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【1st.Nov.】Rational Design of Metal-based Supermolecules

2018-11-01


题目:Rational Design of Metal-based Supermolecules 
报告人:Prof. Mitsuhiko Shionoya, The University of Tokyo
时间:2018年11月1日(周四),上午10:00
地点:化学A楼518会议室
邀请人:周永丰教授


Rational Design of Metal-based Supermolecules


Mitsuhiko Shionoya
Department of Chemistry, Graduate School of Science, The University of Tokyo 
7-3-1 Hongo, Bunkyo-ku, 113-0033 Tokyo, Japan
shionoya@chem.s.u-tokyo.ac.jp


Abstract
Supramolecular self-assembly of a certain number of designer organic/inorganic building blocks by directional interactions such as metal coordination is the basis of elaborate molecular systems functionalized with well-defined array, space and motion. Most molecular architectures are purpose-designed in light of the size, shape and surface natures of building blocks as well as chemical environments. On the other hand, we have occasionally come across unexpected structures and functions as a result of more complicated self-assembly processes than expected, which have often opened a new frontier in chemistry. The present lecture will highlight rational molecular design and serendipity in supramolecular chemistry by taking our recent examples of artificial metallo-DNAs,1-4 metallo-containers,5,6 molecular gearing systems7-9 and metal macrocycle framework (MMF).10-14





 
References 
1. K. Tanaka, A. Tengeiji, T. Kato, N. Toyama, M. Shionoya, Science 2003, 299, 1212.
2. K. Tanaka, G. Clever, Y. Takezawa, Y. Yamada, C. Kaul, M. Shionoya, T. Carell, Nat. Nanotechnol. 2006, 1, 190.
3. Y. Takezawa, S. Yoneda, J.-L. Duprey, T. Nakama, M. Shionoya, Chem. Sci. 2016, 7, 3006.
4. Y. Takezawa, J. Müller, M. Shionoya, Chem. Lett. (Highlight Review) 2017, 46, 622.
5. T. Nakamura, H. Ube, R. Miyake, M. Shionoya, J. Am. Chem. Soc. 2013, 135, 18790.
6. K. Omoto, S. Tashiro, M. Kuritani, M. Shionoya, J. Am. Chem. Soc. 2014, 136, 17946-.
7. K. Sanada, H. Ube, M. Shionoya, J. Am. Chem. Soc. 2016, 138, 2945.
8. H. Ube, Y. Yasuda, H. Sato, M. Shionoya, Nat. Commun. 2017, 8, 14296.
9. H. Ube, R. Yamada, J. Ishida, H. Sato, M. Shiro, M. Shionoya, J. Am. Chem. Soc. 2017, 139, 16470. 
10. S. Tashiro, R. Kubota, M. Shionoya, J. Am. Chem. Soc. 2012, 134, 2461.
11. S. Tashiro, T. Umeki, R. Kubota, M. Shionoya, Angew. Chem., Int. Ed. 2014, 53, 8310.
12. R. Kubota, S. Tashiro, M. Shiro, M. Shionoya, Nat. Chem. 2014, 6, 913.
13. R. Kubota, S. Tashiro, M. Shionoya, Chem. Sci. 2016, 7, 2217.
14. S. Tashiro, H. Yonezawa, R. Kubota, T. Umeki, M. Shionoya, Chem. Commun. 2016, 52, 7657-7660.


CV of Mitsuhiko SHIONOYA




Mitsuhiko SHIONOYA, Professor, Bioinorganic Chemistry Lab.
Department of Chemistry, Graduate School of Science
The University of Tokyo
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Phone/Fax: +81-3-5841-8061, E-mail: shionoya@chem.s.u-tokyo.ac.jp

Educational and Professional Experience
1982-1986 The University of Tokyo (Pharmaceutical Sciences)
1986-1988 Assistant Professor, Hiroshima University
1988-1990 Assistant Professor, Institute for Molecular Science
1990-1991 Assistant Professor, Hiroshima University
1991-1994 Lecturer, Hiroshima University
1991 Visiting Researcher, University of Texas at Austin, USA
1994-1995 Associate Professor, Hiroshima University
1995-1999 Professor, Institute for Molecular Science (分子科学研究所)
1995-1999 Professor, The Graduate University for Advanced Studies
1999-present Professor, The University of Tokyo (Department of Chemistry)

Awards
2003 Visiting Professor, University of Louis Pasteur
2007 Visiting Professor, Ludwig-Maximilians-Universität Munich
2007 Inoue Prize for Science (井上学術賞)
2007 The Chemical Society of Japan Award for Creative Work (日本化学会学術賞)
2008 University of Louis Pasteur Medal (ルイ・パスツール大学メダル)
2014 Visiting Professor, University of Strasbourg
2016 The Special Prize for Science and Technology, 
Prizes for Science and Technology, Research Category (文部科学大臣表彰 科学技術賞)
2018 Japan Society of Coordination Chemistry Award (錯体化学会賞)

Social Activities
Editorial Board of Supramol. Chem. (2001–)
Chemistry Society of Japan, Associate Editor of Bull. Chem. Soc. Jpn (2002–2004)
Chemistry Society of Japan, Senior Associate Editor of Bull. Chem. Soc. Jpn (2004–2008)
ULP-UT International Exchange Program Coordinator (2004–2009)
UDS-UT International Exchange Program Coordinator (2009–)
International Organizing Committee Member of ISMSC (2012–)
Chemistry Society of Japan, Director (2012–2014)
Senior Program Officer, JSPS / Research Center for Science Systems (2012.4–2015.3)
Editor-in-Chief, Chemistry Letters (2013–)
Science Council of Japan, Member (2014.10–)
Editorial Board member of Acc. Chem. Res. (2014–)

Research Interests and Subjects
Bio-Inorganic Chemistry, Supramolecular Chemistry, Coordination Chemistry, Organometallic Chemistry
(1) Nano-Array: Templated Metal Arrays with Bio-Inspired Molecules, Synthetic Molecules, and Atoms
(2) Nano-Space: Molecular Recognition and Reactions in Organic and Coordination Capsules and Cages
(3) Nano-Motion: Supramolecular Nano-Machines
(4) Coordination Asymmetry 
Selected Review Articles and Book Chapters
(1) Chiral Supramolecular Architectures, L.-J. Chen, H.-B. Yang, M. Shionoya, Chem. Soc. Rev. 46, 2555–2576 (2017).
(2) Self-Assemblies Based on Metal-Mediated Artificial Nucleobase Pairing, Y. Takezawa, J. Müller, M. Shionoya, Comprehensive Supramolecular Chemistry II, Elsevier Ltd., pp 259–293 (2017). 
(3) Artificial DNA Base Pairing Mediated by Diverse Metal Ions, Y. Takezawa, J. Müller, M. Shionoya, Chem. Lett. (Highlight Review) 46, 622–633 (2017).
(4) DNA Inspired Self-Assembled Metal Arrays, Y. Takezawa, M. Shionoya, Biomimetic Bioinspired Materials, Mechanics, and Dynamics, Vol. 1 of Handbook of Biomimetics and Bioinspiration, World Scientific Publishing, pp 217-245 (2014). 
(5) Metal-Aided Construction of Unusual DNA Structural Motifs, Y. Takezawa, J.-L. H. A. Duprey, M. Shionoya, DNA in Supramolecular Chemistry and Nanotechnology, E. Stulz, G. H. Clever Eds.; John Wiley & Sons, Inc. (2014). 
(6) Cavity-Assembled Porous Solids (CAPS) for Nanospace-Specific Functions, S. Tashiro M. Shionoya, Bull. Chem. Soc. Jpn. (Award Account) 87, 643–654 (2014).
(7) Artificial DNA directed toward Synthetic Metallo-Foldamers, G. H. Clever, M. Shionoya, Metallofoldamers: Supramolecular Architectures from Helicates to Biomimetics, G. Maayan, M. Albrecht, Eds.; Wiley, Chichester, Chapter 9, pp 303-332 (2013).
(8) Artificial DNA directed toward Synthetic Metallo-Foldamers, G. H. Clever, M. Shionoya, Metallofoldamers: Supramolecular Architectures from Helicates to Biomimetics, G. Maayan, M. Albrecht, Eds.; Wiley, Chichester, Chapter 9, pp 303-332 (2013).
(9) Elaborate Metallosupramolecular Architectures through Desymmetrization Self-Assembly of Symmetric Building Blocks, T. Nakamura, H. Ube, M. Shionoya, Chem. Lett. (Highlight Review) 42, 328–334 (2013).
(10) Stimuli-Responsive Synthetic Metallopeptides, S. Tashiro M. Shionoya, Chem. Lett. (Highlight Review) 42, 456–462 (2013).
(11) DNA in a modern world, E. Stulz, G. H. Clever, M. Shionoya, C. Mao (Eds.), Chem. Soc. Rev. 40, 5633–5635 (2011).
(12) Alternative DNA Base Pairing through Metal Coordination, G. H. Clever, M. Shionoya, Interplay between Metal Ions and Nucleic Acids, Vol. 10 of 'Metal Ions in Life Sciences', A. Sigel, H. Sigel, R. K. O. Sigel, Eds.; Springer Science + Business Media B.V., Dordrecht, pp 264-294 (2012).
(13) Metal-Base Pairing in DNA, G. H. Clever, M. Shionoya, Coord. Chem. Rev. 254, 2391–2402 (2010).
(14) Programmable Metal Assembly on Bio-inspired Templates, K. Tanaka M. Shionoya, Coord. Chem. Rev. 251, 2732–2742 (2007).
(15) Supramolecular Metal Arrays on Artificial Metallo-DNAs and Peptides, M. Shionoya, Frontiers in Transition Metal-Containing Polymers, Ed. by A. S. Abd-El-Aziz, I. Manners; Wiley-Interscience; New Jersey, pp 499-505 (2007).
(16) A Supramolecular Approach to Metal Array Programming Using Artificial DNA, M. Shionoya, Nanotechnology: Science and Computation, Ed. by J. Chien, N. Jonoska, Grzegorz Rozenberg; Springer; Berlin, Heidelberg, Part IV, Electronics, Nanowire and DNA, pp 191-197 (2006). 


 
Selected Publications at the University of Tokyo (2002-2016)
(1) A Carbon-Centered Hexagold(I) Complex Supported by N-Heterocyclic Carbene Ligands, H. Ube, Q. Zhang, M. Shionoya, Organometallics in press (2018). 
(2) Metal-Centred Azaphosphatriptycene Gear with a Photo- and Thermally Driven Mechanical Switching Function based on Coordination Isomerism, H. Ube, Y. Yasuda, H. Sato, M. Shionoya, Nat. Commun. 8, 14296 (2017).
(3) A Circularly Arranged Sextupled Triptycene Gear Molecule, H. Ube, R. Yamada, J. Ishida, H. Sato, S. Motoo, M. Shionoya, J. Am. Chem. Soc. 139, 16470–16473 (2017). (Supplementary Cover, Highlighted in Nature, 2017)
(4) Multi-functional Octamethyltetrasila[2.2]cyclophanes: Conformational Variations, Circularly Polarized Luminescence, and Organic Electroluminescence, M. Shimada, Y. Yamanoi, T. Ohto, S. Pham, R. Yamada, H. Tada, K. Omoto, S. Tashiro, M. Shionoya, M. Hattori, K. Jimura, S. Hayashi, H. Koike, M. Iwamura, K. Nozaki, H. Nishihara, J. Am. Chem. Soc. 139, 11214–11221 (2017).
(5) Rotational Control of a Dirhodium-Centered Supramolecular Four-Gear System by Ligand Exchange, K. Sanada, H. Ube, M. Shionoya, J. Am. Chem. Soc. 138, 2945–2948 (2016). (Spotlights)
(6) Metal-responsive Structural Transformation between Artificial DNA Duplexes and Three-way Junctions, Y. Takezawa, S. Yoneda, J.-L. H. A. Duprey, T. Nakama, M. Shionoya, Chem. Sci. 7, 3006–3010 (2016). (Inside Back Cover)
(7) Enzymatic Synthesis of Artificial Metallo-DNAs Utilising Template-independent DNA Polymerases, T. Kobayashi, Y. Takezawa, A. Sakamoto, M. Shionoya, Chem. Chem. 52, 3762–3765 (2016). (Back Cover) (8) Chiral Metal-Macrocycle Frameworks: Supramolecular Chirality Induction and Helicity Inversion of the Helical Metal-Macrocyclic Structures, R. Kubota, S. Tashiro, M. Shionoya, Chem. Sci. 7, 2217–2221 (2016).
(9) Iridium-Catalyzed Reductive Carbon-Carbon Bond Cleavage Reaction on a Curved Pyridylcorannulene Skeleton, D. Tashiro, M. Yamada, M. Shionoya, Angew. Chem. Int. Ed. 54, 5351–5354 (2015).
(10) Multipoint Recognition of Ditopic Aromatic Guest Molecules via Ag-π Interactions within a Dimetal Macrocycle, K. Omoto, S. Tashiro, M. Shiro, M. Shionoya, J. Am. Chem. Soc. 136, 17946–17949 (2014).
(11) In situ X-ray Snapshot Analysis of Transient Mollecular Adsorption in a Crystalline Channel, R. Kubota, S. Tashiro, M. Shiro, M. Shionoya, Nat. Chem. 6, 913–918 (2014).
(12) Simultaneous Arrangement of up to Three Different Molecules on the Pore Surface of Metal–Macrocycle Framework (MMF): Cooperation and Competition, S. Tashiro, T. Umeki, R. Kubota, M. Shionoya, Angew. Chem. Int. Ed. 53, 8310–8315 (2014). (Frontispiece).
(13) A C60-Templated Tetrameric Porphyrin Barrel Complex via Zinc-Mediated Self-Assembly Utilizing Labile Capping Ligands, T. Nakamura, H. Ube, R. Miyake, M. Shionoya, J. Am. Chem. Soc. 135, 18790–18793 (2013).
(14) Silver-Mediated Formation of a Cofacial Porphyrin Dimer with High Intercalation Ability of Aromatic Molecules, T. Nakamura, H. Ube, M. Shionoya, Angew. Chem. Int. Ed. 52, 12096–12100 (2013).
(15) Metal Locked DNA Three-Way Junction, J.-L. H. A. Duprey, Y. Takezawa, M. Shionoya, Angew. Chem. Int. Ed. 52, 1212–1216 (2013).
(16) A Self-Assembled Multi-Porphyrin Cage Complex through Three Different ZnII Center Formation under Well-Balanced Aqueous Conditions, T. Nakamura, H. Ube, M. Shiro, M. Shionoya, Angew. Chem. Int. Ed. 52, 720–723 (2013).
(17) Metal-Mediated DNA Base Pairing: Alternatives to Hydrogen-Bonded Watson-Crick Base Pairs, Y. Takezawa, M. Shionoya, Acc. Chem. Res. 45, 2066–2076 (2012).
(18) Metallo-Foldamers with Backbone-Coordinative Oxime-Peptides: Control of Secondary Structures, S. Tashiro, K. Matsuoka, A. Minoda, M. Shionoya, Angew. Chem. Int. Ed. 51, 13123–13127 (2012).
(19) Metal-Macrocycle Framework (MMF): Supramolecular Nano-Channel Surface with Shape Sorting Capability, S. Tashiro, R. Kubota, M. Shionoya, J. Am. Chem. Soc. 134, 2461–2464 (2012).
(20) Stacked Platinum Complexes of the Magnus’ Salt Type Inside a Coordination Cage, G. H. Clever, W. Kawamura, S. Tashiro, M. Shiro, M. Shionoya, Angew. Chem. Int. Ed. 51, 2602–2609 (2012) (Inside Cover & Hot paper).
(21) Direct Conductance Measurement of Individual Metallo-DNA Duplexes within Single-Molecule Break Junctions, S. Liu, G. H. Clever, Y. Takezwa, M. Kaneko, K. Tanaka, X. Guo, M. Shionoya, Angew. Chem. Int. Ed. 50, 8886–8890 (2011) (Inside Cover).
(22) In-Water Truly Monodisperse Aggregation of Gear-Shaped Amphiphiles Based on Hydrophobic Surface Engineering, S. Hiraoka, T. Nakamura, M. Shiro, M. Shionoya, J. Am. Chem. Soc. 132, 13223–13225 (2010). 
(23) Light-Triggered Crystallization of a Molecular Host-Guest Complex, G. H. Clever, S. Tashiro, M. Shionoya, J. Am. Chem. Soc. 132, 9973–9975 (2010).
(24) Site-Selective Internally-Cross-Linking between Hg(II)-Centered Apexes of an Octahedral Hexanuclear Hg(II) Capsule by a Rod-Shaped Ditopic Ligand, S. Hiraoka, M. Kiyokawa, M. Shionoya, Angew. Chem. Int. Ed. 49, 138–143 (2010).
(25) A Molecular Double Ball Bearing: An AgI-PtII Dodecanuclear Quadruple-Decker Complex with Three Rotors, S. Hiraoka, Y. Hisanaga, M. Shiro, M. Shionoya, Angew. Chem. Int. Ed. 49, 1669–1673 (2010). (Highlighted in SYNFACTS (2010)).
(26) Template-Directed Synthesis of a Covalent Organic Capsule based on a 3 nm-Sized Metallo-Capsule, S. Hiraoka, Y. Yamauchi, R. Arakane, M. Shionoya, J. Am. Chem. Soc. 131, 11646–11647 (2009) (Highlighted in Nat. Chem. (2009)).
(27) Inclusion of Anionic Guests in a Molecular Cage with Pd-Centers as Electrostatic Anchors, G. H. Clever, S. Tashiro, M. Shionoya, Angew. Chem. Int. Ed. 48, 7010–7012 (2009).
(28) Induced-Fit Formation of a Tetrameric Organic Capsule consisting of Hexagram-Shaped Amphiphile Molecules, S. Hiraoka, K. Harano, T. Nakamura, M. Shiro, M. Shionoya, Angew. Chem. Int. Ed. 48, 7006–7009 (2009).
(29) Alternate Arrangements of Two Different Metals at Chemically-Equivalent Binding Sites on a Circle, S. Hiraoka, M. Goda, M. Shionoya, J. Am. Chem. Soc. 131, 4592–4593 (2009).
(30) Discrete Self-Assembly of Iron Ions inside Triple-Stranded Artificial DNA, Y. Takezawa, W. Maeda, K. Tanaka, M. Shionoya, Angew. Chem. Int. Ed. 48, 1081–1084 (2009).
(31) A Self-Assembled Organic Capsule Formed from the Union of Six Haxagon-Shaped Amphiphile Molecules, S. Hiraoka, K. Harano, M. Shiro, M. Shionoya, J. Am. Chem. Soc. 130, 14368–14369 (2008).
(32) Ti(IV)-Centered Dynamic Inerconversion between Pd(II), Ti(IV)-Containing Ring and Cage Molecules, S. Hiraoka, Y, Sakata, M. Shionoya, J. Am. Chem. Soc. 130, 10058–10059 (2008). 
(33) Ni(II)-Mediated Self-Assembly of Artificial -Dipeptides Forming a Macrocyclic Tetranuclear Complex with Interior Spaces for In-Line Molecular Arrangement, M. Miyake, S. Tashiro, M. Shiro, K. Tanaka, M. Shionoya, J. Am. Chem. Soc. 130, 5646–5647 (2008).
(30) Ranging Correlated Motion (1.5 nm) of Two Coaxially Arranged Rotors Mediated by Helix Inversion of a Supramolecular Transmitter, S. Hiraoka, E. Okuno, T. Tanaka, M. Shiro, M. Shionoya, J. Am. Chem. Soc. 130, 9089–9098 (2008) (Highlighted in Science (2008)).
(34) 3 nm-Scale Molecular Switching between Fluorescent Coordination Capsule and Nonfluorescent Cage, K. Harano, S. Hiraoka, M. Shionoya, J. Am. Chem. Soc. 129, 5300–5301 (2007).
(35) Programmable Self-Assembly of Metal Ions in Artificial DNA, K. Tanaka, G. H. Clever, Y. Takezawa, Y. Yamada, C. Kaul, M. Shionoya, T. Carell, Nat. Nanotechnol. 1, 190–194 (2006) (Highlighted in Nature (2006)).
(36) Electrostatically Controlled Hierarchical Arrangement of Monocationic Silver (I) and Dicationic Merucury (II) Ions between Disk-Shaped Template Ligands, S. Hiraoka, T. Tanaka, M. Shionoya, J. Am. Chem. Soc. 128, 13038–13039 (2006).
(37) Isostructural Coordination Capsules for a Series of 10 Different d5 to d10 Transition-Metal Ions, S. Hiraoka, K. Harano, M. Shiro, Y. Ozawa, N. Yasuda, K. Toriumi, M. Shionoya, Angew. Chem. Int. Ed. 45, 6488–6491 (2006) (VIP and Cover picture).
(38) Quantitative Dynamic Interconversion between Ag(I)-Mediated Capsule and Cage Complexes Accompanying Guest Encapsulation/Release, S. Hiraoka, K. Harano, M. Shiro, M. Shionoya, Angew. Chem. Int. Ed. 44, 2727–2731 (2005).
(39) A Molecular Ball Bearing Mediated by Multi-Ligand Exchange in Concert, S. Hiraoka, K. Hirata, M. Shionoya, Angew. Chem. Int. Ed. 43, 3814–3818 (2004).
(40) Heterotopic Assemblage of Two Different Disk-Shaped Ligands through Trinuclear Silver(I) Complexation: Ligand Exchange-Driven Molecular Motion, S. Hiraoka, M. Shiro, M. Shionoya, J. Am. Chem. Soc. 126, 1214–1218 (2004) (Highlighted in Nature (2004)).
(41) A Discrete Self-Assembled Metal Array in Artificial DNA, K. Tanaka, A. Tengeiji, T. Kato, N. Toyama, M. Shionoya, Science 299, 1212–1213 (2003).
(42) Quantitative Formation of Sandwich-Shaped Trinuclear Silver(I) Complexes and Dynamic Nature of Their (P) ⇄ (M) Flip Motion in Solution, S. Hiraoka, K. Harano, T. Tanaka, M. Shiro, M. Shionoya, Angew. Chem. Int. Ed. 42, 5182–5185 (2003).
(43) Efficient Incorporation of a Copper Hydroxypyridone Base Pair in DNA, K. Tanaka, A. Tengeiji, T. Kato, N. Toyama, M. Shiro, M. Shionoya, J. Am. Chem. Soc. 124, 12494–12498 (2002).
(44) Formation of Silver(I)-Mediated DNA Duplex and Triplex through an Alternative Base Pair of Pyridine Nucleobases, K. Tanaka, Y. Yamada, M. Shionoya, J. Am. Chem. Soc. 124, 8802–8803 (2002).
(45) Triangular and Tetrahedral Array of Silver(I) Ions by a Novel Disk-Shaped Tridentate Ligand: Dynamic Control of Coordination Equilibrium of the Silver(I) Complexes, S. Hiraoka, T. Yi, M. Shiro, M. Shionoya, J. Am. Chem. Soc. 124, 14510–14511 (2002). 








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