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 Photobioljournal_title
Photochemistry and photobiologyauthors
Aloisi GG,Elisei F,Moro S,Miolo G,Dall'Acqua Fdoi
10.1562/0031-8655(2000)071<0506:ppotle>2.0.co;2subject
Has Abstractpub_date
2000-05-01 00:00:00pages
506-13issue
5eissn
0031-8655issn
1751-1097journal_volume
71pub_type
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