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ID 37981
本文ファイル
著者
Rizzo, Thomas R.
Boyarkin, Oleg V.
キーワード
alkali metal ions
18-crown-6
encapsulation
water
crown ether
infrared
ion trap
electrospray
solvent effect
NDC
化学
抄録(英)
We have measured electronic and conformer-specific vibrational spectra of hydrated dibenzo-18-crown-6 (DB18C6) complexes with potassium ion, K+・DB18C6・(H2O)n (n = 1-5), in a cold, 22-pole ion trap. We also present for comparison spectra of Rb+・DB18C6・(H2O)3 and Cs+・DB18C6・(H2O)3 complexes. We determine the number and the structure of conformers by analyzing the spectra with the aid of quantum chemical calculations. The K+・DB18C6・(H2O)1 complex has only one conformer under the conditions of our experiment. For K+・DB18C6・H2O)n with n = 2 and 3, there are at least two conformers even under the cold conditions, whereas Rb+・DB18C6・(H2O)3 and Cs+・DB18C6・(H2O)3 each exhibit only one isomer. The difference can be explained by the optimum matching in size between the K+ ion and the crown cavity; since the K+ ion can be deeply encapsulated by DB18C6 and the interaction between the K+ ion and the H2O molecules becomes weak, different kinds of hydration geometries can occur for the K+・DB18C6 complex, giving multiple conformations in the experiment. For K+・DB18C6・(H2O)n (n = 4 and 5) complexes, only a single isomer is found. This is attributed to a cooperative effect of the H2O molecules on the hydration of K+・DB18C6; the H2O molecules form a ring, which is bound on top of the K+・DB18C6 complex. According to the stable structure determined in this study, the K+ ion in the K+・DB18C6・(H2O)n complexes tends to be pulled largely out from the crown cavity by the H2O molecules with increasing n. Multiple conformations observed for the K+ complexes will have an advantage for the effective capture of the K+ ion over the other alkali metal ions by DB18C6 because of entropic effects on the formation of hydrated complexes.
内容記述
This is a preprint of an article published by American Chemical Society in Journal of the American Chemical Society, 2014, available online: http://pubs.acs.org/doi/abs/10.1021/ja4086066.
This work is partly supported by JSPS KAKENHI Grant Number 21350016, and the Swiss National Science foundation through grant 200020_130579 and École Polytechnique Fédérale de Lausanne (EPFL).
掲載誌名
Journal of the American Chemical Society
136巻
5号
開始ページ
1815
終了ページ
1824
出版年月日
2014-02-05
出版者
American Chemical Society
ISSN
0002-7863
出版者DOI
PubMedID
言語
英語
NII資源タイプ
学術雑誌論文
広大資料タイプ
学術雑誌論文
DCMIタイプ
text
フォーマット
application/pdf
著者版フラグ
author
権利情報
Copyright (c) 2014 American Chemical Society
関連情報URL(IsVersionOf)
http://dx.doi.org/10.1021/ja4086066
部局名
理学研究科