Photochemical strategies for the synthesis of gold nanoparticles from Au(III) and Au(I) using photoinduced free radical generation.

A comprehensive study of the ketone-photoinduced formation of gold nanoparticles (AuNPs) from gold ions in aqueous and micellar solution has been carried out. Ketones are good photosensitizers for nanoparticle synthesis not because of the energy they can absorb or deliver but rather because of the reducing free radicals they can generate; thus, efficient nanoparticle generation requires a careful selection of substrates and experimental conditions to ensure that free-radical generation occurs with high quantum efficiency and that gold ion precursors do not cause UV screening of the organic photosensitizers. A key consideration in achieving AuNP synthesis with short exposure times is minimizing excited-state quenching by gold ions; this can be achieved by temporal or spatial segregation or a combination of the two. Temporal segregation can be accomplished by using unimolecular precursors, such as benzoins, that yield ketyl radicals from triplet precursors with lifetimes of a few nanoseconds. Spatial segregation can be achieved by using self-assembled structures such as micelles. In this case, the process can be assisted by selecting ketones with n,pi* triplet states and by adding good hydrophobic hydrogen donors such as 1,4-cyclohexadiene. Systems involving bimolecular reactions of ketones are catalytic in that the ketone is recovered at the end of the reductive process. Rate constants have been determined for the quenching of excited triplets and for the scavenging of ketyl radicals by Au(I) and Au(III); in general, these values are within an order of magnitude of the rate constant for diffusion control. This article provides a paradigm for the photochemical production of nanoparticles of gold and other metal ions that highlights ten aspects that must be considered in order to design successful photochemical systems for nanoparticle generation.