UV and IR Spectroscopic Studies of Cold Alkali Metal Ion-Crown Ether Complexes in the Gas Phase
Journal of the American Chemical Society Volume 133 Issue 31
Page 12256-12263
published_at 2011-08-10
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| File | |
| Title ( eng ) |
UV and IR Spectroscopic Studies of Cold Alkali Metal Ion-Crown Ether Complexes in the Gas Phase
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| Creator |
Boyarkin Oleg V.
Kusaka Ryoji
Rizzo Thomas R.
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| Source Title |
Journal of the American Chemical Society
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| Volume | 133 |
| Issue | 31 |
| Start Page | 12256 |
| End Page | 12263 |
| Abstract |
We report UV photodissociation (UVPD) and IR-UV double-resonance spectra of dibenzo-18-crown-6 (DB18C6) complexes with alkali metal ions (Li+, Na+, K+, Rb+, and Cs+) in a cold, 22-pole ion trap. All the complexes show a number of vibronically resolved UV bands in the 36000－38000 cm-1 region. The Li+ and Na+ complexes each exhibit two stable conformations in the cold ion trap (as verified by IR-UV double-resonance), whereas the K+, Rb+, and Cs+ complexes exist in a single conformation. We analyze the structure of the conformers with the aid of density functional theory (DFT) calculations. In the Li+ and Na+ complexes, DB18C6 distorts the ether ring to fit the cavity size to the small diameter of Li+ and Na+. In the complexes with K+, Rb+, and Cs+, DB18C6 adopts a boat-type (C2v) open conformation. The K+ ion is captured in the cavity of the open conformer thanks to the optimum matching between the cavity size and the ion diameter. The Rb+ and Cs+ ions sit on top of the ether ring, because they are too large to enter the cavity of the open conformer. According to time-dependent DFT calculations, complexes that are highly distorted to hold metal ions open the ether ring upon S1－S0 excitation, and this is confirmed by extensive low-frequency progressions in the UVPD spectra.
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| Descriptions |
This is a preprint of an article published by American Chemical Society in Journal of the American Chemical Society, 2011, available online: http://pubs.acs.org/doi/abs/10.1021/ja2046205.
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 and the Swiss National Science foundation through grant 200020_130579.
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| NDC |
Chemistry [ 430 ]
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| Language |
eng
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| Resource Type | journal article |
| Publisher |
American Chemical Society
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| Date of Issued | 2011-08-10 |
| Rights |
Copyright (c) 2011 American Chemical Society
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| Publish Type | Author’s Original |
| Access Rights | open access |
| Source Identifier |
[ISSN] 0002-7863
[DOI] 10.1021/ja2046205
[DOI] http://dx.doi.org/10.1021/ja2046205
isVersionOf
[PMID] 21728334
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