par Seery, Michael M.K.;Guerin, Liz;Forster, Robert R.J.;Gicquel, Etienne 
;Hultgren, Victoria;Bond, Alan A.M.;Wedd, Anthony A.G.;Keyes, Tia T.E.
Référence The Journal of Physical Chemistry. A, 108, 36, page (7399-7405)
Publication Publié, 2004-09
;Hultgren, Victoria;Bond, Alan A.M.;Wedd, Anthony A.G.;Keyes, Tia T.E.Référence The Journal of Physical Chemistry. A, 108, 36, page (7399-7405)
Publication Publié, 2004-09
Article révisé par les pairs
| Résumé : | The interactions between [Ru(bpy)3]2+ and the polyoxotungstate anion [S2W18O62]4- in acetonitrile solution were investigated using a combination of photophysics and optical and Raman spectroscopies. The presence of ion clusters of {[Ru(bpy)3][S2W18O62]}2- (K2 = 7.7 × 105) and [Ru(bpy)3] 2[S2W18O62] (K1 = 1.0 × 106 mol-2 dm-6) are inferred. The 2:1 complex is weakly luminescent, with a lifetime at room temperature of 20 ns under aerobic conditions. Difference electronic absorption, excitation, and resonance Raman spectroscopies indicate that the tungstate anion participates in this transition. Under conditions where [Ru(bpy)3]2+ alone is photolabile, the ion clusters are photostable, with no photodecomposition or photoinduced ligand exchange reactions evident in acetonitrile. This characteristic is examined employing temperature-dependent luminescent studies which demonstrate that the observed activation energy and preexponential factor are considerably different from those of free [Ru(bpy)3]2+ and are characteristic of a photostable polypyridylruthenium complex. |
