Preparation of Coordination Asymmetry at Solid Surfaces

• Project Area: Coordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
• Project/Area Number: 16H06512
• 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: Nagoya University
• Principal Investigator: Tada Mizuki 名古屋大学, 物質科学国際研究センター, 教授 (70396810)
• Project Period (FY): 2016-06-30 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥38,610,000 (Direct Cost: ¥29,700,000、Indirect Cost: ¥8,910,000); Fiscal Year 2020: ¥7,540,000 (Direct Cost: ¥5,800,000、Indirect Cost: ¥1,740,000); Fiscal Year 2019: ¥7,540,000 (Direct Cost: ¥5,800,000、Indirect Cost: ¥1,740,000); Fiscal Year 2018: ¥7,540,000 (Direct Cost: ¥5,800,000、Indirect Cost: ¥1,740,000); Fiscal Year 2017: ¥8,450,000 (Direct Cost: ¥6,500,000、Indirect Cost: ¥1,950,000); Fiscal Year 2016: ¥7,540,000 (Direct Cost: ¥5,800,000、Indirect Cost: ¥1,740,000)
• Keywords: 配位アシンメトリー / 固体表面 / 金属錯体 / 固定化 / 表面修飾 / 触媒 / アシンメトリー / 配位構造 / 固定化錯体 / キラリティー / 配位 / 表面 / ヘリシティー / 触媒・化学プロセス / ナノ材料 / 無機化学 / 配位化学

Outline of Final Research Achievements

Unique metal coordination asymmetry on solid surfaces were prepared by metal-complex attachment and surface functionalization techniques. By the collaborative works in the research unit, the attachment and functionalization of Co3 cluster, V complex, Tb complex were achieved on SiO2 surfaces and new asymmetric coordination structures were prepared at the surfaces. We characterized the prepared asymmetric coordination structures by XAFS, CD, CPL, theoretical calculation etc. and their unique reaction performances were investigated.

Academic Significance and Societal Importance of the Research Achievements

固体表面を活用して、溶液中における金属錯体の構造とは異なる新しい配位構造や配位アシンメトリーの構築が展開できる。また、これらの表面でのみ形成できる配位アシンメトリー構造を用いた触媒特性や反応性、応答性の開拓とそれらを利用した機能性の創出が期待できる。

Research Products

• [Int'l Joint Research] Univ. Munster(ドイツ)
• [Int'l Joint Research] ミュンスター大学(ドイツ)
• [Int'l Joint Research] ミュンスター大学(ドイツ)
• [Journal Article] Oxygen Reduction Reaction Performance Tuning on Pt Nanoparticle/MWCNT Catalysts by Gd Species (2020)
  • Author(s): K. Ichihashi, S. Muratsugu, H. Matsui, K. Higashi, O. Sekizawa, T. Uruga, and M. Tada
  • Journal Title: J. Phys. Chem. C Volume: 124 Issue: 49 Pages: 26925-26936
  • DOI: 10.1021/acs.jpcc.0c09308
  • Peer Reviewed
• [Journal Article] Recent progress in molecularly imprinted approach for catalysis (2020)
  • Author(s): Muratsugu Satoshi、Shirai Sora、Tada Mizuki
  • Journal Title: Tetrahedron Letters Volume: 61 Issue: 11 Pages: 151603-151603
  • DOI: 10.1016/j.tetlet.2020.151603
  • Peer Reviewed
• [Journal Article] Enhanced Oxygen Reduction Reaction Performance of Size-controlled Pt Nanoparticles on Polypyrrole-functionalized Carbon nanotubes (2019)
  • Author(s): Kentaro Ichihashi, Satoshi Muratsugu, Shota Miyamoto, Kana Sakamoto, Nozomu Ishiguro, Mizuki Tada
  • Journal Title: Dalton Transactions Volume: 印刷中 Issue: 21 Pages: 7130-7137
  • DOI: 10.1039/c9dt00158a
  • Peer Reviewed
• [Journal Article] Chemoselective epoxidation of cholesterol derivatives on a surface-designed molecularly imprinted Ru-porphyrin catalyst (2018)
  • Author(s): Muratsugu Satoshi、Baba Hiroshi、Tanimoto Tatsuya、Sawaguchi Kana、Ikemoto Satoru、Tasaki Masahiro、Terao Yosuke、Tada Mizuki
  • Journal Title: Chemical Communications Volume: 54 Issue: 40 Pages: 5114-5117
  • DOI: 10.1039/c8cc00896e
  • Peer Reviewed
• [Journal Article] Molecular Adsorbates Switch on Heterogeneous Catalysis: Induction of Reactivity by N-Heterocyclic Carbenes (2017)
  • Author(s): J. B. Ernst, C. Schwermann, G. Yokota, M. Tada, S. Muratsugu, N. L. Doltsinis, and F. Glorius
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 27 Pages: 9144-9147
  • DOI: 10.1021/jacs.7b05112
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Size Regulation and Stability Enhancement of Pt Nanoparticle Catalyst via Polypyrrole Functionalization of Carbon-Nanotube-Supported Pt Tetranuclear Complex (2017)
  • Author(s): S. Muratsugu, S. Miyamoto, K. Sakamoto, K. Ichihashi, C. K. Kim, N. Ishiguro, and M. Tada
  • Journal Title: Langmuir Volume: 33 Issue: 39 Pages: 10271-10282
  • DOI: 10.1021/acs.langmuir.7b02114
  • Peer Reviewed
• [Journal Article] Preparation and catalytic performance of a molecularly imprinted Pd complex catalyst for Suzuki cross-coupling reactions (2017)
  • Author(s): S. Muratsugu, N. Maity, H. Baba, M. Tasaki, M. Tada
  • Journal Title: Dalton Trans. Volume: 46 Issue: 10 Pages: 3125-3134
  • DOI: 10.1039/c7dt00124j
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Tunable Heterogeneous Catalysis: N-Heterocyclic Carbenes as Ligands for Supported Heterogeneous Ru/K-Al2O3 Catalysts To Tune Reactivity and Selectivity (2016)
  • Author(s): J. B. Ernst, S. Muratsugu, F. Wang, M. Tada, F. Glorius
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 34 Pages: 10718-10721
  • DOI: 10.1021/jacs.6b03821
  • Peer Reviewed / Int'l Joint Research
• [Presentation] 1,4-Arylation Reaction Activity Enhanced by Organic Ligand Modification on Cr and Rh-incorpodated Ceria Catalysts (2021)
  • Author(s): S. Ikemoto, S. Muratsugu, M. Tada
  • Organizer: 日本化学会第101回春季年会
• [Presentation] Chirality Inducement of Luminescent Tb Complex with SiO2 Surface-Attached Chiral Ligands (2021)
  • Author(s): S. Shirai, S. Muratsugu, H. Nakai, M. Tada
  • Organizer: 日本化学会第101回春季年会
• [Presentation] キラル配位子修飾シリカを用いた固定化キラルバナジウム錯体の創出 (2021)
  • Author(s): 稲垣実咲, 日比恵子, 白井そら, 邨次智, 唯美津木
  • Organizer: 日本化学会第101回春季年会
• [Presentation] キラルV、Tb錯体の酸化物表面への固定化と構造 (2020)
  • Author(s): 白井そら, 日比恵子, 邨次智, 唯美津木
  • Organizer: 錯体化学会オンライン研究会「錯体化学に基づく分子の構造変換設計と機能制御」
• [Presentation] キラル配位子修飾シリカ表面の調製と発光性プロキラルTb錯体の固定化 (2020)
  • Author(s): 白井そら, 邨次智, 中井英隆, 唯美津木
  • Organizer: 錯体化学会第70回討論会
• [Presentation] Creation of Surface Chiral Metal Complex via Achiral Metal Complex and Solid Surface with Chiral Ligands (2020)
  • Author(s): S. Muratsugu, K. Hibi, S. Shirai, M. Inagaki, and M. Tada
  • Organizer: 錯体化学会第70回討論会
• [Presentation] Enhanced Electrocatalytic Oxygen Reduction Activity on Pt-based Nanoparticle Catalysts Prepared from Platinum and Lanthanide Complexes (2019)
  • Author(s): S. Muratsugu, K. Ichihashi, M. Tada
  • Organizer: 錯体化学会第69回討論会
• [Presentation] キラル配位子修飾シリカを用いた表面キラル錯体の創出 (2019)
  • Author(s): 日比恵子, 邨次智, 唯美津木
  • Organizer: 錯体化学会第69回討論会
• [Presentation] Preparation and Operando Imaging of Pt-bimetallic Electrocatalysts for Polymer Electrolyte Fuel Cell (2019)
  • Author(s): M. Tada, S. Muratsugu, H. Matsui
  • Organizer: 5th Japan-Taiwan-Singapore-Hong Kong Quadrilateral Symposium on Coordination Chemistry (QSCC2019)
  • Int'l Joint Research / Invited
• [Presentation] キラル配位子を修飾したシリカ表面へのバナジウム錯体の固定化 (2019)
  • Author(s): 日比恵子, 邨次智, 唯美津木
  • Organizer: 日本化学会第99春季年会
• [Presentation] Tuning the Structure and Catalytic Hydrogenation Performance of Microscopic Ru Nanoclusters by 3d Metal Atoms in the Supported Metal-Porphyrin-Ru12 Complex on SiO2 Surface (2018)
  • Author(s): S. Muratsugu, A. Yamaguchi, G. Yokota, T. Maeno, and M. Tada
  • Organizer: 錯体化学会第68回討論会
• [Presentation] Enhancement of Elecrocatalytic Oxygen Reduction Performance of Pt-based Nanoparticle - Polymer- Carbon Nanotube Composite Catalysts Prepared from Pyrrole-Modified Pt Tetranuclear Complex and Lanthanide Complex (2018)
  • Author(s): K. Ichihashi, S. Muratsugu, and M. Tada
  • Organizer: 錯体化学会第68回討論会
• [Presentation] Preparation of a Molecularly-Imprinted Ru Porphyrin Catalyst for Chemoselective Epoxidation of Cholesterol Derivatives (2018)
  • Author(s): S. Muratsugu, H. Baba, T. Tanimoto, S. Ikemoto, M. Tasaki, Y. Terao, and M. Tada
  • Organizer: 43rd International Conference on Coordination Chemistry
  • Int'l Joint Research
• [Presentation] Preparation of Polypyrrole-modified Pt-based Nanoparticles on Carbon Nanotube from Pt4 Complex with Pyrrole Units and its Application to Fuel Cell Electrocatalyst (2018)
  • Author(s): K. Ichihashi, S. Miyamoto, K. Sakamoto, S. Muratsugu, and M. Tada
  • Organizer: 43rd International Conference on Coordination Chemistry
  • Int'l Joint Research
• [Presentation] Surface Coordination and Catalysis with Metal Complexes (2017)
  • Author(s): M. Tada
  • Organizer: 日本化学会第97春季年会 アジア錯体シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2017-03-16
  • Int'l Joint Research / Invited
• [Presentation] モレキュラーインプリンティングRu Porphyrin触媒を用いたステロイド類選択酸化 (2017)
  • Author(s): 馬場寛, 谷本達也, 寺尾陽介, 邨次智, 唯美津木
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 東京
  • Year and Date: 2017-03-16
• [Presentation] N-Heterocyclic Carbene-funcionalized Ru/K-Al2O3 Catalysts: Preparation, Surface Characterization, and Tunable Selective Hydrogenation Performances (2017)
  • Author(s): S. Muratsugu, J. Ernst, F. Wang, M. Tada, and F. Glorius
  • Organizer: 253rd ACS National Meeting
  • Int'l Joint Research
• [Presentation] Surface Design of a Molecularly-Imprinted Ru Porphyrin Catalyst for Selective Oxidation of Cholesterol Derivatives (2017)
  • Author(s): S. Muratsugu, H. Baba, T. Tanimoto, Y. Terao, and M. Tada
  • Organizer: 錯体化学会第67回討論会
• [Presentation] ピロールユニット修飾Pt4核錯体を起点とした粒形制御Ptナノクラスターの創製と燃料電池電極触媒への展開 (2017)
  • Author(s): 市橋健太郎, 宮本翔太, 阪本加奈, 邨次智, 唯美津木
  • Organizer: 錯体化学会第67回討論会
• [Presentation] Regioselective Oxidation of Cholesterol Derivatives on Molecular Imprinted Ru Catalysts (2017)
  • Author(s): M. Tada and S. Muratsugu
  • Organizer: 錯体化学日米二国間会議
  • Int'l Joint Research / Invited
• [Presentation] Pt Nanoclusters Prepared on Carbon Nanotube/Polypyrrole Composite for Electrocatalysis (2017)
  • Author(s): K. Ichihashi, S. Muratsugu, and M. Tada
  • Organizer: 11th Japan-China Joint Symposium on Metal Cluster Compounds
  • Int'l Joint Research / Invited
• [Presentation] 錯体－ピロールモノマー共重合法によるPt系ナノクラスター－ポリピロール－カーボンナノチューブ複合型触媒の調製と酸化還元特性評価 (2017)
  • Author(s): 市橋健太郎, 宮本翔太, 邨次智, 唯美津木
  • Organizer: 第98回日本化学会春季年会
• [Presentation] コバルト三核メタロホスト錯体のシリカ表面固定化とヘリシティー制御 (2017)
  • Author(s): 澤口加奈, 知場舜介, 白男川貴史, 酒田陽子, 馬場寛, 邨次智, 江原正博, 秋根茂久, 唯美津木
  • Organizer: 第98回日本化学会春季年会
• [Presentation] Ruポルフィリン錯体を用いた表面モレキュラーインプリンティング触媒の調製とステロイド類の選択酸化反応 (2016)
  • Author(s): 馬場寛, 谷本達哉, 寺尾陽介, 邨次智, 唯美津木
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡
  • Year and Date: 2016-09-10