Correlating structure and ion recognition properties of [Ni( salen)]-based polymer films

The structural origins of ion recognition by electrochemically addressable poly[Ni( salen)] thin films are explored using in situ X-ray spectroscopy. XANES and EXAFS provided the local environment (nearest and next-nearest neighbours) around the Ni atom and solution-derived Ba 2+ bound to the film....

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Bibliographic Details
Published in:Journal of electroanalytical chemistry (Lausanne, Switzerland) Switzerland), 2007-11, Vol.610 (1), p.46-56
Main Authors: Tedim, J., Carneiro, A., Bessada, R., Patrício, S., Magalhães, A.L., Freire, C., Gurman, S.J., Hillman, A.R.
Format: Article
Language:English
Subjects:
Analytical chemistry
Barium
Chemistry
Electrochemical methods
Electrochemistry
Exact sciences and technology
EXAFS
Nickel Schiff bases
X-ray absorption spectroscopy
X-ray photoelectron spectroscopy
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Summary:The structural origins of ion recognition by electrochemically addressable poly[Ni( salen)] thin films are explored using in situ X-ray spectroscopy. XANES and EXAFS provided the local environment (nearest and next-nearest neighbours) around the Ni atom and solution-derived Ba 2+ bound to the film. The Ni is covalently bound to two N and two O donors in square planar geometry, irrespective of film redox state and the presence (or absence) of bound Ba 2+. The role of the Ni is purely structural; dramatic changes in i– E response accompanying Ba 2+ uptake are assigned to the delocalised poly( salen) polymer spine. Ba 2+ is trapped in a pseudo-crown formed by two methoxy O donors and two O donors shared with the Ni atom. The Ba 2+ EXAFS signal from thick films (10 μm) is significantly below that anticipated from electrochemical observations on thin films (
ISSN:1572-6657
1873-2569
DOI:10.1016/j.jelechem.2007.06.025