このエントリーをはてなブックマークに追加
ID 37981
file
creator
Rizzo, Thomas R.
Boyarkin, Oleg V.
subject
alkali metal ions
18-crown-6
encapsulation
water
crown ether
infrared
ion trap
electrospray
solvent effect
NDC
Chemistry
abstract
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.
description
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).
journal title
Journal of the American Chemical Society
volume
Volume 136
issue
Issue 5
start page
1815
end page
1824
date of issued
2014-02-05
publisher
American Chemical Society
issn
0002-7863
publisher doi
pubmed id
language
eng
nii type
Journal Article
HU type
Journal Articles
DCMI type
text
format
application/pdf
text version
author
rights
Copyright (c) 2014 American Chemical Society
relation is version of URL
http://dx.doi.org/10.1021/ja4086066
department
Graduate School of Science



Last 12 months's access : ? times
Last 12 months's DL: ? times


This month's access: ? times
This month's DL: ? times