A01 Mitsuhiko Shionoya

Mitsuhiko Shionoya

Area leader A01


Graduate School of Science, The University of Tokyo





Research Project

Novel Development of Asymmetry Chemistry in Inorganic Nanocrystals


Shohei Tashiro (Associate Professor, Graduate School of Science, The University of Tokyo)

Hitoshi Ube (Assistant Professor, Graduate School of Science, The University of Tokyo)

Yusuke Takezawa (Assistant Professor, Graduate School of Science, The University of Tokyo)


This project aims at developing constructive methods for asymmetric coordination spheres and anisotropically assembled structures of metal complexes by theory, experiment, and instrumentation, focusing on metal elements and their coordination spheres as platforms for steric control, reactions, and functional expression. According to this purpose, methods to create asymmetric and steric/electronic structures of metal complexes and their nano– to micron–size assembled structures will be developed by the molecule–based control of the coordination spheres to establish a scientific principle of “Coordination Asymmetry”. In particular, constructive methods for chiral metal complexes, including asymmetric induction of prochiral metal complexes, and asymmetric assembled structures are expected to develop new molecules and materials with anisotropic and directional structures and functions.

Research Areas

Coordination Chemistry, Supramolecular Chemistry, Bioinorganic Chemistry


Coordination Asymmetry, Metal-Centered Chirality, Asymmetric Induction, Asymmetric Self-Assembly, Chiral Space


[31] Multipoint Hydrogen Bonding-based Molecular Recognition of Amino Acids and Peptide Derivatives in a Porous Metal-Macrocycle Framework: Residue-Specificity, Diastereoselectivity, and Conformational Control,
Shohei Tashiro; Kosuke Nakata; Ryunosuke Hayashi; Mitsuhiko Shionoya, Small, 17, 22, 2005803, 2021
DOI: 10.1002/smll.202005803.
[30] Phase-Dependent Reactivity and Host-Guest Behaviors of a Metallo-Macrocycle in Liquid and Solid-State Photosensitized Oxygenation Reactions,
Kenichiro Omoto; Shohei Tashiro; Mitsuhiko Shionoya, J. Am. Chem. Soc., 143, 14, 5406 - 5412, 2021
DOI: 10.1021/jacs.0c13338.
[29] Metal-responsive Reversible Binding of Triplex-forming Oligonucleotides with 5-Hydroxyuracil Nucleobases,
Kotaro Nishiyama; Keita Mori; Yusuke Takezawa; Mitsuhiko Shionoya, Chem. Commun., 57, 20, 2487 - 2490, 2021
DOI: 10.1039/d1cc00553g.
[28] Reconstituting the C-Centered Hexagold(I) Clusters with N-Heterocyclic Carbene Ligands,
Zhen Lei; Xiao-Li Pei; Hitoshi Ube; Mitsuhiko Shionoya, Bull. Chem. Soc. Jpn., accepted, 2021.
[27] Face-selective adsorption of a prochiral compound on the chiral pore-surface of metal-macrocycle framework (MMF) directed towards stereoselective reactions,
Shohei Tashiro; Tsutomu Umeki; Ryou Kubota; Mitsuhiko Shionoya, Faraday Discuss., 225, 1, 197 - 209, 2021
DOI: 10.1039/D0FD00019A.
[26] Site-specific polymerase incorporation of consecutive ligand-containing nucleotides for multiple metal-mediated base pairing,
Takahiro Nakama; Yusuke Takezawa ; Mitsuhiko Shionoya , Chem. Commun., 57, 11, 1392 - 1395, 2021
DOI: 10.1039/D0CC07771B.
[25] Mechanistic Studies on Photoinduced Catalytic Olefin Migration Reactions at the Pd(II) Centers of a Porous Crystal, Metal-Macrocycle Framework,
Hirotaka Yonezawa; Takafumi Shiraogawa; Mengying Han; Shohei Tashiro; Masahiro Ehara; Mitsuhiko Shionoya, Chem. Asian. J., 16, 3, 202 - 206, 2021
DOI: 10.1002/asia.202001306.


[24] Metal-Dependent DNA Base Pairing of 5-Carboxyuracil with Itself and All Four Canonical Nucleobases,
Yusuke Takezawa; Akira Suzuki; Manabu Nakaya; Kotaro Nishiyama; Mitsuhiko Shionoya, J. Am. Chem. Soc., 142, 52, 21640 - 21644, 2020
DOI: 10.1021/jacs.0c11437 .
[23] Sharp Switching of DNAzyme Activity through the Formation of a Cu(II)‐mediated Carboxyimidazole Base Pair,
Yusuke Takezawa; Lingyun Hu; Takahiro Nakama; Mitsuhiko Shionoya, Angew. Chem. Int. Ed., 59, 48, 21488 - 21492, 2020
DOI: 10.1002/anie.202009579.
[22] Asymmetric construction of tetrahedral chiral zinc with high configurational stability and catalytic activity,
Kenichi Endo; Yuanfei Liu; Hitoshi Ube; Koichi Nagata; Mitsuhiko Shionoya, Nat. Commun., 11, 6263, 2020
DOI: 10.1038/s41467-020-20074-7 .
[21] Protonation-induced Self-assembly of Bis-phenanthroline Macrocycles into Nanofibers Arrayed with Tetrachloroaurate, Hexachloroplatinate or Phosphomolybdate Ions,
Shohei Tashiro; Shun Shimizu; Masumi Kuritani; Mitsuhiko Shionoya, Dalton Trans., 49, 40, 13948 - 13953, 2020
DOI: 10.1039/D0DT03287E.
[20] Allosteric Regulation of DNAzyme Activities through Intrastrand Transformation Induced by Cu(II)-Mediated Artificial Base Pairing,
Takahiro Nakama; Yusuke Takezawa; Daisuke Sasaki; Mitsuhiko Shionoya, J. Am. Chem. Soc., 142, 22, 10153 - 10162, 2020
DOI: 10.1021/jacs.0c03129.
[19] Ligand Effects on the Photophysical Properties of N,N’-diisopropylbenzimidazolydene-protected C-centered hexagold(I) Clusters,
Zhen Lei; Koichi Nagata; Hitoshi Ube; Mitsuhiko Shionoya, J. Organomet. Chem., 917, 121271, 2020
DOI: 10.1016/j.jorganchem.2020.121271.
[18] Core-shell metal-macrocycle framework (MMF): spatially selective dye inclusion through core-to-shell anisotropic transport along crystalline 1D-channels connected by epitaxial growth,
Shohei Tashiro; Shinya Mitsui; David W. Burke; Ryou Kubota; Nobuyuki Matsushita; Mitsuhiko Shionoya, CrystEngComm, 22, 8, 1306 - 1309, 2020
DOI: 10.1039/D0CE00120A.
[17] Multi-Stimuli Responsive Interconversion between Bowl- and Capsule-Shaped Self-Assembled Zinc(II) Complexes,
Kenichi Endo; Hitoshi Ube; Mitsuhiko Shionoya, J. Am. Chem. Soc., 142, 1, 407 - 416, 2020
DOI: 10.1021/jacs.9b11099.
[16] Supramolecular DNA Three-way Junction Motifs with a Bridging Metal Center,
Yusuke Takezawa; Mitsuhiko Shionoya, Front. Chem., 7, 925, 2020
DOI: 10.3389/fchem.2019.00925.
[15] Novel Porous Crystals with Macrocycle-Based Well-Defined Molecular Recognition Sites,
Shohei Tashiro; Mitsuhiko Shionoya, Acc. Chem. Res., 53, 3, 632 - 643, 2020
DOI: 10.1021/acs.accounts.9b00566.
[14] Self-assembled Porphyrin-based Cage Complexes, M11L6 (M = ZnII, CdII), with Inner Coordination Sites in Their Crystal Structure,
Iizuka Fumiya; Hitoshi Ube; Hiroyasu Sato; Takashi Nakamura; Mitsuhiko Shionoya, Chem. Lett., 49, 323 - 326, 2020
DOI: 10.1246/cl.190943.


[13] Enzymatic Synthesis of Cu(II)-responsive Deoxyribozymes through Polymerase Incorporation of Artificial Ligand-type Nucleotides,
Yusuke Takezawa; Takahiro Nakama; Mitsuhiko Shionoya, J. Am. Chem. Soc., 141, 49, 19342 - 19350, 2019
DOI: 10.1021/jacs.9b08955.
[12] Molecular Recognition of Planar and Non-Planar Aromatic Hydrocarbons through Multipoint Ag–π Bonding in a Dinuclear Metallo-Macrocycle,
Kenichiro Omoto; Shohei Tashiro; Mitsuhiko Shionoya, Chem. Sci., 10, 30, 7172 - 7126, 2019
DOI: 10.1039/C9SC02619C.
[11] Synthesis of Hetero-multinuclear Metal Complexes by Site-Selective Redox Switching and Transmetalation on a Homo-multinuclear Complex,
Hitoshi Ube; Kenichi Endo; Hiroyasu Sato; Mitsuhiko Shionoya, J. Am. Chem. Soc., 141, 26, 10384 - 10389, 2019
DOI: 10.1021/jacs.9b04123.


[10] A Carbon-Centered Hexagold(I) Cluster Supported by N-Heterocyclic Carbene Ligands,
Hitoshi Ube; Qian Zhang; Mitsuhiko Shionoya, Organometallics, 37, 13, 2007 - 2009, 2018
DOI: 10.1021/acs.organomet.8b00291.
[9] Preferential Photoreaction in a Porous Crystal, Metal–Macrocycle Framework: PdII-Mediated Olefin Migration over [2+2] Cycloaddition,
Hirotaka Yonezawa; Shohei Tashiro; Takafumi Shiraogawa; Masahiro Ehara; Rintaro Shimada; Takeaki Ozawa; Mitsuhiko Shionoya, J. Am. Chem. Soc., 140, 48, 16610 - 16614, 2018
DOI: 10.1021/jacs.8b08534.
[8] Rational Synthesis of Benzimidazole[3]arenes by CuII-Catalyzed Post-Macrocyclization Transformation,
Shohei Tashiro; Tsutomu Umeki; Ryou Kubota; Mitsuhiko Shionoya , Chem. Sci., 9, 39, 7614 - 7619, 2018
DOI: 10.1039/c8sc03086c.


[7] A Circularly Arranged Sextuple Triptycene Gear Molecule,
Hitoshi Ube; Ryo Yamada; Jun-ichi Ishida; Hiroyasu Sato; Motoo Shiro; Mitsuhiko Shionoya, J. Am. Chem. Soc., 139, 46, 16470 - 16473, 2017
DOI: 10.1021/jacs.7b09439.
[6] Multi-functional Octamethyltetrasila[2.2]cyclophanes: Conformational Variations, Circularly Polarized Luminescence, and Organic Electroluminescence,
Masaki Shimada; Yoshinori Yamanoi; Tatsuhiko Ohto; Song-Toan Pham; Ryo Yamada; Hirokazu Tada; Kenichiro Omoto; Shohei Tashiro; Mitsuhiko Shionoya; Mineyuki Hattori; Keiko Jimura; Shigenobu Hayashi; Hikaru Koike; Munetaka Iwamura; Koichi Nozaki; Hiroshi Nishihara, J. Am. Chem. Soc., 139, 32, 11214 - 11221, 2017
DOI: 10.1021/jacs.7b05671.
[5] Chiral Metallosupramolecular Architectures,
Li-Jun Chen; Hai-Bo Yang; Mitsuhiko Shionoya , Chem. Soc. Rev., 46, 9, 2555 - 2576, 2017
DOI: 10.1039/c7cs00173h.
[4] Artificial DNA Base Pairing Mediated by Diverse Metal Ions,
Yusuke Takezawa; Jens Müller; Mitsuhiko Shionoya, Chem. Lett., 46, 5, 622 - 633, 2017
DOI: 10.1246/cl.160985.
[3] Arrangement of Proteinogenic α-Amino Acids on a Cyclic Peptide comprising Alternate Biphenyl-Cored ζ-Amino Acids,
Shohei Tashiro; Masayuki Chiba; Mitsuhiko Shionoya, Chem. Asian J., 12, 10, 1087 - 1094, 2017
DOI: 10.1002/asia.201700203.
[2] Metal-Centred Azaphosphatriptycene Gear with a Photo- and Thermally Driven Mechanical Switching Function Based on Coordination Isomerism,
Hitoshi Ube; Yoshihiro Yasuda; Hiroyasu Sato; Mitsuhiko Shionoya, Nat. Commun., 8, 14296, 2017
DOI: 10.1038/ncomms14296.


[1] pH-Dependence of the Thermal Stability of Metallo-DNA Duplexes Containing Ligand-Type 5-Hydroxyuracil Nucleobases,
Kotaro Nishiyama; Yusuke Takezawa; Mitsuhiko Shionoya, Inorg. Chim. Acta, 452, 176 - 180, 2016
DOI: 10.1016/j.ica.2016.04.040.