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ID 40789
本文ファイル
著者
Morishima, Fumiya
Dedonder, Claude
Feraud, Geraldine
Jouvet, Christophe
NDC
化学
抄録(英)
The geometric and electronic structures of cold host-guest complex ions of crown ethers (CEs) in the gas phase have been investigated by ultraviolet (UV) fragmentation spectroscopy. As host CEs, we chose 15-crown-5 (15C5), 18-crown-6 (18C6), 24-crown-8 (24C8), and dibenzo-24-crown-8 (DB24C8), and as guests protonated-aniline (aniline•H+) and protonated-dibenzylamine (dBAM•H+) were chosen. The ions generated by an electrospray ionization (ESI) source were cooled in a quadrupole ion-trap (QIT) by cryogenic cooler, and the UV spectra were obtained by UV photodissociation (UVPD) spectroscopy. The UV spectroscopy was complemented by quantum chemical calculations of the most probable complex structures. The UV spectrum of aniline•H+•CE is very sensitive to the symmetry of CE; aniline•H+•18C6 shows sharp electronic spectrum similar to aniline•H+, while aniline•H+•15C5 shows very broad structure with poor Franck-Condon factors. In addition, a remarkable cage effect in the fragmentation process after UV excitation was observed in both complex ions. In the aniline•H+•CE complexes, the cage effect completely removed the dissociation channels of the aniline•H+ moiety. A large difference in the fragmentation yield between dBAM•H+•18C6 and dBAM•H+•24C8 was observed due to a large barrier for releasing dBAM•H+ from the axis of rotaxane in the latter complex.
内容記述
This study was supported in part by the France-Japan Collaboration Program (SAKURA), the Japan Society for Promotion of Science and the ANR Research Grant (ESPEM- ANR2010BLANC040501).
掲載誌名
Physical Chemistry Chemical Physics
17巻
39号
開始ページ
25925
終了ページ
25934
出版年月日
2015-10-21
出版者
Royal Society of Chemistry
ISSN
1463-9076
出版者DOI
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
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フォーマット
application/pdf
著者版フラグ
author
権利情報
Copyright (c) the Owner Societies 2015
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
関連情報URL(IsVersionOf)
http://doi.org/10.1039/C5CP01960E
部局名
理学研究科