Crystal downsizing of two-dimensional coordination polymers for control of their structural dynamics

• Project/Area Number: 18K14245
• Research Category: Grant-in-Aid for Early-Career Scientists
• Allocation Type: Multi-year Fund
• Review Section: Basic Section 34010:Inorganic/coordination chemistry-related
• Research Institution: Kyushu University
• Principal Investigator: Ohtani Ryo 九州大学, 理学研究院, 准教授 (30733729)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: 配位高分子 / ナノ粒子 / 熱膨張 / 水吸着

Outline of Final Research Achievements

This work demonstrated that crystal downsizing of two-dimensional flexible coordination polymers incorporating cyanido-bridged structures impacted on the thermal expansion behavior and water adsorption isotherms by comparing them with those of bulk particles. The nanoparticles exhibited a smaller coefficient of thermal expansion than the bulk particles. Moreover, structural changes in the nanoparticles due to water adsorption occurred in the lower pressure region than the bulk. Interestingly, it was found that the amount of water accommodation by the nanoparticles increased by one molecule than the bulk. These characteristics were caused by structural changes via crystal downsizing, where the zigzag layers had the corresponding contracted structures.

Academic Significance and Societal Importance of the Research Achievements

配位高分子は、配位結合に由来する構造柔軟性により多彩な機能性を示すことから次世代の無機材料として活発に研究されている。近年、粒子サイズが機能性に影響を及ぼし、さらなる機能化につながることが報告されつつある。しかし、柔軟な二次元シート構造を有する配位高分子に対して粒子サイズの影響を研究した例はなかった。本研究では、柔軟な二次元配位高分子のナノ粒子化で構造特性を制御できることを世界で初めて示した。

Research Products

• [Int'l Joint Research] シドニー大学(オーストラリア)
• [Int'l Joint Research] クイーンズランド大学/シドニー大学(オーストラリア)
• [Journal Article] Theoretical investigation of tetrahedral distortion of four-coordinate iron(ii) centres in FePd(CN)4 (2021)
  • Author(s): Fujii Susumu、Ohtani Ryo、Kuwabara Akihide
  • Journal Title: Dalton Transactions Volume: 50 Issue: 6 Pages: 1990-1994
  • DOI: 10.1039/d0dt04155f
  • Peer Reviewed
• [Journal Article] Coordination Geometry Changes in Amorphous Cyanide-Bridged Metal Organic Frameworks upon Water Adsorption (2021)
  • Author(s): Yoshino Haruka、Yamagami Kohei、Wadati Hiroki、Yamagishi Hirona、Setoyama Hiroyuki、Shimoda Sayuri、Mishima Akio、Le Ouay Benjamin、Ohtani Ryo、Ohba Masaaki
  • Journal Title: Inorganic Chemistry Volume: 60 Issue: 5 Pages: 3338-3344
  • DOI: 10.1021/acs.inorgchem.0c03742
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Light-induced excited spin state trapping in iron(iii) complexes (2021)
  • Author(s): Nakaya Manabu、Ohtani Ryo、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Inorganic Chemistry Frontiers Volume: 8 Issue: 2 Pages: 484-498
  • DOI: 10.1039/d0qi01188f
  • Peer Reviewed
• [Journal Article] Responsive Four‐Coordinate Iron(II) Nodes in FePd(CN) 4 (2020)
  • Author(s): Ohtani Ryo、Matsunari Hiromu、Yamamoto Takafumi、Kimoto Koji、Isobe Masaaki、Fujii Kotaro、Yashima Masatomo、Fujii Susumu、Kuwabara Akihide、Hijikata Yuh、Noro Shin‐ichiro、Ohba Masaaki、Kageyama Hiroshi、Hayami Shinya
  • Journal Title: Angewandte Chemie International Edition Volume: 59 Issue: 43 Pages: 19254-19259
  • DOI: 10.1002/anie.202008187
  • Peer Reviewed / Open Access
• [Journal Article] Pseudo‐Membrane Jackets: Two‐Dimensional Coordination Polymers Achieving Visible Phase Separation in Cell Membrane (2020)
  • Author(s): Ohtani Ryo、Kawano Kenichi、Kinoshita Masanao、Yanaka Saeko、Watanabe Hikaru、Hirai Kenji、Futaki Shiroh、Matsumori Nobuaki、Uji‐i Hiroshi、Ohba Masaaki、Kato Koichi、Hayami Shinya
  • Journal Title: Angewandte Chemie International Edition Volume: 59 Issue: 41 Pages: 17931-17937
  • DOI: 10.1002/anie.202006600
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Luminescent ionic liquid formed from a melted rhenium(V) cluster (2020)
  • Author(s): J. Yanagisawa, T. Hiraoka, F. Kobayashi, D. Saito, M. Yoshida, M. Kato, F. Takeiri, G. Kobayashi, M. Ohba, L. F. Lindoy, R. Ohtani, S. Hayami
  • Journal Title: Chem. Commun. Volume: 56 Issue: 57 Pages: 7957-7960
  • DOI: 10.1039/d0cc02937h
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Vapor Switching of the Luminescence Mechanism in a Re(v) Complex (2020)
  • Author(s): Kenta Sasaki, Hitomi Yamate, Haruka Yoshino, Hiroki Miura, Yuushi Shimoda, Kiyoshi Miyata, Ken Onda, Ryo Ohtani, Masaaki Ohba
  • Journal Title: Chem. Commun. Volume: 56 Issue: 85 Pages: 12961-12964
  • DOI: 10.1039/d0cc05462c
  • Peer Reviewed
• [Journal Article] Double-layered honeycomb architectures constructed via hierarchical self-assembly of hexagonal spin crossover cobalt(ii) metallacycles (2020)
  • Author(s): Akiyoshi Ryohei、Kuroiwa Keita、Sakuragi Mina、Yoshimoto Soichiro、Ohtani Ryo、Nakamura Masaaki、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Chemical Communications Volume: 56 Issue: 43 Pages: 5835-5838
  • DOI: 10.1039/d0cc02628j
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Swift and Efficient Nuclear Spin Conversion of Molecular Hydrogen Confined in Prussian Blue Analogs (2020)
  • Author(s): Yuta Ohtsubo, Akio Mishima, Akihiro Hori, Ryotaro Matsuda, Ryo Ohtani, Masaaki Ohba
  • Journal Title: Chem. Lett. Volume: 49 Issue: 2 Pages: 149-152
  • DOI: 10.1246/cl.190829
  • NAID: 130007795207
  • Peer Reviewed / Open Access
• [Journal Article] Guest Modulated Spin States of Metal Complex Assemblies (2020)
  • Author(s): Nakaya Manabu、Ohtani Ryo、Hayami Shinya
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2020 Issue: 39 Pages: 3709-3719
  • DOI: 10.1002/ejic.202000553
  • Peer Reviewed
• [Journal Article] Homo- and Heterosolvent Modifications of Hofmann-Type Flexible Two-Dimensional Layers for Colossal Interlayer Thermal Expansions (2019)
  • Author(s): Ohtani Ryo、Yanagisawa Junichi、Matsunari Hiromu、Ohba Masaaki、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Inorganic Chemistry Volume: 58 Issue: 19 Pages: 12739-12747
  • DOI: 10.1021/acs.inorgchem.9b01660
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Slow Magnetic Relaxation Triggered by a Structural Phase Transition in Long-Chain-Alkylated Cobalt(II) Single-Ion Magnets (2019)
  • Author(s): Kobayashi Fumiya、Ohtani Ryo、Nakamura Masaaki、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Inorganic Chemistry Volume: 58 Issue: 11 Pages: 7409-7415
  • DOI: 10.1021/acs.inorgchem.9b00543
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Water‐Induced Breaking of the Coulombic Ordering in a?Room‐Temperature Ionic Liquid Metal Complex (2019)
  • Author(s): Hiraoka Tomoaki、Ohtani Ryo、Nakamura Masaaki、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Chemistry - A European Journal Volume: 25 Issue: 31 Pages: 7521-7525
  • DOI: 10.1002/chem.201900069
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Weak ferromagnetism derived from spin canting in an amido-bridged homochiral Mn(iii) 1-D coordination polymer (2019)
  • Author(s): Kusumoto Sotaro、Koga Atsushi、Kobayashi Fumiya、Ohtani Ryo、Kim Yang、Lindoy Leonard F.、Hayami Shinya、Nakamura Masaaki
  • Journal Title: Dalton Transactions Volume: 48 Issue: 24 Pages: 8617-8622
  • DOI: 10.1039/c9dt00593e
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Phosphorescence at Low Temperature by External Heavy‐Atom Effect in Zinc(II) Clusters (2019)
  • Author(s): Kobayashi Fumiya、Ohtani Ryo、Teraoka Saki、Yoshida Masaki、Kato Masako、Zhang Yingjie、Lindoy Leonard F.、Hayami Shinya、Nakamura Masaaki
  • Journal Title: Chemistry - A European Journal Volume: 25 Issue: 23 Pages: 5875-5879
  • DOI: 10.1002/chem.201900343
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Consecutive oxidative additions of iodine on undulating 2D coordination polymers: Formation of I-Pt-I chains and inhomogeneous layers (2019)
  • Author(s): Ryo Ohtani, Riho Yamamoto, Hiroyoshi Ohtsu, Masaki Kawano, Jenny Pirillo, Yuh Hijikata, Masaaki Sadakiyo, Leonard F. Lindoye, and Shinya Hayami
  • Journal Title: Dalton Transactions Volume: 印刷中 Issue: 21 Pages: 7198-7202
  • DOI: 10.1039/c8dt04624g
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Wheel-type heterometallic ferromagnetic clusters: [Ni7?xMx(HL)6(μ3-OMe)4(μ3-OH)2]Cl2 (M = Zn, Co, Mn; x = 1, 3) (2018)
  • Author(s): Kobayashi Fumiya、Ohtani Ryo、Kusumoto Sotaro、Lindoy Leonard F.、Hayami Shinya、Nakamura Masaaki
  • Journal Title: Dalton Transactions Volume: 47 Issue: 46 Pages: 16422-16428
  • DOI: 10.1039/c8dt03275k
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Positive and Negative Two-Dimensional Thermal Expansion via Relaxation of Node Distortions (2018)
  • Author(s): Ohtani Ryo、Yamamoto Riho、Aoyama Takuya、Grosjean Arnaud、Nakamura Masaaki、Clegg Jack K.、Hayami Shinya
  • Journal Title: Inorganic Chemistry Volume: 57 Issue: 18 Pages: 11588-11596
  • DOI: 10.1021/acs.inorgchem.8b01617
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Abrupt spin transition in a modified-terpyridine cobalt(ii) complex with a highly-distorted [CoN6] core (2018)
  • Author(s): Nakaya Manabu、Ohtani Ryo、Shin Jong Won、Nakamura Masaaki、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Dalton Transactions Volume: 47 Issue: 39 Pages: 13809-13814
  • DOI: 10.1039/c8dt02367k
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Creating capsules with cubanes (2018)
  • Author(s): Kusumoto Sotaro、Kobayashi Fumiya、Ohtani Ryo、Zhang Yingjie、Harrowfield Jack、Kim Yang、Hayami Shinya、Nakamura Masaaki
  • Journal Title: Dalton Transactions Volume: 47 Issue: 29 Pages: 9575-9578
  • DOI: 10.1039/c8dt01911h
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Ferroelectric and luminescence properties of zinc(ii) and platinum(ii) soft complexes (2018)
  • Author(s): Akiyoshi Ryohei、Hirota Yuma、Kosumi Daisuke、Ohtani Ryo、Nakamura Masaaki、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Dalton Transactions Volume: 47 Issue: 40 Pages: 14288-14292
  • DOI: 10.1039/c8dt01100a
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Proton Relaxation Time in Water-soluble Metal Complex Nanoparticles (2018)
  • Author(s): Tsukiashi Asami、Min Kil Sik、Terasawa Hiroaki、Yoshinaga Sosuke、Takeda Mitsuhiro、Ohtani Ryo、Nakamura Masaaki、Lindoy Leonard F.、Hayami Shinya
  • Journal Title: Chemistry Letters Volume: 47 Issue: 4 Pages: 598-600
  • DOI: 10.1246/cl.180038
  • NAID: 130006638867
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed / Int'l Joint Research
• [Presentation] Melting of a 1D cyanide-bridged coordination polymer (2019)
  • Author(s): Ryo Ohtani
  • Organizer: 7th Asian Conference on Coordination Chemistry (ACCC7) (Kuala Lumpur, Malaysia)
  • Int'l Joint Research
• [Presentation] Ionic liquid metal complexes consisting of tetracyano-metalate units (2019)
  • Author(s): Ryo Ohtani
  • Organizer: 第69回錯体化学討論会（名古屋大学・名古屋）
• [Presentation] Control of structural distortions for polar materials (2019)
  • Author(s): Ryo Ohtani
  • Organizer: the Symposium of Functional Coordination Chemistry 2019 (Sun Yet-Sen university, Guangzhou, China)
  • Int'l Joint Research / Invited
• [Presentation] Structural Dynamics of 1D and 2D Cyanide-bridged Coordination Polymers: Thermal Expansion and Melting (2019)
  • Author(s): R. Ohtani
  • Organizer: 日本化学会第99回春季年会 the Asian International Symposium -Coordination Chemistry and Organometallic Chemistry-
  • Invited
• [Presentation] Tunable anisotropic thermal expansions of two-dimensional coordination polymers (2019)
  • Author(s): R. Ohtani, T. Hiraoka, H. Matsunari, S. Hayami
  • Organizer: 43rd International Conference on Coordination Chemistry
  • Int'l Joint Research / Invited
• [Remarks]
  • URL: https://sites.google.com/view/ryoohtani-chem/publications
• [Remarks]
  • URL: https://hyoka.ofc.kyushu-u.ac.jp/search/details/K007155/index.html