複合機能を有する分子性導体の創製

• Project/Area Number: 15073219
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Tokyo Metropolitan University
• Principal Investigator: 伊與田 正彦 (伊与田 正彦 / 伊興田 正彦) Tokyo Metropolitan University, 都市教養学部, 教授 (50115995)
• Co-Investigator(Kenkyū-buntansha): 西長 亨 首都大学東京, 都市協学部, 准教授 (30281108) ; 桑谷 善之 首都大学東京, 大学院理工学研究科, 准教授B (00234625) ; 三宅 由寛 東京都立大学, 理学研究科, 助手 (00347270)
• Project Period (FY): 2003 – 2007
• Project Status: Completed (Fiscal Year 2007)
• Budget Amount: ¥26,300,000 (Direct Cost: ¥26,300,000); Fiscal Year 2007: ¥4,900,000 (Direct Cost: ¥4,900,000); Fiscal Year 2006: ¥6,000,000 (Direct Cost: ¥6,000,000); Fiscal Year 2005: ¥6,100,000 (Direct Cost: ¥6,100,000); Fiscal Year 2004: ¥6,100,000 (Direct Cost: ¥6,100,000); Fiscal Year 2003: ¥3,200,000 (Direct Cost: ¥3,200,000)
• Keywords: テトラチアフルバレン / TTFオリゴマー / ソルバトクロミズム / サーモクロミズム / 自己会合挙動 / 分子ワイヤー / カラム構造 / ヘキサゴナル構造 / ナノ構造 / ナノワイヤー / 分子導線 / 半導性物性 / ナノ材料 / 分子性固体 / 有機導体 / 複核磁性体 / 複合機能 / サンドイッチ錯体 / 巨大分子 / 分子電線

Research Abstract

複数のTTFユニットが規則的に並んだ構造をもつTTFオリゴマーは、自己会合によって種々の機能性を示す分子である。本研究では、トリス(テトラチアフルバレノ)ヘキサデヒドロ〔14〕アヌレン、トリス(テトラチアフルバレノ)ドデカデヒドロ〔18〕アヌレン、ヘキサキス(テトラチアフルバレニルエチニル)ベンゼンを合成してその自己会合挙動に基づく機能性の発現を調べた。
TTF〔14〕アヌレンの物性で最も特徴的であるのは、ソルバトクロミズムであり、二硫化炭素中で顕著な色の変化と電子スペクトルの長波長シフトを示した。また、TTF〔14〕アヌレンは銀カチオンと2対1の錯体を作り、非常に大きなサンドイッチ構造を溶液中で形成した。TTF〔18〕アヌレンはベンゼンおよびトルエン中で会合挙動を示し、そのトルエン溶液を冷却すると溶液の色が赤から紫に変化した。このサーモクロミズムは分子の会合挙動によっており、室温ではモノマーであるが、低温では多量体に変化することに起因している。
ヘキサキス(テトラチアフルバレニルエチニル)ベンゼンは対応するヨードTTFとヘキサエチニルベンゼンの菌頭反応によって比較的好収率で合成することができた。この分子は、フレキシブルであるが分子内CH…S相互作用によってディスク状の構造をとり、中性状態およびカチオンラジカル状態のいずれにおいても非常に強く自己会合する分子であった。このような性質から、この分子は中性状態・溶液中でシリンダー状のカラム構造を作り、さらに固体状態では分岐の多い分子ワイヤーを形勢した。またこの分子ワイヤーのXRD測定からこの分子のワイヤーはヘキサゴナル構造をもつことがわかった。さらに、この化合物を固体基板上で薄膜とすると、基盤に対して垂直に並ぶ性質をもち、この薄膜のXRDは分子ワイヤーのそれとは異なっていた。興味深いことに、この薄膜は弱いながらFET特性を示した。

Research Products

• [Journal Article] Supramolecular Structures and Nanoassemblies of Oligothiophenes and Terathiafulvalenes (2009)
  • Author(s): M. Iyoda, M. Takase, T. Nishinaga
  • Journal Title: Topics Heterocyclic Chem. (印刷中)
  • Peer Reviewed
• [Journal Article] Copper-Medeated Aryl-Aryl Couplings for the Construction of Oligophenylenes and Related Heteroaromatics (2009)
  • Author(s): M. Iyoda
  • Journal Title: Adv. Synth. Catal. 351 Pages: 984-998
  • Peer Reviewed
• [Journal Article] Giant Macrocycles Composed of Thiophene, Acetylene, and Ethylene Units (2009)
  • Author(s): M. Iyoda
  • Journal Title: Comptes Rendus Chimie 12 Pages: 395-402
  • Peer Reviewed
• [Journal Article] Long-distance ferromagnetic coupling through spin polarization in a linear heterotrinuclear iron(III)-copper(II)-iron(III) complex derived from 5-ferrocenyl-2-aminotropone (2008)
  • Author(s): Y. Miyake, S. Watanabe, S. Aono, T. Nishinaga, A. Miyazaki, T. Enoki, H. Miyasaka, H. Otani, M. Iyoda
  • Journal Title: Chem. Commun. Pages: 6167-6169
  • Peer Reviewed
• [Journal Article] Giant Thienylene-Acetylene-Ethylene Macrocycles with Large Two-Photon Absorption Cross Section and Semishape-Persistence (2008)
  • Author(s): M. Williams-Harry, A. Bhaskar, G. Ramakrishna, T. Goodson, III, M. Imamura, A. Mawatari, K. Nakao, H. Enozawa, T. Nishinaga, M. Iyoda
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 3252-3253
  • Peer Reviewed
• [Journal Article] Synthesis of Nonaphenylenes and Dodecaphenylenes Using Electron-Transfer Oxidation of Lipshutz Cuprates and Formation of Nanostructural Materials from Hexadodecyloxy-nonaphenylene (2008)
  • Author(s): M. J. Rahman, J. Yamakawa, A. Matsumoto, H. Enozawa, T. Nishinaga, K. Kamada, M. Iyoda
  • Journal Title: J. Org. Chem. 73 Pages: 5542-5548
  • Peer Reviewed
• [Journal Article] Hexagonally Ordered Nanostructures Comprised of a Fiexible Disk-like Molecule with High Self-Assembling Properties at Neutral and Cationic States (2007)
  • Author(s): M. Hasegawa, H. Enozawa, Y. Kawabata, M. Iyoda
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 3072-3073
  • Peer Reviewed
• [Journal Article] Short-Step Syntheses and Complexation Properties of Z, Z-tribenzodidehydro- and all-Z-tribenzo[12]annulenes (2007)
  • Author(s): S. Sirinintasak, Y. Kuwatani, S. Hoshi, E. Isomura, T. Nishinaga, M. Iyoda
  • Journal Title: Tetrahedron Lett. 48 Pages: 3433-3436
  • Peer Reviewed
• [Journal Article] Electroactive Nanowires based on Simple 4, 5-Bis(dodecylthio)- and 4, 5-Bis(octadecylthio)-4', 5'-bis(methoxycarbonyl)tetrathiafulvalenes (2007)
  • Author(s): Y. Kobayashi, M. Hasegawa, H. Enozawa, M. Iyoda
  • Journal Title: Chemistry Lett. 36 Pages: 720-721
  • NAID: 130004424762
  • Peer Reviewed
• [Journal Article] Crystal structure and physical properties of conducting molecular magnets with a halogen-substituted donor: (EDO-TTFBr_2)_2FeX_4 (X = Cl, Br) (2007)
  • Author(s): A. Miyazaki, H. Yamazaki, Aimatsu, T. Enoki, R. Watanabe, E. Ogura, Y. Kuwatani, M. Iyoda
  • Journal Title: Inorg. Chem. 46 Pages: 3353-3366
  • Peer Reviewed
• [Journal Article] Hexagonally Ordered Nanostructures Comprised of a Flexible Disk-like Molecule with High Self-Assembling Properties at Neutral and Cationic States (2007)
  • Author(s): M.Hasegawa, H.Enozawa, Y.Kawabata, M.Iyoda
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 3072-3073
  • Peer Reviewed
• [Journal Article] Short-Step Syntheses and Complexation Properties of Z,Z-tribenzodidehydro-and all-Z-tribenzo[12]annulenes (2007)
  • Author(s): S.Sirinintasak, Y.Kuwatani, S.Hoshi, E.Isomura, T.Nishinaga, M.Iyoda
  • Journal Title: Tetrahedron Lett 48 Pages: 3433-3436
  • Peer Reviewed
• [Journal Article] Electroactive Nanowires based on Simple 4,5-Bis(dodecylthio)-and 4,5-Bis(octadecylthio)-4',5'-bis(methoxycarbonyl)tetrathiafulvalenes (2007)
  • Author(s): Y.Kobayashi, M.Hasegawa, H.Enozawa. M.Ivoda
  • Journal Title: Chemistry Lett 36 Pages: 720-721
  • Peer Reviewed
• [Journal Article] Hexagonally Ordered Nanostructures Comprised of a Flexible Disk-Like Molecule with High Self-Assembling Properties at Neutral and Cationic States (2007)
  • Author(s): M.Hasegawa, H.Enozawa, Y.Kawabata, M.Iyoda
  • Journal Title: Journal of the American Chemical Society 129 Pages: 3072-3073
• [Journal Article] Short-step syntheses and silver complex formation of Z,Z-tribenzodidehydro- and all-Z-tribenzo[12]annulenes (2007)
  • Author(s): S.Sirinintasak, Y.Kuwatani, S.Hoshi, E.Isomura, T.Nishinaga, M.Iyoda
  • Journal Title: Tetrahedron Letters 48 Pages: 3433-3436
• [Journal Article] Synthesis of Tris(tetrathiafulvaleno)dodecadehydro[18]annulenes and Their Self-Assembly (2006)
  • Author(s): H.Enozawa, M.Hasegawa, D.Takamatsu, K.Fukui, M.Iyoda
  • Journal Title: Organic Letters 8 Pages: 1917-1920
• [Journal Article] Selective Hydrosilylation of Alkynes Using Iridium Complexes in the Presence of Biphosphinine (2006)
  • Author(s): Y.Miyake, E.Isomura, M.Iyoda
  • Journal Title: Chemistry Letters 35 Pages: 836-837
• [Journal Article] Efficient Construction of Biaryls and Macrocyclic Cyclophanes via Electron- Transfer Oxidation of Lipshutz Cuprates (2006)
  • Author(s): Y.Miyake, M.Wu, M.J.Rahman, Y.Kuwatani, M.Iyoda
  • Journal Title: Journal of Organic Chemistry 71 Pages: 6110-6117
• [Journal Article] Giant Macrocycles Composed of Thiophene, Acetylene, and Ethylene Building-Blocks (2006)
  • Author(s): K.Nakao, M.Nishimura, T.Tamachi, Y.uwatani, H.Miyasaka, T.Nishinaga, M.Iyoda
  • Journal Title: Journal of the American Chemical Society 128 Pages: 16740-16747
• [Journal Article] Synthesis of Tris(tetrathiafulvaleno)dodecadehydro[18]annulenes and Their Self-Assembly (2006)
  • Author(s): H.Enozawa, M.Hasegawa, D.Takamatsu, K.Fukui, M.Iyoda
  • Journal Title: Organic Letters 8(印刷中)
• [Journal Article] Novel electron-transfer oxidation of Lipshutz cuprates with 1,4-benzoquinones : An efficient homo-coupling reaction of aryl halides and its application to the construction of macrocyclic systems (2005)
  • Author(s): Y.Miyake, M.Wu, M.J.Rahman, M.Iyoda
  • Journal Title: Chemical Communications Pages: 411-413
• [Journal Article] Bis(ethylenedioxy)-1,4,5,8-tetraselenanaphthalene : The First Example of Tetraselenanaphthalene (2005)
  • Author(s): R.Watanabe, Y.Miyake, Y.Kuwatani, M.Iyoda
  • Journal Title: Chemistry Letters 34 Pages: 68-69
  • NAID: 10014218055
• [Journal Article] d-Electron-Induced Negative Magnetoresistance of π-d Interaction System Including Brominated-TTF Donor (2005)
  • Author(s): J.Nishijo, A.Miyazaki, T.Enoki, R.Watanabe, Y.Kuwatani, M.Iyoda
  • Journal Title: Inorganic Chemistry 44 Pages: 2493-2506
• [Journal Article] Synthesis of Nonaphenylenes and Dodecaphenylenes Using Electron-Transfer Oxidation of Lipshutz Cuprate Intermediates (2005)
  • Author(s): M.Iyoda, M.Wu, Y.Kuwatani, Y.Miyake
  • Journal Title: Chemistry Letters 34 Pages: 1474-1475
  • NAID: 10016843796
• [Journal Article] Nickel-catalyzed Dimerization of [5]Cumulenes (Hexapentaenes) (2005)
  • Author(s): Y.Kuwatani, G.Yamamoto, M.Oda, M.Iyoda
  • Journal Title: Bull.Chem.Soc.Jpn 78 Pages: 2188-2208
  • NAID: 10017074742
• [Journal Article] Bi-TTF, Bis-TTF, and Related Oligomers (2004)
  • Author(s): 伊与田正彦他
  • Journal Title: Chemical Review誌 vol.104 Pages: 5085-5114
• [Journal Article] Mono- and Bis(tetrathiafulvaleno)hexadehydro-[12]annulenes (2004)
  • Author(s): 原憲司他
  • Journal Title: Chemical Communications誌 Pages: 2042-2043
• [Journal Article] Bis(tetrathiafulvaleno)octadehydro[20]annulene with Multi-Functionality (2004)
  • Author(s): 伊与田正彦他
  • Journal Title: Chemistry Letters誌 Pages: 1098-1099
  • NAID: 10013527207
• [Journal Article] Aggregation of Strar-Shaped Tris(tetrathiafulvelenylethynyl)benzene in Solution and in the Solid State (2004)
  • Author(s): 長谷川真士他
  • Journal Title: Tetrahedron Letters誌 vol.45 Pages: 4109-4112
• [Journal Article] Association of Poly(tetrathiafulvalenyl)benzenes in Neutral and Cationic States (2004)
  • Author(s): 長谷川真士他
  • Journal Title: J.Phys.IV France誌 vol.114 Pages: 505-507
• [Journal Article] Interaction and Aggregation of TTF Oligomers towards Supramolecular Chemistry (2004)
  • Author(s): 伊与田正彦他
  • Journal Title: J.Phys.IV France誌 vol.114 Pages: 455-5458
• [Presentation] 有機π電子系を用いるナノ集積体の構築 (2008)
  • Author(s): 伊輿田正彦
  • Organizer: 第2回有機π電子系シンポジウム
  • Place of Presentation: 広島県宮島
• [Presentation] Functional Nanoscopic and Mesoscopic Architectures of Self-Assembled Organicπ-Donors (2008)
  • Author(s): M. Iyoda
  • Organizer: Conference of Innovative Science and Technology
  • Place of Presentation: 韓国
• [Presentation] Nanostmctures of Self-Assembled TTF Oligomers and Giant π-Expanded Macrocyclic Oligothiophenes (2007)
  • Author(s): M. Iyoda
  • Organizer: バングラデシュ国際化学会(基調講演)
  • Place of Presentation: ダッカ(バングラデシュ)
• [Presentation] Nanostructures of Self-Assembled TTF Oligomers and Giant π-Expanded Macrocyclic Oligothiophenes (2007)
  • Author(s): M.Iyoda
  • Organizer: バングラデシュ国際化学会(基調講演)
  • Place of Presentation: ダッカ(バングラデシュ)
• [Book] Radialenes (2009)
  • Author(s): M. Iyoda
  • Total Pages: 35
  • Publisher: Georg Thieme Verlag KG
• [Book] マテリアルサイエンス有機化学 (2007)
  • Author(s): 伊与田 正彦、横山 泰、西長 亨
  • Publisher: 東京化学同人
• [Book] チオフェンと電子材料 in サルファーケミカルのフロンティア (2007)
  • Author(s): 伊与田 正彦
  • Publisher: シーエムシー出版
• [Book] Bi-and Bis-TTFs"In TTF Chemistry (2004)
  • Author(s): M. Iyoda
  • Total Pages: 27
  • Publisher: Springer
• [Publications] Y.Kuwatani, G.Yamamoto, M.Iyoda: "A twin-rotor system created on the [4]radialene frame"Org.Lett.. 5. 3371-3374 (2003)
• [Publications] T.Enoki, H.Yamazaki, K.Okabe, K.Enomoto, T.Kato, A.Miyazaki, E.Ogura, Y.Kuwatani, M.Iyoda: "Unconventional TTF-Based Molecular Magnets"Synth.Met.. 133-134. 501-503 (2003)
• [Publications] J.Nshijo, E.Ogura, J.Yamaura, A.Miyazaki, T.Enoki, T.Takano, Y.Kuwatani, M.Iyoda: "Ferromagnetic Interaction and Metallic Conductivity of Radical Ion Salts (DIEDO)_2M(mnt)_2 (M = Ni, Pt)"Synth.Met.. 133-134. 539-541 (2003)
• [Publications] T.Enoki, H.Yamazaki, J.Nishijo, A.Miyazaki, K.Ugawa, E.Ogura, Y.Kuwatani, M.Iyoda, Y.V.Sushko: "Novel Magnetism of EDO-TTFX_2 Salts (X = Br, I)"Synth.Met.. 137. 1173-1174 (2003)
• [Publications] M.Ohkoshi, T.Horino, M.Yoshida, M.Iyoda: "Synthesis and Inclusion Properties of a Novel Macrocyclic Hexaketone Monohydrate with a Hemiacetal Structure"J.Chem.Soc., Chem.Commun.. 2586-2587 (2003)
• [Publications] Y.Kuwatani, J.Igarashi, M.Iyoda: "All-Z-Hexabenzo[24]annulene with a triangular benzene cluster substructure"Tetrahedron Lett.. 45. 359-362 (2004)