Solvent dynamical control of ultrafast ground state electron transfer: implications for Class II-III mixed valency

We relate the solvent and temperature dependence of the rates of intramolecular electron transfer (ET) of mixed valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}-1, where L = pyridyl ligand and BL = pyrazine. Complexes were reduced chemically or electrochemically to obtain the mixed valence anions in seven solvents: acetonitrile, methylene chloride, dimethylformamide, tetrahydrofuran, dimethylsulfoxide, chloroform, and hexamethylphosphoramide. Rate constants for intramolecular ET were estimated by simulating the observed degree of nu(CO) IR band shape coalescence in the mixed valence state. Correlations between rate constants for ET and solvent properties including static dielectric constant, optical dielectric constant, the quantity 1/epsilonop - 1/epsilonS, microscopic solvent polarity, viscosity, cardinal rotational moments of inertia, and solvent relaxation times were examined. In the temperature study, the complexes displayed a sharp increase in the ket as the freezing points of the solvents methylene chloride and acetonitrile were approached. The solvent phase transition causes a localized-to-delocalized transition in the mixed valence ions and an acceleration in the rate of ET. This is explained in terms of decoupling the slower solvent motions involved in the frequency factor nuN which increases the value of nuN. The observed solvent and temperature dependence of the ket for these complexes is used in order to formulate a new definition for Robin-Day class II-III mixed valence compounds. Specifically, it is proposed that class II-III compounds are those for which thermodynamic properties of the solvent exert no control over ket, but the dynamic properties of the solvent still influence ket.     

On L-Tychonoff spaces II

This paper is a sequel to the 1995 paper On L-Tychonoff spaces. The embedding theorem for L-topological spaces is shown to hold true for L an arbitrary complete lattice without imposing any order reversing involution (·)^′ on L. Some results on completely L-regular spaces and on L-Tychonoff spaces, which have previously been known to hold true for (L,^′) a frame, are exhibited as ones holding for (L,^′) a meet-continuous lattice. For such a lattice an insertion theorem for completely L-regular spaces is given. Some weak forms of separating families of maps are discussed. We also clarify the dependence between the sub-T₀ separation axiom of Liu and the L-T₀ separation axiom of Rodabaugh.     

ChemInform Abstract: Structural and Electrochemical Study od a New Crystalline Hydrate Iron(III) Phosphate FePO4·H2O Obtained from LiFePO4(OH) by Ion Exchange.

FePO₄·H₂O is prepared by Li⁺/H⁺ exchange from an aqueous HNO₃ suspension of LiFePO₄(OH) at about 60 °C.