Efficiency of Hole Transfer from Photoexcited Quantum Dots to Covalently Linked Molecular Species

Hole transfer from high photoluminescence quantum yield (PLQY) CdSe-core CdS-shell semiconductor nanocrystal quantum dots (QDs) to covalently linked molecular hole acceptors is investigated. H-1 NMR is used to independently calibrate the average number of hole acceptor molecules per QD, N, allowing us to measure PLQY as a function of N, and to extract the hole transfer rate constant per acceptor, k(ht). This value allows for reliable comparisons between nine different donoracceptor systems with variant shell thicknesses and acceptor ligands, with kht spanning over 4 orders of magnitude, from single acceptor time constants as fast as 16 ns to as slow as 0.13 ms. The PLQY variation with acceptor coverage for all kht follows a universal equation, and the shape of this curve depends critically on the ratio of the total hole transfer rate to the sum of the native recombination rates in the QD. The dependence of k(ht) on the CdS thickness and the chain length of the acceptor is investigated, with damping coefficients beta measured to be (0.24 +/- 0.025) angstrom(-1) and (0.85 +/- 0.1) angstrom(-1) for CdS and the alkyl chain, respectively. We observe that QDs with high intrinsic PLQYs (>79%) can donate holes to surface-bound molecular acceptors with efficiencies up to 99% and total hole transfer time constants as fast as 170 ps. We demonstrate the merits of a system where ill-defined nonradiative channels are suppressed and well-defined nonradiative channels are engineered and quantified. These results show the potential of QD systems to drive desirable oxidative chemistry without undergoing oxidative photodegradation.