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The trinuclear [{Ru(NH3)4(py-COOH)}(μ-CN){Ru(bpy)2}(μ-CN){Ru(NH3)4(py-COOH)}]6+ (py-COOH = isonicotinic acid, bpy = 2,2'-bipyridine) (1) and dinuclear [{Ru(dcb)2}2L]7- (dcb = 2,2'-bipyridine-4,4'-dicarboxylic acid, H3L = 9-phenyl-2,3,7-trihydroxy-6-fluorone) (2) complexes were prepared and their spectroelectrochemical behaviour characterised in solution and on conductive glass electrodes layered with Sb-doped nanocrystalline SnO2. The systems display a reversible redox response in a narrow potential range (-0.5 to +0.5 V vs SCE) and offer the possibility of controlling colour changes of electrochromic devices through variations of the coordinated and bridging ligands at the metal centres. SnO2(Sb) electrodes loaded with these dyes show switching times of the order of ms.

A series of Ru(bpy)(2)-dioxolene complexes 1-4 (bpy = 2,2'- bipyridine) and corresponding Ru(dcb)(2)-dioxolene complexes 5-8 (dcbH(2) = 2,2'-bipyridine-4,4'-dicarboxylic acid) have been prepared, and their spectroelectrochemical behavior in solution has been investigated. The complexes show reversible electrochemical behavior accompanied by a strong NIR absorption in their semiquinone forms due to a Ru(dpi) --sq(pi) MLCT band. Complete quenching of the NIR absorption occurs both upon oxidation (to the quinone form) and upon reduction (to the catechol form) very close to 0 V. The color of the systems can be tuned by using a wide range of ligands. The complexes 5-8 can be anchored onto nanocrystalline inorganic semiconductors allowing incorporation into potential electrochromic devices. As a proof of principle, compound 8 has been adsorbed on nanocrystalline Sb-doped SnO(2) supported on FTO glass, and it displays reversibly switchable electrochromic behavior in the NIR.

A series of cyano-bridged binuclear mixed valence complexes of the general formula M-Ru(III)(NH(3))(4)pyCOOH [pyCOOH = isonicotinic acid; M = cis-Ru(bpy)(2)(CN)(2), 1 (bpy = 2,2' bipyridine); trans-Ru(py)(4)(CN)(2), 2 (py = pyridine); [Ru(CN)(6)](4)(-), 3; [Fe(CN)(6)](4)(-), 4] have been prepared and anchored through the carboxylic function to nanocrystalline TiO(2) or SnO(2) electrodes. The complexes display a reversible electrochromic behavior in the range of applied potential from -0.5 to +0.5 V, versus SCE. Tuning of the electronic transitions in the visible and near-infrared spectral regions is achieved through changes of the solvent and of the cyano-bridged metal moiety M.