Size-selective precipitation was used to successfully separate colloidally stable allylbenzene-capped silicon nanocrystals into several visible emitting monodisperse fractions traversing the quantum size effect range of 1-5 nm. This enabled the measurement of the absolute quantum yield and lifetime of photoluminescence of allylbenzene-capped silicon nanocrystals as a function of size. The absolute quantum yield and lifetime are found to monotonically decrease with decreasing nanocrystal size, which implies that nonradiative vibrational and surface defect effects overwhelm spatial confinement effects that favor radiative relaxation. Visible emission absolute quantum yields as high as 43% speak well for the development of "green" silicon nanocrystal color-tunable light emitting diodes that can potentially match the performance of their toxic heavy metal chalcogenide counterparts.

We report the preparation of monodisperse silicon nanocrystals (ncSi) by size-separation of polydisperse alkyl-capped ncSi using organic density gradient ultracentrifugation. The ncSi were synthesized by thermal processing of trichlorosilane-derived sol-gel glasses followed by HF etching and surface passivation with alkyl chains and were subsequently fractionated by size using a self-generating density gradient of 40 wt % 2,4,6-tribromotoluene in chlorobenzene. The isolated monodisperse fractions were characterized by photoluminescence spectroscopy and high-angle annular dark-field scanning transmission electron microscopy and determined to have polydispersity index values between 1.04 and 1.06. The ability to isolate monodisperse ncSi will allow for the quantification of the size-dependent structural, optical, electrical, and biological properties of silicon, which will undoubtedly prove useful for tailoring property-specific optoelectronic and biomedical devices.

The role of ethylene in promoting metathesis of acetylenic enynes is probed within the context of ring-closing enyne metathesis, using first- and second-generation Grubbs catalysts. Under inert atmosphere, rapid catalyst deactivation is observed by calibrated GC-FID analysis for substrates with minimal propargylic bulk. MALDI-TOF mass spectra reveal a Ru(enyne)(2) derivative that exhibits very low reactivity toward both enyne and ethylene. Under ethylene, formation of this species is suppressed. Enynes with bulky propargylic groups are not susceptible to this catalyst deactivation pathway, even under N(2) atmosphere.

Nanomaterials are becoming increasingly widespread in consumer technologies, but there is global concern about the toxicity of nanomaterials to humans and the environment as they move rapidly from the research laboratory to the market place. With this in mind, it makes sense to intensify the nanochemistry community's global research effort on the synthesis and study of nanoparticles that are purportedly "green". One potentially green nanoparticle that seems to be a most promising candidate in this context is silicon, whose appealing optical, optoelectronic, photonic, and biomedical attributes are recently gaining much attention. In this paper, we outline some of our recent contributions to the development of the growing field of silicon nanocrystals (ncSi) in order to stress the importance of continued study of ncSi as a green alternative to the archetypal semiconductor nanocrystals like CdSe, InAs, and PbS. While a variety of developments in synthetic methods, characterization techniques, and applications have been reported in recent years, the ability to prepare colloidally-stable monodisperse ncSi samples may prove to have the largest impact on the field, as it opens the door to study and access the tunable size-dependent properties of ncSi. Here, we summarize our recent contributions in size-separation methods to achieve monodisperse samples, the characterization of size-dependant property trends, the development of ncSi applications, and their potential impact on the promising future of ncSi.

The size-dependence of the absolute luminescence quantum yield of size-separated silicon nanocrystals reveals a "volcano" behavior, which switches on around 5 nm, peaks at near 3.7-3.9 nm, and decreases thereafter. These three regions respectively define: i) the transition from bulk to strongly quantum confined emissive silicon, ii) increasing confinement enhancing radiative recombination, and iii) increasing contributions favoring non-radiative recombination.