Photophysical properties of the lowest excited singlet and triplet states of thio- and seleno-psoralens

Abstract:

:The decay processes of the lowest excited singlet and triplet states of five heteropsoralens (HPS) were investigated by steady-state and shift-phase fluorometry and by laser-flash photolysis in different solvents. The emission spectra of HPS are detectable only in trifluoroethanol (TFE), where fluorescence lifetimes (tau F) and quantum yields (phi F) were measured. The triplet lifetimes (tau T), triplet (phi T) and singlet-oxygen production (phi delta) quantum yields were determined in benzene, ethanol and TFE by laser-flash photolysis. Semiempirical (INDO/1-CI) calculations allowed the nature of the lowest excited singlet and triplet states and transition probabilities to be obtained. Theoretical and experimental results indicate that the two lowest excited singlet states S1 and S2 of HPS are close-lying and different in nature (pi,pi* and n,pi*). The "proximity effect" between these two states controls the photophysical properties of HPS as it does for the other furocoumarins. However, HPS have a peculiar behavior with respect to the related compounds because they are fluorescent and have, in three cases, detectable intersystem crossing only in TFE. This behavior can be tentatively explained by a different energy gap and/or order between the S1 and S2 states.

journal_name

Photochem Photobiol

authors

Aloisi GG,Elisei F,Moro S,Miolo G,Dall'Acqua F

doi

10.1562/0031-8655(2000)071<0506:ppotle>2.0.co;2

subject

Has Abstract

pub_date

2000-05-01 00:00:00

pages

506-13

issue

5

eissn

0031-8655

issn

1751-1097

journal_volume

71

pub_type

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