A 3D electropolymerized thin film based on an isoporphyrin and on a pyridine end-decorated molybdenum(II) halide cluster: Photoelectrochemical and impedance properties

Herein, the first example of formation a 3D hybrid organic-inorganic copolymer based on an isoporphyrin and pyridine end-decorated molybdenum(II) halide cluster. The thin film was obtained by electropolymerization zinc-5,15-bis(p-tolyl)porphyrin in presence polyiodometalate with 6 pendant pyridyl ligands (((Bu4N)2[{Mo6I8}(OOC-C5H4N)6]). Electrogenerated porphyrin radical cation is powerful electrophile which can rapidly react Mo(II) cluster as nucleophile to form containing stable isoporphyrin. monitored electrochemical quartz crystal microbalance (EQCM). characterized UV-Vis-NIR spectroscopy, X-ray photoelectron spectroscopy (XPS), electrochemistry, atomic force microscopy (AFM). existence proved electron spin resonance (EPR). Interestingly, spectra exhibited broadening splitting Soret band well one additional NIR between 750 nm 1000 nm. photoelectrochemical properties have been studied impedance photocurrent transient measurements under visible-NIR light irradiation. exhibits interesting response even only illumination. In solid state, could be stored for over several months year without any degradation ambient conditions air.