多孔性配位高分子の細孔次元性に注目した細孔内静電場と分子吸着能の相関解明

• Project Area: Coordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
• Project/Area Number: 19H04570
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hokkaido University
• Principal Investigator: 土方 優 北海道大学, 化学反応創成研究拠点, 特任准教授 (70622562)
• Project Period (FY): 2019-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2020: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2019: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: 多孔性配位高分子 / 理論計算 / 静電場 / 吸着

Outline of Research at the Start

多孔性配位高分子はその構造と機能の多様性が注目され、機能性錯体高分子として急速に発展してきた。細孔空間と捕捉されたゲスト分子の相互作用が機能発現・制御に重要であることは広く知られているが、一方で多孔性配位高分子の細孔空間の本質的な性質に関する理解は未だなされていない。本研究では、三次元細孔のみならず、異方的な二次元や一次元細孔の静電場にも注目していく。特に細孔の次元性に注目すると、吸着状態のような静的な状態だけでなく、細孔内拡散や細孔空間の広がり方といった動的な状態に関しても静電場は重要だと考えられ、細孔の次元性、細孔内静電場、吸着特性の関係を明らかにし細孔空間の本質的な理解を目指す。

Outline of Annual Research Achievements

本課題は理論計算によって、多孔性配位高分子骨格が形成する細孔の次元性に依存した細孔空間の静電場に注目し、機能発現機構とその特性を解明することであり、前年度に引き続き本年度（および繰越申請を行ったため翌年度）も二次元層状を有するHofmann型の集積構造の吸着挙動に関する検討を行った。積層数が減ることでゲスト分子の吸着が起きやすくなるという結果が得られていた一方で、ゲスト分子が存在しない状態において、バルク状態と数層が積層した状態で最適化構造（層間距離）と層間の相互作用エネルギーに大きな違いが無かった。そこで、ab initio molecular dynamics計算を行うと、数層の積層構造では層間距離の揺らぎがバルクより大きく、エネルギーの揺らぎも大きかった。つまり数層の積層構造においてはゲスト分子が吸着される際の構造変化が置きやすく、実際に吸着現象を示す室温付近においては積層数がバルクに比べて少ないことで、構造の揺らぎが大きくなり吸着挙動が変化したものと考えられる。
また、一次元細孔構造を有する骨格にも取り組んだ。通常、水はガス分子の選択的吸着の妨げとなるが多いが、その水が新たな相互作用サイトとして選択的ガス吸着に適切な場を形成し、ガス分子吸着の選択性の低下を防いでいる可能性を理論的に示すことができた。
本課題の新学術領域研究のメンバーとの共同研究を展開し、国際共同研究やプレスリリースなども行い、多く成果につなげることができた。

Research Progress Status

令和2年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和2年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] Sandia National Laboratories/Oak Ridge National Laboratory(米国)
• [Int'l Joint Research] Technische University Dresden(ドイツ)
• [Int'l Joint Research] National University of Singapore(シンガポール)
• [Int'l Joint Research] Technical University of Munich(ドイツ)
• [Journal Article] Alkali metal ion binding using cyclic polyketones (2022)
  • Author(s): Ozawa Narito、Shivakumar Kilingaru I.、Murugavel Muthuchamy、Inaba Yuya、Yoneda Tomoki、Ide Yuki、Pirillo Jenny、Hijikata Yuh、Inokuma Yasuhide
  • Journal Title: Chemical Communications Volume: 58 Issue: 18 Pages: 2971-2974
  • DOI: 10.1039/d2cc00361a
  • Peer Reviewed
• [Journal Article] Strain‐Induced Ring Expansion Reactions of Calix[3]pyrrole‐Related Macrocycles (2022)
  • Author(s): Inaba Yuya、Kakibayashi Yu、Ide Yuki、Pirillo Jenny、Hijikata Yuh、Yoneda Tomoki、Inokuma Yasuhide
  • Journal Title: Chemistry -A European Journal Volume: 28 Issue: 17
  • DOI: 10.1002/chem.202200056
  • Peer Reviewed
• [Journal Article] Alkyl decorated metal-organic frameworks for selective trapping of ethane from ethylene above ambient pressures (2021)
  • Author(s): Schneemann Andreas、Jing Yuan、Evans Jack D.、Toyao Takashi、Hijikata Yuh、Kamiya Yuichi、Shimizu Ken-ichi、Burtch Nicholas C.、Noro Shin-ichiro
  • Journal Title: Dalton Transactions Volume: 50 Issue: 30 Pages: 10423-10435
  • DOI: 10.1039/d1dt01477c
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Hydroxide Anion Transport in Covalent Organic Frameworks (2021)
  • Author(s): Tao Shanshan、Xu Hong、Xu Qing、Hijikata Yuh、Jiang Qiuhong、Irle Stephan、Jiang Donglin
  • Journal Title: Journal of the American Chemical Society Volume: 143 Issue: 24 Pages: 8970-8975
  • DOI: 10.1021/jacs.1c03268
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Support Effect of Metal-Organic Frameworks on Ethanol Production through Acetic Acid Hydrogenation (2021)
  • Author(s): Yoshimaru Shotaro、Sadakiyo Masaaki、Maeda Nobutaka、Yamauchi Miho、Kato Kenichi、Pirillo Jenny、Hijikata Yuh
  • Journal Title: ACS Applied Materials & Interfaces Volume: 13 Issue: 17 Pages: 19992-20001
  • DOI: 10.1021/acsami.1c01100
  • Peer Reviewed
• [Journal Article] Insoluble π-conjugated Polyimine as an Organic Adsorbent for Group 10 Metal Ions (2021)
  • Author(s): Hayato Shirakura, Yuh Hijikata, Jenny Pirillo, Tomoki Yoneda, Yumehiro Manabe, Muthuchamy Murugavel, Yuki Ide, Yasuhide Inokuma
  • Journal Title: European Journal of Inorganic Chemistry Volume: 13 Issue: 17 Pages: 1705-1708
  • DOI: 10.1002/ejic.202100172
  • Peer Reviewed
• [Journal Article] Accumulated Lattice Strain as an Internal Trigger for Spontaneous Pathway Selection (2021)
  • Author(s): Huang Hubiao、Sato Hiroshi、Pirillo Jenny、Hijikata Yuh、Zhao Yong Sheng、Cheng Stephen Z. D.、Aida Takuzo
  • Journal Title: Journal of the American Chemical Society Volume: 143 Issue: 37 Pages: 15319-15325
  • DOI: 10.1021/jacs.1c06854
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] An elastic metal-organic crystal with a densely catenated backbone (2021)
  • Author(s): Meng Wenjing、Kondo Shun、Ito Takuji、Komatsu Kazuki、Pirillo Jenny、Hijikata Yuh、Ikuhara Yuichi、Aida Takuzo、Sato Hiroshi
  • Journal Title: Nature Volume: 598 Issue: 7880 Pages: 298-303
  • DOI: 10.1038/s41586-021-03880-x
  • Peer Reviewed / Open Access
• [Journal Article] Multicolour photochromic fluorescence of a fluorophore encapsulated in a metal?organic framework (2020)
  • Author(s): Hirai Kenji、Kitagawa Taisei、Fujiwara Hideki、Pirillo Jenny、Hijikata Yuh、Inose Tomoko、Uji-i Hiroshi
  • Journal Title: Chemical Communications Volume: 56 Issue: 67 Pages: 9651-9654
  • DOI: 10.1039/d0cc03624b
  • NAID: 120007145359
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Photochemically Crushable and Regenerative Metal-Organic Framework (2020)
  • Author(s): Sato Hiroshi、Matsui Toshiya、Chen Zhiyi、Pirillo Jenny、Hijikata Yuh、Aida Takuzo
  • Journal Title: Journal of the American Chemical Society Volume: 142 Issue: 33 Pages: 14069-14073
  • DOI: 10.1021/jacs.0c06615
  • Peer Reviewed
• [Journal Article] Coordinated Water as New Binding Sites for the Separation of Light Hydrocarbons in Metal-Organic Frameworks with Open Metal Sites (2020)
  • Author(s): Pia Vervoorts, Andreas Schneemann, Inke Hante, Jenny Pirillo, Yuh Hijikata, Takashi Toyao, Kenichi Kon, Ken-ichi Shimizu, Takayoshi Nakamura, Shin-ichiro Noro* and Roland A. Fischer*
  • Journal Title: ACS Appl. Mater. Interfaces Volume: 12 Issue: 8 Pages: 9448-9456
  • DOI: 10.1021/acsami.9b21261
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Topological molecular nanocarbons: All-benzene catenane and trefoil knot (2019)
  • Author(s): Segawa Yasutomo、Kuwayama Motonobu、Hijikata Yuh、Fushimi Masako、Nishihara Taishi、Pirillo Jenny、Shirasaki Junya、Kubota Natsumi、Itami Kenichiro
  • Journal Title: Science Volume: 365 Issue: 6450 Pages: 272-276
  • DOI: 10.1126/science.aav5021
  • Peer Reviewed
• [Journal Article] The helix‐inversion mechanism in double‐stranded helical oligomers bridged by rotary cyclic boronate esters (2019)
  • Author(s): Hayashi Taku、Lee Ka Hung、Iida Hiroki、Yashima Eiji、Irle Stephan、Hijikata Yuh
  • Journal Title: Journal of Computational Chemistry Volume: 40 Issue: 23 Pages: 2036-2042
  • DOI: 10.1002/jcc.25856
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] One-Step Synthesis of an Adaptive Nanographene MOF: Adsorbed Gas-Dependent Geometrical Diversity (2019)
  • Author(s): Suginome Shun、Sato Hiroshi、Hori Akihiro、Mishima Akio、Harada Yuki、Kusaka Shinpei、Matsuda Ryotaro、Pirillo Jenny、Hijikata Yuh、Aida Takuzo
  • Journal Title: Journal of the American Chemical Society Volume: 141 Issue: 39 Pages: 15649-15655
  • DOI: 10.1021/jacs.9b07732
  • Peer Reviewed
• [Journal Article] Dynamic Topochemical Reaction Tuned by Guest Molecules in the Nanospace of a Metal-Organic Framework (2019)
  • Author(s): Kusaka Shinpei、Kiyose Atsushi、Sato Hiroshi、Hijikata Yuh、Hori Akihiro、Ma Yunsheng、Matsuda Ryotaro
  • Journal Title: Journal of the American Chemical Society Volume: 141 Issue: 40 Pages: 15742-15746
  • DOI: 10.1021/jacs.9b07682
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Trans Influence across a Metal-Metal Bond of a Paddle-Wheel Unit on Interaction with Gases in a Metal-Organic Framework (2019)
  • Author(s): Pirillo Jenny、Hijikata Yuh
  • Journal Title: Inorganic Chemistry Volume: 59 Issue: 2 Pages: 1193-1203
  • DOI: 10.1021/acs.inorgchem.9b02911
  • Peer Reviewed