Abstract
Studies of melatonin photoreactivity in water solutions: An effect of an external heavy atom I− on UV/Vis absorption, fluorescence and phosphorescence spectra is explored. The data allowed determination of relevant energetics for the system.The heavy atom effect (HAE) of I− on melatonin is clearly found to induce an intersystem crossing from the lowest energy singlet state to the lowest energy triplet state (T1) by a state mixing. Lifetime for the first excited triplet states of melatonin in association with I− and quenching rates for halomethanes (CH2X2, CHX3, CY4, X = Cl, Br, Y = Cl) are determined from Time-Correlated Single-Photon Counting decay curves for the phosphorescence. Dramatic alterations in quenching rate constants with quenchers as CH2X2 < CHX3 < CX4 and Cl < Br are attributed to energy transfer from an I−…Me*(T1) complex to low-lying electronic states of the halomethanes followed by dissociation to form R and X fragments. Relevance of the melatonin photoreactivity to photosensitizer properties in organic media is discussed.Graphical abstract
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