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Title: Unusual coordination environment for barium cations in ion recognition conducting poly[Ni(salen)(receptor)] films.
Authors: Tedim, J
Bessada, R
Patrício, S
Magalhães, AL
Freire, C
Gurman, SJ
Hillman, AR
First Published: 19-Aug-2008
Citation: LANGMUIR, 2008, 24 (16), pp. 8998-9005
Abstract: [Ni( salen)] complexes bearing different crown ether receptors were electropolymerized to give films whose voltammetric signatures responded to Ba2+. In line with DFT calculations, X-ray absorption spectroscopy (XAS) near the Ni K-edge showed the nickel local environment in the monomers and their corresponding polymers (in the presence or absence of barium) to be identical. However, the expectation of crown size-dependent barium local environment (based on geometry and donor atom availability) was not found. XAS near the Ba K-edge showed that Ba2+ in the films coordinated to only two oxygen donors, irrespective of crown size. This surprisingly low coordination number (compared to solution species) is accompanied by a higher barium/crown ratio than the anticipated 1:1 stoichiometry. The implications of these effects for design and performance of sensors based on metal ion recognition chemistry are discussed.
DOI Link: 10.1021/la801424k
ISSN: 0743-7463
Type: Journal Article
Appears in Collections:Published Articles, Dept. of Physics and Astronomy

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