1394164-76-1Relevant articles and documents
Excited-state interactions in diastereomeric flurbiprofen-thymine dyads
Bonancía, Paula,Vayá, Ignacio,Climent, M. José,Gustavsson, Thomas,Markovitsi, Dimitra,Jiménez, M. Consuelo,Miranda, Miguel A.
, p. 8807 - 8814 (2012/11/07)
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.