Efficient and Selective Photogeneration of Stable N-Centered Radicals via Controllable Charge Carrier Imbalance in Cesium Lead Halide Nanocrystals.

ABSTRACT

Despite the versatility of semiconductor nanocrystals (NCs) in photoinduced chemical processes, the generation of stable radicals has been more challenging due to reverse charge transfer or charge recombination even in the presence of sacrificial charge acceptors. Here, we show that cesium lead halide (CsPbX3) NCs can selectively photogenerate either aminium or aminyl radicals from amines, taking advantage of the controllable imbalance of the electron and hole populations achieved by varying the solvent composition. Using dihalomethane as the solvent, irreversible removal of the electrons from CsPbX3 NCs enabled by the photoinduced halide exchange between the NCs and the dihalomethane resulted in efficient oxidative generation of the aminium radical. In the absence of dihalomethane in solvent, the availability of both electrons and holes resulted in the production of an aminyl radical via sequential hole transfer and reductive N-H bond dissociation. The negative charge of the halide ions on the NC's lattice surface appears to facilitate the aminyl radical production, competing favorably with the reversible charge transfer reverting to the reactant.