期刊
POLYHEDRON
卷 48, 期 1, 页码 174-180出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.poly.2012.08.073
关键词
Copper(II); Scorpionates; EXAFS; XANES; Cyclic voltammetry
资金
- University of Bologna
- Sincrotrone Trieste S.C.p.A. [20090307]
Synchrotron radiation X-ray absorption spectroscopy has been used to determine the solution structure of the nitroimidazole conjugated heteroscorpionate copper(II) complex ([(L-MN)(2)Cu]Cl-2) (L-MN = 2,2-bis(3,5-dimethyl-1H-pyrazol-1-yl)-N-(2-(2-methyl-5-nitro-1H-imidazol-1-yl)ethyl)acetamide) at three different pH values. The strategy used for the XAS data analysis for a straightforward data interpretation is presented. The copper center is coordinated by two molecules of ligands, describing a quasi-octahedral figure, in all investigated solutions, demonstrating the stability of the complex in solution. The copper complex displays a pH dependence where the Cu-O first shell distance (from the carbonyl) lengthens at acid pH; the Cu-N equatorial distances are almost the same. XANES spectroscopy also indicates structural rearrangements occurring in solution at various pH, where the spectrum at pH 4.4 displays the largest differences from the other ones. The cyclic voltammetry curves obtained on the same solutions show an irreversible peak due to the reduction of Cu(II) -> Cu(I), which falls at potential of about 0.4-0.5 V versus SCE, and it is found to be depending on pH. The potentiality of the joint XAS and electrochemical approach in the determination of the structural characteristics of the solutions is highlighted. (C) 2012 Elsevier Ltd. All rights reserved.
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