Preparation and multicolor electrochromic performance of a WO3/tris(2,2'-bipyridine)ruthenium(II)/polymer hybrid film.

A tungsten trioxide (WO(3))/tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3); bpy=2,2'-bipyridine)/poly(sodium 4-styrenesulfonate) (PSS) hybrid film was prepared by electrodeposition from a colloidal triad solution containing peroxotungstic acid (PTA), Ru(bpy)(3), and PSS. A binary solution of Ru(bpy)(3) and PTA (30 vol % ethanol in water) gradually gave an orange precipitate, possibly caused by the electrostatic interaction between the cationic Ru(bpy)(3) and the anionic PTA. The addition of PSS to the binary PTA/Ru(bpy)(3) solution remarkably suppressed this precipitation and caused a stable, colloidal triad solution to form. The spectrophotometric measurements and lifetime analyses of the photoluminescence from the excited Ru(bpy)(3) ion in the colloidal triad solution suggested that the Ru(bpy)(3) ion is partially shielded from electrostatic interaction with anionic PTA by the anionic PSS polymer chain. The formation of the colloidal triad made the ternary Ru(bpy)(3)/PTA/PSS solution much more redox active. Consequently, the rate of electrodeposition of WO(3) from PTA increased appreciably by the formation of the colloidal triad, and fast electrodeposition is required for the unique preparation of this hybrid film. The absorption spectrum of the Ru(bpy)(3) ion in the film was close to its spectrum in water, but the photoexcited state of the Ru(bpy)(3) ion was found to be quenched completely by the presence of WO(3) in the hybrid film. The cyclic voltammogram (CV) of the hybrid film suggested that the Ru(bpy)(3) ion performs as it is adsorbed onto WO(3) during the electrochemical oxidation. An ohmic contact between the Ru(bpy)(3) ion and the WO(3) surface could allow the electrochemical reaction of adsorbed Ru(bpy)(3). The composition of the hybrid film, analyzed by electron probe microanalysis (EPMA), suggested that the positive charge of the Ru(bpy)(3) ion could be neutralized by partially reduced WO(3)(-) ions, in addition to Cl(-) and PSS units, based on the charge balance in the film. The electrostatic interaction between the WO(3)(-) ion and the Ru(bpy)(3) ion might be responsible for forming the electron transfer channel that causes the complete quenching of the photoexcited Ru(bpy)(3) ion, as well as the formation of the ohmic contact between the Ru(bpy)(3) ion and WO(3). A multicolor electrochromic performance of the WO(3)/Ru(bpy)(3)/PSS hybrid film was observed, in which transmittances at 459 and 800 nm could be changed, either individually or at once, by the selection of a potential switch. Fast responses, of within a few seconds, to these potential switches were exhibited by the electrochromic hybrid film.