的性質 / 磁性 / 超分子化学 / 分子性固体 / ラジカル / フェリ磁性 / 核酸塩基 / シトシン / グアニン

研究概要

分子の集団から磁性体を作るためには,構成分子の配列を分子レベルで制御する必要がある.本研究では,核酸に特有の相補的水素結合を利用して,磁性体の構成分子(ラジカル分子)の配列様式を制御する方法論を開拓した.化学的に安定なラジカル導入型核酸塩基を新たに合成し,それらから得られた共結晶についてX線結晶構造解析を行ない,Watson-Crick型ヘテロスピン対が形成されていることを明らかにした.また,オリゴヌクレオチド内で特定の塩基配列の中に,ラジカル分子を配列させるためのモデル系を構築した.

研究成果

• [雑誌論文] Diaminotriazine-Substituted Nitronyl Nitroxide: A Novel Building Block for Organic Magnets Possessing Multiple Hydrogen Bonding Substituents as Structure-Determining Supramolecular Synthons (2010)
  • 著者名/発表者名: H. Tanaka, D. Shiomi, S. Suzuki, M. Kozaki, K. Okada, K. Sato, T. Takui
  • 雑誌名: CrystEngComm 12 ページ: 526-531
• [雑誌論文] Diaminotriazine-Substituted Nitronyl Nitroxide : A Novel Building Block for Organic Magnets Possessing Multiple Hydrogen Bonding Substituents as Structure-Determining Supramolecular Synthons (2010)
  • 著者名/発表者名: H.Tanaka
  • 雑誌名: CrystEngComm 12 ページ: 526-531
  • 査読あり
• [雑誌論文] A Pyrene-Dihydrophenazine Bis(radical cation) in a Singlet Ground State (2009)
  • 著者名/発表者名: S. Suzuki, T. Takeda, M. Kuratsu, M. Kozaki, K. Sato, D. Shiomi, T. Takui, K. Okada
  • 雑誌名: Org. Lett 11 ページ: 2816-2818
• [雑誌論文] Random-Orientation High-Spin ESR Spectroscopy and Comprehensive Spectral Analyses of the Quintet Dicarbene and Dinitrene with meta-Topological Linkers: Origins of Peculiar Line-Broadening in Fine-Structure ESR Spectra in Organic Rigid Glasses (2009)
  • 著者名/発表者名: T. Koto, K. Sato, D. Shiomi, K. Toyota, K. Itoh, E. Wasserman, T. Takui
  • 雑誌名: J. Phys. Chem. A 113 ページ: 9521-9526
• [雑誌論文] Molecular electron-spin quantum computers and quantum information processing: pulse-based electron magnetic resonance spin technology applied to matter spin-qubits (2009)
  • 著者名/発表者名: K. Sato, S. Nakazawa, R. Rahimi, T. Ise, S. Nishida, T. Yoshino, N. Mori, K. Toyota, D. Shiomi, Y. Yakiyama, Y. Morita, M. Kitagawa, K. Nakasuji, M. Nakahara, H. Hara, P. Carl, P. Hoefer, T. Takui
  • 雑誌名: J. Mater. Chem 19 ページ: 3739-3754
• [雑誌論文] A New Ferrimagnet Based on a Radical-Substituted Radical Cation Salt (2009)
  • 著者名/発表者名: Y. Masuda, M. Kuratsu, S. Suzuki, M. Kozaki, D. Shiomi, K. Sato, T. Takui, Y. Hosokoshi, X.-Z. Lan, Y. Miyazaki, A. Inaba, K. Okada
  • 雑誌名: J. Am. Chem. Soc 131 ページ: 4670-4673
• [雑誌論文] Ab initio Calculations of Spin-Orbit Contribution to the Zero-Field Splitting Tensors of npi* Excited States by the CASSCF Method with MRMP2 Energy Correction (2009)
  • 著者名/発表者名: K. Sugisaki, K. Toyota, K. Sato, D. Shiomi, M. Kitagawa, T. Takui
  • 雑誌名: Chem. Phy. Lett 477 ページ: 369-373
• [雑誌論文] Ab initio Calculations of Spin-Orbit Contribution to the Zero-Field Splitting Tensors of npi^* Excited States by the CASSCF Method with MRMP2 Energy Correction (2009)
  • 著者名/発表者名: K.Sugisaki
  • 雑誌名: Chem.Phy.Lett. 447 ページ: 369-373
  • 査読あり
• [雑誌論文] A New Ferrimagnet Based on a Radical-Substituted Radical Cation Salt (2009)
  • 著者名/発表者名: Y.Masuda
  • 雑誌名: J.Am.Chem.Soc. 131 ページ: 4670-4673
  • 査読あり
• [雑誌論文] Molecular electron-spin quantum computers and quantum information processing : pulse-based electron magnetic resonance spin technology applied to matter spin-qubits (2009)
  • 著者名/発表者名: K.Sato
  • 雑誌名: J.Mater.Chem. 19 ページ: 3739-3754
  • 査読あり
• [雑誌論文] Random-Orientation High-Spin ESR Spectroscopy and Comprehensive Spectral Analyses of the Quintet Dicarbene and Dinitrene with meta-Topological Linkers : Origins of Peculiar Line-Broadening in Fine-Structure ESR Spectra in Organic Rigid Glasses (2009)
  • 著者名/発表者名: T.Koto
  • 雑誌名: J.Phys.Chem.A 113 ページ: 9521-9526
  • 査読あり
• [雑誌論文] A Pyrene-Dihydrophenazine Bis(radical cation)in a Singlet Ground State (2009)
  • 著者名/発表者名: S.Suzuki
  • 雑誌名: Org.Lett. 11 ページ: 2816-2818
  • 査読あり
• [雑誌論文] Thermochromism in an Organic Crystal Based on the Co-existence of Sigma-and π-dimers (2008)
  • 著者名/発表者名: Y. Morita, S. Suzuki, K. Fukui, S. Nakazawa, H. Kitagawa, H. Kishida, H. Okamoto, A. Naito, A. Sekine, Y. Ohashi, M. Shiro, K. Sasaki, D. Shiomi, K. Sato, T. Takui, K. Nakasuji
  • 雑誌名: Nature Materials 7 ページ: 48-51
• [雑誌論文] Electronic and Molecular Structures of C60-based Polyanionic High-spin Molecular Clusters: Direct Spin Identification and Electron Spin Transient Nutation Spectroscopy for High Spin Chemistry (2008)
  • 著者名/発表者名: S. Nakazawa, K. Sato, D. Shiomi, M. Luisa T.M.B. Franco, M. Celina R.L.R. Lazana, M. Candida B.L. Shohoji, K. Itoh, T. Takui
  • 雑誌名: Inorg. Chim. Acta 361 ページ: 4031-4037
• [雑誌論文] Macrocyclic High-Spin (S=2) Molecule: Spin Identification of A Sterically Rigid Metacyclophane-Based Nitroxide Tetraradical by Two-Dimensional Electron Spin Transient Nutation Spectroscopy (2008)
  • 著者名/発表者名: T. Sawai, K. Sato, T. Ise, D. Shiomi, K. Toyota, Y. Morita, T. Takui
  • 雑誌名: Angew. Chem. Int. Ed. Eng 47 ページ: 3988-3990
• [雑誌論文] Curved Aromaticity of a Corannulene-Based Neutral Radical: Crystal Structure and 3D Unbalanced Delocalization of Spin (2008)
  • 著者名/発表者名: Y. Morita, A. Ueda, S. Nishida, K. Fukui, T. Ise, D. Shiomi, K. Sato, T. Takui, K. Nakasuji
  • 雑誌名: Angew. Chem. Int. Ed. Eng 47 ページ: 2035-2038
• [雑誌論文] Macrocyclic High-Spin (S=2) Molecule : Spin Identification of A Sterically Rigid Metacyclophane-Based Nitroxide Tetraradical by Two-Dimensional Electron Spin Transient Nutation Spectroscopy (2008)
  • 著者名/発表者名: 沢井 隆利
  • 雑誌名: Angew. Chem. Int. Ed. Eng. 47 ページ: 3988-3990
  • 査読あり
• [雑誌論文] Electronic and Molecular structures of C60-based Polyanionic High-spin Molecular Clusters : Direct Spin Identification and Electron Spin Transient Nutation Spectroscopy for High Spin Chemistry (2008)
  • 著者名/発表者名: 中深 重顕
  • 雑誌名: Inorg. Chim. Acta 361 ページ: 4031-4037
  • 査読あり
• [雑誌論文] Curved Aromaticity of a Corannulene-Based Neutral Radical : Crystal Structure and 3D Unbalanced Delocalization of Spin (2008)
  • 著者名/発表者名: 森田 靖
  • 雑誌名: Angew. Chem. Int. Ed. Eng. 47 ページ: 2035-2038
  • 査読あり
• [雑誌論文] Thermochromism in an Organic Crystal Based on the Co-existence of Sigma- and Pi-dimers (2008)
  • 著者名/発表者名: 森田 靖
  • 雑誌名: Nature Materials 7 ページ: 48-51
  • 査読あり
• [雑誌論文] Singlet Biradical Character of Phenalenyl-Based Kekule Hydrocarbon with Naphthoquinoid Structure (2007)
  • 著者名/発表者名: T. Kubo, A. Shimizu, M. Uruichi, K. Yakushi, M. Nakano, D. Shiomi, K. Sato, T. Takui, Y. Morita, K. Nakasuji
  • 雑誌名: Org. Lett 9 ページ: 81-84
• [雑誌論文] A Guanine-Substituted Nitronyl Nitroxide Radical Forming a One-Dimensional Ferromagnetic Chain (2007)
  • 著者名/発表者名: K. Maekawa, D. Shiomi, T. Ise, K. Sato, T. Takui
  • 雑誌名: Org. Biomol. Chem 5 ページ: 1641-1645
• [雑誌論文] Magnetic Interaction of Tri-and Di-oxytriphenylamine Radical Cation FeCl4 Salts (2007)
  • 著者名/発表者名: M. Kuratsu, S. Suzuki, M. Kozaki, D. Shiomi, K. Sato, T. Takui, K. Okada
  • 雑誌名: Inorg. Chem 46 ページ: 10153-10157
• [雑誌論文] Cytosine-Guanine Base Pairing in a Hydrogen-Bonded Complex of Stable Open-Shell Molecules with S = 1 Spins (2007)
  • 著者名/発表者名: H. Tanaka, D. Shiomi, T. Ise, K. Sato, T. Takui
  • 雑誌名: CrystEngComm 9 ページ: 767-771
• [雑誌論文] Zwitterionicπ-radical Involving EDT-TTF-Imidazole and F4TCNQ: Redox Properties and Self-assembled Structure by Hydrogen-bonds and Multiple S・・・S Interactions (2007)
  • 著者名/発表者名: T. Murata, Y. Morita, Y. Yakiyama, Y. Nishimura, T. Ise, D. Shiomi, K. Sato, T. Takui, K. Nakasuji
  • 雑誌名: Chem. Commun ページ: 4009-4011
• [雑誌論文] Preparation, Structure, and Magnetic Interaction of a Mn(hfac)2-Bridged [2-(3-Pyridyl)(Nitronyl Nitroxide)-Mn(hfac)2]2 Chain Complex (2007)
  • 著者名/発表者名: K. Okada, S. Beppu, K. Tanaka, M. Kuratsu, K. Furuichi, M. Kozaki, S. Suzuki, D. Shiomi, K. Sato, T. Takui, Y. Kitagawa, K. Yamaguchi
  • 雑誌名: Chem. Commun ページ: 2485-2487
• [雑誌論文] Cytosine-Substituted Nitronyl Nitroxide Radicals as Building Blocks for Generalized Ferrimagnetic System (2007)
  • 著者名/発表者名: K. Maekawa, T. Ise, D. Shiomi, K. Sato, T. Takui
  • 雑誌名: Polyhedron 26 ページ: 2347-2352
• [雑誌論文] Thymine-Substituted Nitronyl Nitroxide Biradical as a Triplet (S = 1) Component for Bio-Inspired Molecule-Based Magnets (2007)
  • 著者名/発表者名: H. Tanaka, D. Shiomi, T. Ise, K. Sato, T. Takui
  • 雑誌名: Polyhedron 26 ページ: 2230-2234
• [雑誌論文] Preparation and Magnetic Properties of 4, 6-Bis(imino nitroxide)-Substituted Resorcinol and its Cu-Complex (2007)
  • 著者名/発表者名: K. Tanaka, K. Furuichi, M. Kozaki, S. Suzuki, D. Shiomi, K. Sato, T. Takui, K. Okada
  • 雑誌名: Polyhedron 26 ページ: 2021-2026
• [雑誌論文] Benzyl-Phenyl Ether Derivatives of Nitronyl Nitroxide Triradicals as a Model for Single-component Organic Molecule-based Ferrimagnetics (2007)
  • 著者名/発表者名: Y. Kanzaki, D. Shiomi, T. Ise, K. Sato, T. Takui
  • 雑誌名: Polyhedron 26 ページ: 1901-1904
• [雑誌論文] Magnetic Interactions in p-Phenylene-bis(nitronyl nitroxide) Biradicals with Large Torsion Angles (2007)
  • 著者名/発表者名: Y. Kanzaki, D. Shiomi, T. Ise, K. Sato, T. Takui
  • 雑誌名: Polyhedron 26 ページ: 1890-1894
• [雑誌論文] Stable Iminonitroxide Biradicals: Building Blocks for Organic Heterospin, Heteromolecular Complexes (2007)
  • 著者名/発表者名: K. Hayakawa, T. Ise, D. Shiomi, K. Sato, T. Takui
  • 雑誌名: Polyhedron 26 ページ: 1885-1889
• [雑誌論文] Implementation of Molecular Spin Quantum Computing by Pulsed ENDOR Technique: Direct Observation of Quantum Enatnglement and Spinor (2007)
  • 著者名/発表者名: K. Sato, R. Rahimi, N. Mori, S. Nishida, K. Toyota, D. Shiomi, Y. Morita, A. Ueda, S. Suzuki, K. Furukawa, T. Nakamura, M. Kitagawa, K. Nakasuji, M. Nakahara, H. Hara, P. Carl, P. Hoefer, T. Takui
  • 雑誌名: Physica E 40 ページ: 363-366
• [雑誌論文] Preparation,Structure,and Magnetic Interaction of a Mn(hfac)2-Bridged [2-(3-Pyridyl)(Nitronyl Nitroxide)-Mn(hfac)2]2 Chain Complex (2007)
  • 著者名/発表者名: K.Okada
  • 雑誌名: Chem.Commun. 2007 ページ: 2485-2487
  • 査読あり
• [雑誌論文] Zwitterionic π-radical Involving EDT-TIF-Imidazole and F_4TCNQ:Redox Properties and Self-assembled Structure by Hydrogen-bonds and Multiple S-S Interactions (2007)
  • 著者名/発表者名: T.Murata
  • 雑誌名: Chem.Commun. 2007 ページ: 4009-4011
  • 査読あり
• [雑誌論文] Cytosine-Guanine Base Pairing in a Hydrogen-Bonded Complex of Stable Open-Shell Molecules with S=1 Spins (2007)
  • 著者名/発表者名: H.Tanaka
  • 雑誌名: CrystEngComm 2007 ページ: 767-771
  • 査読あり
• [雑誌論文] Magnetic Interaction of Tri-and Di-oxytriphenylamine Radical Cation FeCl4 Salts (2007)
  • 著者名/発表者名: M.Kuratsu
  • 雑誌名: Inorg.Chem. 46 ページ: 10153-10157
  • 査読あり
• [雑誌論文] A Guanine-Substituted Nitronyl Nitroxide Radical Forming a One-Dimensional Ferromagnetic Chain (2007)
  • 著者名/発表者名: K.Maekawa
  • 雑誌名: Org.Biomol.Chem. 5 ページ: 1641-1645
  • 査読あり
• [雑誌論文] Singlet Biradical Character of Phenalenyl-Based Kekule Hydrocarbon with Naphthoquinoid Structure (2007)
  • 著者名/発表者名: T.Kubo
  • 雑誌名: Org.Lett. 9 ページ: 81-84
  • 査読あり
• [雑誌論文] Implementation of Molecular Spin Quantum Computing by Pulsed ENDOR Technique:Direct Observation of Quantum Enatnglement and Spinor (2007)
  • 著者名/発表者名: K.Sato
  • 雑誌名: Physica E 40 ページ: 363-366
  • 査読あり
• [雑誌論文] Benzyl-Phenyl Ether Derivatives of Nitronyl Nitroxide Triadicals as a Model for Single-component Organic Molecule-based Ferrimagnetics (2007)
  • 著者名/発表者名: Y.Kanzaki
  • 雑誌名: Polyhedron 26 ページ: 1901-1904
  • 査読あり
• [雑誌論文] Stable Iminonitroxide Biradicals:Building Blocks for Organic Heterospin,Heteromolecular Complexes (2007)
  • 著者名/発表者名: K.Hayakawa
  • 雑誌名: Polyhedron 26 ページ: 1885-1889
  • 査読あり
• [雑誌論文] Magnetic Interactions in p-Phenylene-bis(nitronyl nitroXide) Biradicals with Large Torsion Angles (2007)
  • 著者名/発表者名: Y.Kanzaki
  • 雑誌名: Polyhedron 26 ページ: 1890-1894
  • 査読あり
• [雑誌論文] Preparation and Magnetic Properties of 4,6-Bis (imino itroxide)-Substituted Resorcinol and its Cu-Comlex (2007)
  • 著者名/発表者名: K.Tanaka
  • 雑誌名: Polyhedron 26 ページ: 2021-2026
  • 査読あり
• [雑誌論文] Thymine-Substituted Nitronyl Nitroxide Biradical as a Triplet(S=1)Component for Bio-Inspired Molecule-Based Magnets (2007)
  • 著者名/発表者名: H.Tanaka
  • 雑誌名: Polyhedron 26 ページ: 2230-2234
  • 査読あり
• [雑誌論文] Cytosine-Substituted Nitronyl Nitroxide Radicals as Buiding Blocks for Generalized Ferrimagnetic System (2007)
  • 著者名/発表者名: K.Maekawa
  • 雑誌名: Polyhedron 26 ページ: 2347-2352
  • 査読あり
• [学会発表] Spin-Labeled Nucleobases as Building Blocks for Molecule-Based Magnetic Systems (2008)
  • 著者名/発表者名: 塩見大輔
  • 学会等名: 11th International Congress on Molecule- based Magnets
  • 発表場所: イタリア, フィレンツェ
  • 年月日: 2008-09-21
• [学会発表] Spin-Labeled Nucleobases as Building Blocks for Molecule-Based Magnetic Systems (2008)
  • 著者名/発表者名: 塩見大輔
  • 学会等名: 11th International Congress on Molecule-based Magnets
  • 発表場所: イタリア, フィレンツェ
  • 年月日: 2008-09-21