Toward a mechanistic understanding of exciton-mediated hydrosilylation on nanocrystalline silicon

White-light initiated hydrosilylation of nanocrystalline porous silicon was found to be far more efficient (in terms of both kinetics and yield) in the presence of electron-accepting molecules with suitably high reduction potentials, particularly halocarbons. It is known that absorption of visible light by nanocrystalline silicon results in the formation of excitons (electron/hole pairs) and that this exciton can be harnessed to drive a hydrosilylation reaction with an alkene; the Si\u2013C bond forms as a result of attack of the \u3c0-electrons of the alkene on the positively charged holes. In order to better understand the white-light initiated mechanism through which this reaction takes place, and to compare with UV-mediated photoemission on Si(111)\u2013H, a series of electron acceptors were screened for their effect on surface alkene hydrosilylation. A very strong correlation between reduction potentials (Ered) of the oxidant and reaction efficiency was observed, with a minimum \u201cturn-on\u201d Ered required for an increase to take place. The oxidant appears to accept, or remove, the electron from the nanocrystallite-bound exciton, favoring attack by the alkene on the positively charged Si nanocrystallite, leading to Si\u2013C bond formation. Radical reactions were discounted for a number of reasons, including lack of effect of radical traps, no apparent Si\u2013Cl bond formation, lack of oxidation of the surfaces, and others. Unlike with other oxidants such as nitro-aromatics, halocarbons do not cause additional surface reactions and promote very clean, fast, and selective hydrosilylation chemistry.Peer reviewed: YesNRC publication: Ye