Dependence of the mechanism and regularities of energy transfer in binuclear lanthanide complexes in solutions on the nature of the anion and solvent

Abstract

The effect of anions contained in solutions on the energy transfer from Tb(III) and Dy(III) ions to different Ln(III) ions is investigated in aqueous and alcohol solutions. It is shown that the regularities revealed in the energy transfer are completely determined by the ratio between the dissociation rate of the binuclear complex and the rate of energy transfer in it. The rate constant k t of energy transfer in solutions in which labile binuclear complexes of Ln(III) ions are linked through the strong acid anions Cl−, NO 3 − , and HSO 4 − depends on the nature of ions in the pairs. It is demonstrated that the energy transfer in all the systems predominantly occurs through the induction-resonance mechanism. The rate constants k t in aqueous solutions of weak (acetic, salicylic, and carbonic) acids also depend on the nature of ions interacting in pairs but do not correlate with the Forster overlap integral of the spectra. In labile binuclear complexes, the interaction between these ions proceeds by the exchange-resonance mechanism at a distance of ≈0.4 nm. It is established that the constants k t in alcohol solutions of Ln(III) ions are virtually independent of the nature of the pairs of the ions interacting through the acetate bridge. A comparison of the dissociation rate constants for Ln-anion complexes in alcohol solutions and the expected intracomplex rates of energy transfer in the binuclear complexes offers a satisfactory explanation of the obtained results and makes it possible to determine the association constants for binuclear lanthanide complexes in these solutions.