Fluorescence quenching of CdS quantum dots by 4-azetidinyl-7-nitrobenz-2- oxa-1,3-diazole: A mechanistic study

Fluorescence quenching of CdS quantum dots (QDs) by 4-azetidinyl-7- nitrobenz-2-oxa-1,3-diazole (NBD), where the two quenching partners satisfy the spectral overlap criterion necessary for Förster resonance energy transfer (FRET), is studied by steady-state and time-resolved fluorescence techniques. The fluorescence quenching of the QDs is accompanied by an enhancement of the acceptor fluorescence and a reduction of the average fluorescence lifetime of the donor. Even though these observations are suggestive of a dynamic energy transfer process, it is shown that the quenching actually proceeds through a static interaction between the quenching partners and is probably mediated by charge-transfer interactions. The bimolecular quenching rate constant estimated from the Stern-Volmer plot of the fluorescence intensities, is found to be exceptionally high and unrealistic for the dynamic quenching process. Hence, a kinetic model is employed for the estimation of actual quencher/QD ratio dependent exciton quenching rate constants of the fluorescence quenching of CdS by NBD. The present results point to the need for a deeper analysis of the experimental quenching data to avoid erroneous conclusions. Fluorescence quenching of CdS quantum dots by 4-azetidinyl-7-nitrobenz-2-oxa-1,3-diazole, which shows FRET-like behaviour, is actually mediated by the static interaction of the two (see picture).