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タイトル: | Properties of fluorosulfate-based ionic liquids and geometries of (FO_2SOH)OSO_2F^- and (FO_2SOH)_2O_2SOF^-. |
著者: | Enomoto, Takeshi Matsumoto, Kazuhiko https://orcid.org/0000-0002-0770-9210 (unconfirmed) Hagiwara, Rika https://orcid.org/0000-0002-7234-3980 (unconfirmed) |
著者名の別形: | 松本, 一彦 |
発行日: | 11-Oct-2011 |
出版者: | Royal Society of Chemistry |
誌名: | Dalton transactions |
巻: | 40 |
開始ページ: | 12491 |
終了ページ: | 12499 |
抄録: | A room temperature ionic liquid (IL) based on the fluorosulfate anion (SO_3F^-) has been synthesized by the reaction of 1-ethyl-3-methylimidazolium (EMIm^+) chloride and fluorosulfuric acid (HOSO_2F). The viscosity, ionic conductivity, and electrochemical window of EMImSO_3F at 25 °C are 46.6 mPa s, 10.8 mS cm^(-1), and 4.3 V, respectively. According to a solvatochromic measurement using ILs, there is a trend in the donor ability of fluoro- and oxofluoroanions, PF_6^- < BF_4^- < N(SO_2CF_3)_2^- < SO_3CF_3^- < SO_3F^- < PO_2F_2^-, which is explained by the atomic charges obtained from quantum mechanical calculations. The 1 : 2 and 1 : 3 stoichiometric reactions of EMImCl and HOSO_2F give EMIm(FO_2SOH)OSO_2F and EMIm(FO_2SOH)_2O_2SOF, respectively. Both the salts are liquid at room temperature without a HOSO_2F dissociation pressure (< 1 Pa) and have low viscosity and high ionic conductivity (9.2 mPa s and 30.8 mS cm^(-1) for EMIm(FO_2SOH)OSO_2F and 5.1 mPa s and 43.2 mS cm^(-1) for EMIm(FO_2SOH)_2O_2SOF). The vibrational modes and bonding properties of these anionic species are discussed with the aid of quantum mechanical calculations. The (FO_2SOH)OSO_2F^- anion in EMIm(FO_2SOH)OSO_2F does not have an inversion centre, which stands in contrast to the one with an inversion centre (e.g. observed in solid Cs(FO_2SOH)OSO_2F). The (FO_2SOH)_2O_2SOF^- anion in EMIm(FO_2SOH)_2O_2SOF is characterized by vibrational spectroscopy under Cs symmetry. |
著作権等: | © The Royal Society of Chemistry 2011. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。 This is not the published version. Please cite only the published version. |
URI: | http://hdl.handle.net/2433/161764 |
DOI(出版社版): | 10.1039/c1dt11014d |
PubMed ID: | 21986936 |
出現コレクション: | 学術雑誌掲載論文等 |
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