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ID 37976
本文ファイル
著者
Boyarkin, Oleg V.
Kusaka, Ryoji
Rizzo, Thomas R.
キーワード
alkali metal ions
18-crown-6
15-crown-5
encapsulation
NDC
化学
抄録(英)
Electronic and vibrational spectra of benzo-15-crown-5 (B15C5) and benzo-18-crown-6 (B18C6) complexes with alkali metal ions, M+・B15C5 and M+・B18C6 (M = Li, Na, K, Rb and Cs), are measured using UV photodissociation (UVPD) and IR-UV double resonance spectroscopy in a cold, 22-pole ion trap. We determine the structure of conformers with the aid of density functional theory calculations. In the Na+・B15C5 and K+・B18C6 complexes, the crown ethers open the most and hold the metal ions at the center of the ether ring, demonstrating the optimum matching in size between the cavity of the crown ethers and the metal ions. For smaller ions, the crown ethers deform the ether ring to decrease the distance and increase the interaction between the metal ions and oxygen atoms; the metal ions are completely surrounded by the ether ring. In the case of larger ions, the metal ions are too large to enter the crown cavity and are positioned on it, leaving one of its sides open for further solvation. Thermochemistry data calculated on the basis of the stable conformers of the complexes suggest that the ion selectivity of crown ethers is controlled primarily by the enthalpy change for the complex formation in solution, which depends strongly on the complex structure.
内容記述
This is a preprint of an article published by American Chemical Society in Journal of Physical Chemistry A, 2012, available online: http://pubs.acs.org/doi/abs/10.1021/jp3011519.
This work is supported by Grant-in-Aids (Grant No. 21350016) for Scientific Research from the Ministry of Education, Culture, Sports, Science, and Technology (MEXT) of Japan, the Swiss National Science foundation through grant 200020_130579 and École Polytechnique Fédérale de Lausanne (EPFL).
掲載誌名
Journal of Physical Chemistry A
116巻
16号
開始ページ
4057
終了ページ
4068
出版年月日
2012-04-26
出版者
American Chemical Society
ISSN
1089-5639
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) 2012 American Chemical Society
関連情報URL(IsVersionOf)
http://dx.doi.org/10.1021/jp3011519
部局名
理学研究科