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ID 46472
file
creator
Rizzo, Thomas R.
subject
lanthanide
europium
18-crown-6
15-crown-5
encapsulation
water
crown ether
infrared
ion trap
electrospray
solvent effect
NDC
Chemistry
abstract
The H2O+ radical ion, produced in an electrospray ion source via charge transfer from Eu3+, is encapsulated in benzo-15-crown-5 (B15C5) or benzo-18-crown-6 (B18C6). We measure UV photodissociation (UVPD) spectra of the (H2O•B15C5)+ and (H2O•B18C6)+ complexes in a cold, 22-pole ion trap. These complexes show sharp vibronic bands in the 35700–37600 cm–1 region, similar to the case of neutral B15C5 or B18C6. These results indicate that the positive charge in the complexes is localized on H2O, giving the forms H2O+•B15C5 and H2O+•B18C6, in spite of the fact that the ionization energy of B15C5 and B18C6 is lower than that of H2O. The formation of the H2O+ complexes and the suppression of the H3O+ production through the reaction of H2O+ and H2O can be attributed to the encapsulation of hydrated Eu3+ clusters by B15C5 and B18C6. On the other hand, the main fragment ions subsequent to the UV excitation of these complexes are B15C5+ and B18C6+ radical ions; the charge transfer occurs from H2O+ to B15C5 and B18C6 after the UV excitation. The position of the band origin for the H2O+•B18C6 complex (36323 cm–1) is almost the same as that for Rb+•B18C6 (36315 cm–1); the strength of the intermolecular interaction of H2O+ with B18C6 is similar to that of Rb+. The spectral features of the H2O+•B15C5 complex also resemble those of the Rb+•B15C5 ion. We measure IR-UV spectra of these complexes in the CH and OH stretching region. Four conformers are found for the H2O+•B15C5 complex, but there is one dominant form for the H2O+•B18C6 ion. This study demonstrates the production of radical ions by charge transfer from multivalent metal ions, their encapsulation by host molecules, and separate detection of their conformers by cold UV spectroscopy in the gas phase.
description
This work is partly supported by the Swiss National Science foundation through grant 200020_152804 and École Polytechnique Fédérale de Lausanne (EPFL). YI and TE thank the support from JSPS through the program “Strategic Young Researcher Overseas Visits Program for Accelerating Brain Circulation”.
journal title
Journal of Physical Chemistry A
volume
Volume 119
issue
Issue 45
start page
11113
end page
11118
date of issued
2015-11-12
publisher
American Chemical Society
issn
1089-5639
1520-5215
publisher doi
language
eng
nii type
Journal Article
HU type
Journal Articles
DCMI type
text
format
application/pdf
text version
author
rights
Copyright (c) 2015 American Chemical Society
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see 10.1021/acs.jpca.5b07033.
relation url
department
Graduate School of Science



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