Quantum Dot Photoluminescence Quenching by Cr(Ⅲ) Complexes. Photosensitized Reactions and Evidence for a FRET Mechanism

摘要

Reported are quantitative studies of the energy transfer from water-soluble CdSe/ZnS and CdSeS/ZnS core/shell quantum dots (QDs) to the Cr(Ⅲ) complexes trans-Cr(N_4)(X)_2~+ (N_4 is a tetraazamacrocyde ligand, X~- is CN~-, Cl~-, or QNO~-) in aqueous solution. Variation of N_4, of X~-, and of the QD size and composition allows one to probe the relationship between the emission/absorption overlap integral parameter and the efficiency of the quenching of the QD photoluminescence (PL) by the chromium(Ⅲ) complexes. Steady-state studies of the QD PL in the presence of different concentrations of trans-Cr(N_4)(X)_2~+ indicate a clear correlation between quenching efficiency and the overlap integral largely consistent with the predicted behavior of a Forster resonance energy transfer (FRET)-type mechanism. PL lifetimes show analogous correlations, and these results demonstrate that spectral overlap is an important consideration when designing supramolecular systems that incorporate QDs as photosensitizers. In the latter context, we extend earlier studies demonstrating that the water-soluble CdSe/ZnS and CdSeS/ZnS QDs photosensitize nitric oxide release from the frans-Cr(cydam)(ONO)_2~+ cation (cyclam = 1,4,8,11-tetraazacyclotetradecane) and report the efficiency (quantum yield) for this process. An improved synthesis of ternary CdSeS core/shell QDs is also described.