Structural, electrochemical, and spectroscopic characterization of a redox pair of sulfite-based polyoxotungstates:: α-[W18O54(SO3)2]4- and α-[W18O54(SO3)2]5-

The synthesis, isolation, and structural characterization of the fully oxidized sulfite-based polyoxotungstate cluster (Pr4N)(4){alpha-[W18O54(SO3)(2)]}center dot 2CH(3)CN and the one-electron reduced form (Pr4N)(5){alpha-[W18O54(SO3)(2)]}center dot 2CH(3)CN has been achieved. alpha-[W18O54(SO3)(2)](5-) was obtained as a Pr4N+ salt by reducing the "Trojan Horse" [W18O56(SO3)(2)(H2O)(2)](8-) cluster via a template orientation transformation. Acetonitrile solutions of pure alpha-[W18O54(SO3)(2)](5-) also were prepared electrochemically by one-electron bulk reductive electrolysis of alpha-[W18O54(SO3)(2)](4-). Cyclic voltammetry of alpha-[W18O54(SO3)(2)](4-) and alpha-[W18O54(SO3)(2)](5-) in CH3CN (0.1 M Hx(4)NClO(4)) produces evidence for an extensive series of reversible one-electron redox processes, that are associated with the tungsten-oxo framework of the polyoxometalate cluster. Hydrodynamic voltammograms in CH3CN exhibit the expected sign and magnitude of the steady-state limiting current values for the alpha-[W18O54(SO3)(2)](4-/5-/6-) series and confirm the existence of a stable one-electron reduced species, alpha-[W18O54(SO3)(2)](5-). Employment of the Randles-Sevcik (cyclic voltammetry) and Levich (rotating disk electrode) equations at a glassy carbon electrode (d = 3 mm) enable diffusion coefficient values of 3.7 and 3.8 x 10(-6) cm(2) s(-1) to be obtained for alpha-[W18O54(SO3)(2)](4-) and alpha-[W18O54(SO3)(2)](5-), respectively. The tungsten polyoxometalates are highly photoactive, since measurable photocurrents and color changes are detected for both species upon irradiation with white light. EPR spectra obtained from both acetonitrile solution and solid samples, down to temperatures as low as 2.3 K, of the chemically and electrochemically prepared one-electron reduced species provided evidence that the unpaired electron in alpha-[W18O54(SO3)(2)](5-) is delocalized over a number of atoms in the polyoxometalate structure, even at very low temperatures.