American Chemical Society, The Journal of Physical Chemistry A, 35(116), p. 8807-8814, 2012
DOI: 10.1021/jp3063838
Full text: Unavailable
Excited-state interactions between (S)- or (R)- flurbiprofen ((S)- or (R)-FBP) and thymidine (dThd) covalently linked in dyads 1 or 2 have been investigated. In both dyads, the only emitting species is 1FBP*, but with a lower fluorescence quantum yield (ϕF) and a shorter fluorescence lifetime (τF) than when free in solution. These results indicate that dynamic quenching occurs either by electron transfer or via exciplex formation, with FBP as the charge-donating species. In acetonitrile, both mechanisms are favored, while in dioxane exciplex formation is predominating. Isomer 1 displays lower values of ϕF and τF than its analogue 2, indicating that the relative spatial arrangement of the chromophores plays a significant role. The triplet quantum yields (ϕT) of 1 and 2 are significantly higher than the expectations based solely on 1FBP*−dThd intersystem crossing quantum yields (ϕISC), with ϕT (1) > ϕT (2). This can be explained in terms of intramolecular charge recombination at the radical ion pairs and/or the exciplexes, which would be again dependent on geometrical factors. The triplet lifetimes (τT) of 3FBP*−dThd and free 3FBP* are similar, indicating the lack of excited-state interactions at this stage. The FBP−dThd dyads could, in principle, constitute appropriate model systems for the elucidation of the excited-state interactions in noncovalent DNA−ligand complexes.