Abstract
This paper reports the formation of hybrid polyoxometalate-porphyrin copolymeric films obtained by the electro-oxidation of zinc-β-octaethylporphyrin (ZnOEP) in the presence of a functionalized Dawson-type polyoxometalate bearing two pyridyl groups (POMdbme3,3, Py-POM-Py) which will be compared to the copolymer obtained from ZnOEP and a dipyridyl compound without POM (ibme3,3). The resulting film has been characterized by UV-visible absorption spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. Electrochemical quartz crystal microbalance was employed to investigate the poly-porphyrin-POMs deposition mass.Graphical Abstract
Highlights
Polyoxometalates (POMs) form a unique class of inorganic metal-oxygen cluster compounds with applications in medicine, analytical chemistry, catalysis, electronic, and materials science [1]
In the present paper, we report the electropolymerization of ZnOEP in the presence of a functionalized Dawson-type polyoxometalate bearing two pyridyl groups (POM-dbme3,3, Scheme 1) which will be compared to the copolymer obtained from ZnOEP and a dipyridyl compound without POM
X-ray photoelectron spectra (XPS) was used to check the chemical composition of the films. poly-ibme3,3-ZnOEP (Fig. 6, black curve) exhibited peaks corresponding to Zn 2p3 (1,022.8), O 1s (533.0), N 1s (400.4, 404.4) and C 1s (285.4 eV) electrons, originating from the porphyrin and the dipyridyl ibme3,3 spacer, while the signals for F 1s (687.2 eV), and P 2p3 (136.6 eV) electrons came from the counterion PF6− that equilibrates the charges of the pyridiniums
Summary
Polyoxometalates (POMs) form a unique class of inorganic metal-oxygen cluster compounds with applications in medicine, analytical chemistry, catalysis, electronic, and materials science [1]. In the case of the formation of poly-ZnOEP-ibme3,3 (Fig. 1), iterative scans between −1.30 and +1.60 V lead to an increase of the large reduction peak between For poly-ZnOEP-POM-dbme3,3 (Scheme 1), the signals between −0.50 and −1.00 V observed during the first scan (Fig. 2) correspond to the reduction of the three vanadium ions in POM-dbme3,3 (redox couples VV/VIV) which was not well defined using an ITO electrode.
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