Internal heavy atom effect on the radiative and non-radiative rate constants in xanthene dyes

Flourescence quantum yield (ø_f), phosphorescence and fluorescence quantum yield ratio (ø_p/ø_f) and the observed triplet decay time (τ_po) of fluorescein and its halogen derivatives have been measured. On halogen substitution an increase in ø_p/ø_f and a decrease in ø_f and τ_po is observed in the sequence of Cl, Br, and I. The increase in ø_p/ø_f is not in the same proportion as the decrease in τ_po. Although ø_p/ø_f is higher for cations than for dianions, it increases more for dianions on halogen substitution. However, the increase in 1/τ_po is about 10³ times more for cations than for dianions. The radiative and non-radiative rate constants viz., k_is, k_p and k_qp have been calculated. On halogen substitution k_f remains almost constant, whereas an increase in k_p, k_is and k_qp is observed. For dianions the increase occurs in the order k_qp> k_is> k_p while for cations the order is k_qp> k_p> k_is. The deuterium solvent effect on triplet decay time and intensity is also observed.