Silicene Quantum Dots: Synthesis, Spectroscopy, and Electrochemical Studies.

Organically functionalized silicene quantum dots (SiQDs) were synthesized by chemical exfoliation of calcium silicide and stabilized by hydrosilylation with olefin/acetylene derivatives forming Si-CH2-CH2- or Si-CH═CH- interfacial bonds. Transmission electron microscopy and atomic force microscopy measurements showed that the resultant SiQDs were ca. 2 nm in diameter and consisted of ca. four atomic layers of silicon. The structure was further characterized by 1H and 29Si NMR and X-ray photoelectron spectroscopic measurements. In photoluminescence measurements, the SiQDs exhibited a strong emission at 385 nm and the intensity varied with the interfacial linkage. In electrochemical measurements, both ethynylferrocene- and vinylferrocene-functionalized SiQDs exhibited a pair of well-defined voltammetric peaks at +0.15 V (vs Fc+/Fc) in the dark for the redox reaction of the ferrocene/ferrocenium couple; yet under UV photoirradiation, an additional pair of voltammetric peaks appeared at -0.41 V, most likely because of the redox reaction of ferrocene anions formed by photoinduced electron transfer from the SiQD to the ferrocene metal centers.