Deirdre Leane

Electronic properties of Ru(II) complexes bound to a bisphenolate bridge with low lying π* orbitals

The synthesis and a detailed investigation into the electronic properties of mononuclear and dinuclear Ru(II) complexes of the ligand bis(2-hydroxyphenyl)-2,5-dihydropyrazine (H(2)BHD) is described. In these complexes the Ru(II) moieties are bound through O,N coordination to an anionic phenolate and the pyrazine bridge. Relatively few reports are available on the dinuclear complexes bridged across a phenolate and this study provides an opportunity to examine the impact of reduced oxygen donor ligands on metal-metal communication. The results presented here reveal some very unusual behavior whereby the apparent location of the LUMO changes between the mononuclear and dinuclear complexes. The lowest energy optical transition appears to involve the peripheral bipyridine ligand as acceptor in the mononuclear complex, whereas this ligand is not involved in the lowest energy optical transition in the dinuclear complex. The origin of this difference is not clear, however, significant changes in the electronic properties of the mononuclear complex are observed on coordination of the second metal, reflected in significant alterations in the electrochemistry of the bridge and metals as well as changes in the optical spectroscopy. The BHD(2-) bridge is shown to support weakly coupled class II behavior according to the Robin and Day classification, reflected in a K(c) of 335.

Sensitization of photo-reduction of the polyoxometalate anions [S2M18O62]4− (M = Mo, W) in the visible spectral region by the [Ru(bpy)3]2+ cation

Voltammetric, photo-physical and photo-electrochemical properties of the Dawson polyoxometalate anions alpha-[S(2)M(18)O(62)](4-) (M = Mo, W) are presented, both in the presence and absence of a series of [Ru(II)L(n)](+/2+) cations [L(n) = (bpy)(3), (bpy)(2)(Im)(2), (bpy)(2)(dpq), (bpy)(2)(box) and (biq)(2)(box)]. Electrochemical processes for both the anion and Ru(II/III) couples were detected in solutions of the salts [Ru(II)L(n)](2)[S(2)M(18)O(62)] in dimethylformamide (0.1 M Bu(4)NPF(6)) by both cyclic and hydrodynamic voltammetries. Responses were also detected when the solid salts were adhered to the surface of a glassy carbon electrode in contact with an electrolyte in which they are insoluble (CH(3)CN; 0.1M Bu(4)NPF(6)). Photolysis experiments were performed on solutions of the salts [R(4)N](4)[S(2)M(18)O(62)] (R = n-butyl or n-hexyl) and [Ru(II)L(n)](2)[S(2)M(18)O(62)] at 355 and 420 nm in dimethylformamide and acetonitrile in the presence and absence of benzyl alcohol (10% v/v). When associated with [Ru(bpy)(3)](2+), the molybdate anion exhibited a large increase in the quantum yield for photo-reduction at 420 nm. The quantum yield for the tungstate analogue was lower but the experiments again provided clear evidence for sensitization of the photo-reduction reaction in the visible spectral region. The origin of this sensitization is ascribed to the new optical transition observed around 480 nm in static ion clusters {[Ru(bpy)(3)][S(2)M(18)O(62)]}(2-) and {[Ru(bpy)(3)](2)[S(2)M(18)O(62)]} present in solution. Measurable photocurrents resulted from irradiation of solutions of the anions with white light in the presence of the electron donor dimethylformamide. Evidence is also presented for possible quencher-fluorophore interactions in the presence of certain [Ru(II)L(n)](+) cations.