Anion Effects to Electrochromic Properties of Ru-based Metallo-supramolecular Polymers

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Ru(II)-based metallo-supramolecular polymers with different counter anions (Cl-, (CF3SO2)2N-, CF3SO3-, BF4-, ClO4-, PF6- and CO32-) were prepared by anion exchange reaction in the film state. In the UV-vis. spectra, the MLCT absorption was observed around 510 nm and the maximum wavelength was slightly different among the polymers. The polymers with “soft” counter anions such as (CF3SO2)2N-, CF3SO3-, ClO4- and PF6- showed a reversible redox wave based on the redox of Ru(II)/(III). It was revealed that the redox is diffusion-controlled. The polymers with (CF3SO2)2N-, CF3SO3-, ClO4-, PF6- and BF4- showed reversible EC behavior. The polymers with (CF3SO2)2N- and ClO4- exhibited the highest durability and the quickest response (3.69/0.98 s), respectively, among the polymers. The polymer with (C3SO2)2N- has the highest color efficiency (270.3 cm2 C-1). These results suggested that the hardness/softness of counter anions greatly influences the EC properties of the Ru(II)-based metallo-supramolecular polymers.

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