科学研究費助成事業　　研究成果報告書

様　式　Ｃ－１９、Ｆ－１９、Ｚ－１９ （共通）

機関番号：

研究種目：

課題番号：

研究課題名（和文）

研究代表者

研究課題名（英文）

交付決定額（研究期間全体）：（直接経費）

１２６０１

基盤研究(S)

2014～2009

動的化学に立脚した超分子錯体システムの創製

Creation of Supramolecular Complex Systems based on Dynamic Chemistry

６０１８７３３３研究者番号：

塩谷　光彦（SHIONOYA, Mitsuhiko）

東京大学・理学（系）研究科（研究院）・教授

研究期間：

２１２２５００３

平成 年 月 日現在２７ ６ ４

円 168,500,000

研究成果の概要（和文）：　本研究は、自己集合情報を内包した有機分子を合理設計し、金属イオンの特性を駆使した10 nmサイズの多成分系超分子の構築法を確立し、これらを｢エネルギー変換｣・｢運動変換・伝播｣・｢物質変換・輸送｣といった複合機能を有する超分子錯体システムに発展させることを目指した。その結果、複数の異なる基質分子（反応性有機分子、金属錯体等）の精密配列や変換反応を可能とする超分子反応場を構築し、分子配列の動的過程を世界で初めて観察することに成功した。また、金属イオンの自在配列、光エネルギーを用いた回転運動伝播制御、光駆動型多電子反応のための新しい超分子構造・機能モチーフの創出を達成した。

研究成果の概要（英文）： We started this research project with the aim of achieving the rational design of organic molecules containing self-assembly information, using metal ions to establish a constructive method for 10 nm-sized multi-component supramolecules, and thereby developing supramolecular systems which perform diverse functions related to “energy transformation”, “motional control”, and “material transformation”. For this purpose, we have developed a supramolecular space which allows precise arrangement and transformation of a variety of molecules (reactive organic molecules and metal complexes). We could also show the world’s first visualization of a transient state of molecular arrangement. Moreover, novel supramolecular structural and functional motives have been achieved directed toward controllable metal array, light-driven control of rotary motions and multi-electron reactions.

研究分野： 化学

キーワード： 超分子錯体　金属錯体　金属配列　分子認識　分子配列　動的解析　配位空間

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� ��7A�6�ňƐƚ28ŕ�5Ǟ·õǸĄǻ¤Z\czHŔƥ'D,!25 �·õǿƍ�¥Ƃ�ǫƯƊ6Ƭ<�GD6ACǬǂ'D·õÕƏȘdz¸ș7ÄƊr�^\H��ƅ6­ȕ!1ƌİNJÿ'D#36ģÀ%�ňƐƚHȓǟƊ6ƈă$)D#3�2�+� Ƞț�5ƈDŽǕĸƣ �ȇǑǕĸ�ȘǍ 47�ș � K. Omoto, S. Tashiro, M. Kuritani, M. Shionoya, Multipoint Recognition of Ditopic Aromatic Guest Molecules via Ag–π Interactions within a Dimetal-Macrocycle, J. Am. Chem. Soc. 136, 17946–17949 (2014).ȘŏǓņș DOI: 10.1021/ja5106249 � R. Kubota, S. Tashiro, M. Shiro, M. Shionoya, In situ X-ray Snapshot Analysis of Transient Molecular Adsorption in a Crystalline Channel, Nat. Chem. 6, 913–918 (2014).ȘŏǓņș DOI: 10.1038/nchem.2044 � S. Tashiro, T. Umeki, R. Kubota, M. Shionoya, Simultaneous Arrangement of up to Three Different Molecules on the Pore Surface of Metal–Macrocycle Framework (MMF): Cooperation and Competition, Angew. Chem. Int. Ed. 53, 8310–8315 (2014).ȘŏǓņș DOI: 10.1002/anie.201404179 � T. Nakamura, H. Ube, R. Miyake, M. Shionoya, A C60-Templated Tetrameric Porphyrin Barrel Complex via Zinc-Mediated Self-Assembly Utilizing Labile Capping Ligands, J. Am. Chem. Soc. 135, 18790–18793 (2013).ȘŏǓņș DOI: 10.1021/ja4110446

� T. Nakamura, H. Ube, M. Shionoya, Silver-Mediated Formation of a Cofacial Porphyrin Dimer with High Intercalation Ability of Aromatic Molecules, Angew. Chem., Int. Ed. 52, 12096–12100 (2013).ȘŏǓņș DOI: 10.1002/anie.201306510 � J.-L. H. A. Duprey, Y. Takezawa, M. Shionoya, Metal Locked DNA Three-Way Junction, Angew. Chem., Int. Ed. 52, 1212–1216 (2013).ȘŏǓņș DOI: 10.1002/anie.201207338 � T. Nakamura, H. Ube, M. Shiro, M. Shionoya, A Self-Assembled Multiporphyrin Cage Complex through Three Different Zn(II) Center Formation under Well-Balanced Aqueous Conditions, Angew. Chem., Int. Ed. 52, 720–723 (2013).ȘŏǓņș DOI: 10.1002/anie/201208040 S. Tashiro, K. Matsuoka, A. Minoda, M. Shionoya, Metallo-Foldmers with Backbone-Coordinative Oxime-Peptides: Control of Secondary Structure, Angew. Chem. Int. Ed. 51, 13123–13127 (2012).ȘŏǓņș DOI: 10.1002/anie.201206968 S. Tashiro, R. Kubota, M. Shionoya, Metal-Macrocycle Framework (MMF): Supramolecular Nano-Channel Surfaces with Shape Sorting Capability, J. Am. Chem. Soc. 134, 2461–2464 (2012).ȘŏǓņș DOI: 10.1021/ja209422m � G. H. Guido, W. Kawamura, S. Tashiro, M. Shiro, M. Shionoya, Stacked Platinum Complexes of the Magnus’ Salt-type Inside a Coordination Cage, Angew. Chem. Int. Ed. 51, 2602–2609 (2012).ȘŏǓņș DOI: 10.1002/anie.201108197 � S. Liu, G. H. Guido. Y. Takezawa, M. Kaneko, K. Tanaka, X. Guo, M. Shionoya, Direct Conductance Measurement of Individual Metallo-DNA Duplexes within Single-Molecule Break Junctions, Angew. Chem. Int. Ed. 50, 8886–8890 (2011).ȘŏǓņș DOI: 10.1002/anie.201102980 S. Hiraoka, T. Nakamura, M. Shiro, M. Shionoya, In-Water Truly Monodisperse Aggregation of Gear-Shaped Amphiphiles Based on Hydrophobic Surface Engineering, J. Am. Chem. Soc. 132, 13223–13225 (2010).ȘŏǓņș DOI: 10.1021/ja1069135 � S. Hiraoka, Y. Hisanaga, M. Shiro, M. Shionoya, A Molecular Double Ball Bearing: An AgI-PtII Dodecanuclear Quadruple-Decker Complex with Three Rotors, Angew. Chem. Int. Ed. 49, 1669–1673 (2010).ȘŏǓņș DOI: 10.1002/anie.200905947 � S. Hiraoka, Y. Yamauchi, R. Arakane, M. Shionoya, Template-Directed Synthesis of a Covalent Organic Capsule based on a 3 nm-Sized Metallo-Capsule, J. Am. Chem. Soc. 131, 11646–11647 (2009).ȘŏǓņș

DOI: 10.1021/ja903324r �ù�ƈDŽ�ȘǍ 236�ș � Mitsuhiko Shionoya, ”Supramolecular Array in Metal-Macrocycle Framework”, 5th Asian Conference on Coordination Chemistry (ACCC5), 12-16 July (2015), The University of Hong Kong, Hong Kong.ȘĪĕǖůș � Mitsuhiko Shionoya, ”Metal-mediated Base Pairing in DNA: Alternatives to Hydrogen-bonded Watson-Crick Base Pairs”, 13th International Symposium on Applied Bioinorganic Chemistry (ISABC13), 12-15 June (2015), NUI Galway, Galway, Ireland.Șåǔǖůș � Mitsuhiko Shionoya, ”Molecular Behaviors in Metal-Macrocycle Framework”, 41st International Conference on Coordination Chemistry (ICCC41), 21-25 July (2014), Suntec Singapore Convention & Exhibition Centre, Singapore.ȘĪĕǖůș � Mitsuhiko Shionoya, ”Metal-locked DNA Three-way Junction as a Novel Structural Motif of Artificial Metallo-DNA”, The 15th Asian Chemical Congress (ACC15), 19-23 August (2013), Resorts World Sentosa, Singapore.ȘĪĕǖůș � Mitsuhiko Shionoya, ”Self-assembly of Metallo-Macrocycles: Channels, Tubes, and Spherical Aggregates”, International Conference on Macrocycle and Supramolecular Chemistry (ISMSC7), 29 January-2 February (2012), Dunedin, New Zealand.ȘĪĕǖůș �ßŃ�ȘǍ 4�ș � Y. Takezawa, J.-L. H. A. Duprey, M. Shionoya, “Metal-Aided Construction of Unusual DNA Structural Motifs” in DNA in Supramolecular Chemistry and Nanotechnology. John Wiley & Sons, Inc., in press (2015). � Y. Takezawa, M. Shionoya, “DNA Inspired Self-Assembled Metal Arrays” in Biomimetics Bioinspired Materials, Mechanics, and Dynamics, Vol. 1 of Handbook of Biomimetics and Bioinspiration. World Scientific Publishing, pp. 217–245 (2014). � E. Nolan, M. Shionoya, “Bioinorganic Chemistry: Recent Advances in Bioinorganic Chemistry”, Current Opinion in Chemical Biology, Vol. 19 (2014). � G. H. Clever, M. Shionoya, “Artificial DA directed toward Synthetic Metallo-Foldamers” in Metallofoldamers: Supramolecular Architectures from Helicates to Biomimetics. G. Maayan, M. Albrecht, Eds.; Wiley, Chichester, Chapter 9, pp. 303–332 (2013). �ƁŒǚƁŗ� �ÌĘŹţȘǍ 1�ș

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