UV photodissociation spectroscopy of cryogenic cooled gas phase host-guest complex ions of crown ethers
Use this link to cite this item : https://ir.lib.hiroshima-u.ac.jp/00040789
ID | 40789 |
file | |
creator |
Morishima, Fumiya
Dedonder, Claude
Feraud, Geraldine
Jouvet, Christophe
|
NDC |
Chemistry
|
abstract | 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.
|
description | 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).
|
journal title |
Physical Chemistry Chemical Physics
|
volume | Volume 17
|
issue | Issue 39
|
start page | 25925
|
end page | 25934
|
date of issued | 2015-10-21
|
publisher | Royal Society of Chemistry
|
issn | 1463-9076
|
publisher doi | |
language |
eng
|
nii type |
Journal Article
|
HU type |
Journal Articles
|
DCMI type | text
|
format | application/pdf
|
text version | author
|
rights | Copyright (c) the Owner Societies 2015
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
|
relation is version of URL | http://doi.org/10.1039/C5CP01960E
|
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