Cluster Structure of Ionic Liquids and their Solvent Properties for Reactions in Solution

2007 Fiscal Year Final Research Report Summary

• Project/Area Number: 17350037
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Analytical chemistry
• Research Institution: Kyushu University
• Principal Investigator: ISHIGURO Shin-ichi Kyushu University, Faculty of Sciences, Chemistry Department, Professor (80111673)
• Co-Investigator(Kenkyū-buntansha): UMEBAYASHI Yasuhiro KYUSHU UNIVERSITY, Faculty of Sciences, Chemistry Department, Associate Professor (90311836) ; KANZAKI Ryo KYUSHU UNIVERSITY, Faculty of Sciences, Chemistry Department, Assistant Professor (50363320)
• Project Period (FY): 2005 – 2007
• Keywords: Ionic Liquids / Imidazolium / Pyrolidinium / Ammonium / Super acids / Liquid Structure / Proton transfer / Xray scattering

Research Abstract

Ionic Liquids have complicated molecular structures, and intramolecular and intermolecular interactions are overlapped over the range of 300-700 pm. In the present study, we aimed to isolate these interactions using X-ray scattering and theoretical DFT and MD simulation. Finally, we succeeded to extract not only short range cation-anion interactions, but also long range cation anion, cation-cation and anion-anion interactions in the range of < 2000 pm. Such a long-range interaction has been obtained for the first time over the world, and this method of approach can be applied for various types of ionic liquids. Indeed, this method of approach was applied for ionic liquids composed of imidazolium and pyrolidinium cations with varying length of alkyl chains, and the space distribution of anions around the cation, and detailed atom-atom interactions can be extracted.
On the other hand, ionic liquids composed of alkylammonium ions anions are called as protic ionic liquids. Protic ionic liquids involve dissociable protons, and a part of protons within cations are transferred to anions to give acid and base molecules. The extent of proton transfer is expressed in terms of K_IL= [acid] [base], and the K_IL, is a measure of the acid-base property of protic ionic liquids. We determined the K_IL, value of ethylanmmonium nitrate ionic liquid directly by potentiometry using an IS FET (ion-selective field-effect transistor) electrode, for the first time over the world The K_IL, value strongly depends on the nature of anion, the hydrogen bonding ability of which usually leads to a Jorge K_IL, (or small pK_IL).

Research Products

• [Journal Article] A Tale of Two Ions : the conformational landscapes bis(trifluoromethanesulfonyl)amide and N,N-dialkylpyrrolidinium (2008)
  • Author(s): J. N. C., Lopes, K., Shimizua, A. A. H.,Padua, Y., Umebayashi, S., Fukuda, K., Fujii, S., Ishiguro
  • Journal Title: J. Phys. Chem. B
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Liquid Structure of Room-Temperature Ionic Liquid, 1-Ethy1-3-methylimidazolium Bis-(trifluromethanesulfonyl) Imide (2008)
  • Author(s): K., Fujii, Y., Soejima, Y., Kyoshoin, S., Fukuda, R., Kanzaki, Y., Umebayashi, T., Yamaguchi, T., Takamuku, S., Ishiguro
  • Journal Title: J. Phys. Chem. B
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Liquid structure and conformation of a low-viscosity ionic liquid, N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl) imide studied by high-energy X-ray scattering (2008)
  • Author(s): K., Fujii, S., Shiro, S., Fukuda, T., Takamuku, Y., Umebayashi, S.,Ishiguro
  • Journal Title: J Mol. Liquids (in press)
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Liquid structure of N-butyl-N-methylpyrrolidinium bis-(trifluoromethanesulfonyl) amide ionic liquid studied by large angle X-ray scattering and molecular dynamics simulations (2008)
  • Author(s): S., Fukuda, M., Takeuchi, K., Fujii, R., Kanzaki, T., Takamuku, K., Chiba, H., Yamamoto, Y., Umebayashi, S.,Ishiguro
  • Journal Title: J. MoL Liquids (in press)
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Anion conformation of low-viscosity room-temperature ionic liquid, 1-ethyl-3-methyllimidazolium, bis(fluoroslufonyl) imide (2008)
  • Author(s): K., Fujii, Y., Umebayashi, S., Seki, S., Ishiguro
  • Journal Title: J. Phys. Chem. B 111 Pages: 12829-12833
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Lithium-Ion Solvation in Room Temperature Ionic Liquids involving bis-( Trifluoromethanesulfonyl) Imide Anion studied by Raman spectroscopy and DFT calculations (2007)
  • Author(s): Y.Umebayashi
  • Journal Title: Journal of Physical Chemistry 111 Pages: 13028-13032
  • Description: 「研究成果報告書概要(和文)」より
  • Peer Reviewed
• [Journal Article] Anion conformation of low-viscosity room-temperature ionic liquid, 1-ethyl-3-methyllimidazolium bis(fluoroslufonyl) imide (2007)
  • Author(s): K.Fujii
  • Journal Title: Journal of Physical Chemistry 111 Pages: 12829-12833
  • Description: 「研究成果報告書概要(和文)」より
  • Peer Reviewed
• [Journal Article] Solvation Structure of Li^+ in concentrated LiPF_6-propylene carbonate solutions (2007)
  • Author(s): Y.Kameda
  • Journal Title: Journal of Physical Chemistry 111 Pages: 6104-6109
  • Description: 「研究成果報告書概要(和文)」より
  • Peer Reviewed
• [Journal Article] Lithium-Ion Solvation in Room-Temperature Ionic Liquids involving bis-(Trifluoromethanesulfonyl) Imide Anion studied by Raman spectroscopy and DFT calculations (2007)
  • Author(s): Y., Umebayashi, T., Mitsugi, S., Fukuda, T., Fujimori, K., Fujii, R., Kanzaki, M., Takeuchi, S., Ishiguro
  • Journal Title: J. Phys. Chem. B 111 Pages: 13028-13032
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Solvation Structure of Li+ in concentrated LiPF6-propylene carbonate solutions (2007)
  • Author(s): Y., Kameda, Y., Umebayashi, M., Takeuchi, A., Wahab, S., Fukuda, S., Ishiguro, M., Sasaki, Y., Amo, T., Usuki
  • Journal Title: J. Phys. Chem 111 Pages: 6104-6109
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Vibrational spectroscopy and molecular orbital calculations of N,N-dimethylacrylamide and N,N-dimethylpropionamide (2007)
  • Author(s): M., Asada, T., Fujimori, K., Fujii, R., Kanzaki, Y., Umebayashi, S., Ishiguro
  • Journal Title: J. MoL Liquids 136 Pages: 138-146
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Acid-Base Property of Ethylammonium Nitrate Ionic Liquid directly obtained using Ion-Selective Field Effect Transistor Electrode (2007)
  • Author(s): R., Kanzaki, K., Uchida, S., Hara, Y., Umebayashi, S., Ishiguro, S., Nomura
  • Journal Title: .Chem. Lett. 36 Pages: 684-685
  • Description: 「研究成果報告書概要(欧文)」より
• [Presentation] Solvation number and conformation of N,N-dimethylacrylamide and N,N-dimethylpropionamide in the coordination sphere of the cobalt(II) ion in solution studied by FT-IR and FT-IRaman spectroscopy (2007)
  • Author(s): S.Ishiguro
  • Organizer: 29th International Conference on Solution Chemistry
  • Place of Presentation: Murdoch Univ. (Perth, Austria)
  • Year and Date: 2007-07-17
  • Description: 「研究成果報告書概要(和文)」より
• [Presentation] An approach to solvation of reaction intermediates by combining kinetic and thermodynamic solvent effects on the metal-ion complexation(Invited) (2005)
  • Author(s): S., Ishiguro, Y., Umebayashi, T., Ogura, N., Sigeta, R., Kanzaki, Y., Murakami
  • Organizer: PACIFICHEM 2005
  • Place of Presentation: Hawaii, USA
  • Year and Date: 20051215-20
  • Description: 「研究成果報告書概要(欧文)」より
• [Presentation] Solvent Conformation and Ion Solvation-form Molecular to Ionic Liquid(Invited) (2005)
  • Author(s): S., Ishiguro
  • Organizer: 29th Inter.Conf. on Solution Chemistry
  • Place of Presentation: Portoroz(Slovenia)
  • Year and Date: 20050821-25
  • Description: 「研究成果報告書概要(欧文)」より