Mixed 1D-2D inorganic polymeric zinc ferrocenylphosphonate: crystal structure and electrochemical study

Journal of the American Chemical Society
Olivier OmsAndré Vioux

Abstract

Needs for ferrocene immobilization on robust host structures are considerable since derivative materials may find applications in medical areas, optical devices, or catalysis. Synthesis of phosphonate functionalized ferrocene allowed its subsequent inorganic polymerization with a zinc salt. The crystallographic structure of the compound obtained, Zn(HO(3)PFc)(2).2H(2)O, shows a unique two-dimensional ferrocene arrangement anchored on a one-dimensional Zn-O-P-O-Zn backbone. The ferrocene packing in the title compound is very similar to the packing found in molecular ferrocene. The electroactivity of Zn(HO(3)PFc)(2).2H(2)O is thoroughly studied. It shows a reversible surface oxidation of ferrocene. Mössbauer spectroscopy for the oxidized compound shows an isomer shift of IS(2b) = 0.432 mm x s(-1) and a quadrupolar splitting of QS(2b) = 0.205 mm x s(-1), which is consistent with a stable S = 1/2 ferrocenium state. The magnetic susceptibility study, Mössbauer spectroscopy, and galvanostatic titration show that only the ferrocene moieties present at the surface of the crystallites are reversibly oxidized. This observation is reinforced by a complex impedance study showing mainly resistive behavior and conductivity measurements indic...Continue Reading

Citations

Nov 4, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Ruibiao FuXintao Wu
May 25, 2006·Chemistry : a European Journal·Jie WuYu Zhu
Jun 6, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Dipankar SahooVadapalli Chandrasekhar

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