UV and IR Spectroscopic Studies of Cold Alkali Metal Ion-Crown Ether Complexes in the Gas Phase
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.
Journal
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- Journal of the American Chemical Society
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Journal of the American Chemical Society 133 (31), 12256-12263, 2011-08-10
American Chemical Society
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Details 詳細情報について
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- CRID
- 1050296265985073408
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- NII Article ID
- 120005627697
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- ISSN
- 15205126
- 00027863
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- Text Lang
- en
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- Article Type
- journal article
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- Data Source
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- IRDB
- Crossref
- CiNii Articles
- KAKEN