John DiBenedetto

Pressure effects on the photochemical reactions of transition metal complexes

Abstract Investigations of pressure effects on the chemical and physical deactivation pathways of transition metal excited states are summarized and discussed. Particular emphasis is placed on the calculation of the activation volumes of the rate constants for the various deactivation channels and the interpretation of these in terms of reaction mechanisms.

Dual photoemissions from the room temperature solutions of the tetranuclear copper(I) clusters Cu4I4(py-X)4 (py-X=substituted pyridine)

The time-resolved emission spectra of the tetranuclear clusters Cu4I4(py-X)4(X = H, 3-Cl, 4-Ph, 4-PhCH2, or 4-But) at 296 K in toluene each display separate, uncoupled emissions from two states, a short-lived (0.13–0.56 µs) metal-to-ligand charge transfer in the range 473–537 nm and a much more intense and longer lived (10–13 µs) metal cluster centred (MCC) emission in the range 678–698 nm; for X = 4-Ph the MCC emission exhibits an unusual, temperature dependent rise-time.