Rational Phase Control in the Synthesis of Cobalt Sulfides.

A library of substituted thioureas was used as sulfur reagents in the synthesis of cobalt sulfides. The substitution pattern of the thioureas controls the decomposition rate of precursors into sulfur monomers and thereby aids in the exploration of decomposition kinetics on cobalt sulfide-phase formation, including phase-pure jaipurite (CoS), cobalt pentlandite (Co8S9), linnaeite (Co3S4), and cattierite (CoS2). We hypothesize that the available transformation pathways between phases during synthesis are dictated by the approximate ccp or hcp stacking of the sulfur lattice. Through gaining a complex understanding of the cobalt sulfide crystal system, phase-pure syntheses of all four naturally occurring crystalline structures in the cobalt sulfide system were achieved.

Five Hypotheses on the Origins of Temperature Dependence of 77Se NMR Shifts in Diselenides.

Notable thermal shifts in diselenides have been documented in 77Se NMR for more than 50 years, but no satisfactory explanation has been found. Here, five hypotheses are considered as possible explanations for the large temperature dependence of the 77Se chemical shifts of diaryl and dialkyl diselenides compared to monoselenides and selenols. Density functional theory calculations are provided to bolster hypotheses and better understand the effects of barrier height and dipole energies. It is proposed that the temperature dependence of diselenide 77Se NMR chemical shifts is due to rotation around the Se-Se bond and sampling of twisted conformers at higher temperatures. The molecular twisting is solvent dependent; here, DMSO-d6 and toluene-d8 were evaluated. No correlation was established between para-substituents on diaryl diselenides and the magnitude of the change in the 77Se NMR shift (Δδ) with temperature.

Controlling Phase in Colloidal Synthesis.

A fundamental precept of chemistry is that properties are manifestations of the elements present and their arrangement in space. Controlling the arrangement of atoms in nanocrystals is not well understood in nanocrystal synthesis, especially in the transition metal chalcogenides and pnictides, which have rich phase spaces. This Perspective will cover some of the recent advances and current challenges. The perspective includes introductions to challenges particular to chalcogenide and pnictide chemistry, the often-convoluted roles of bond dissociation energies and mechanisms by which precursors break down, using very organized methods to map the synthetic phase space, a discussion of polytype control, and challenges in characterization, especially for solving novel structures on the nanoscale and time-resolved studies.

Harmonic Generation up to Fifth Order from Al/Au/CuS Nanoparticle Films.

Dual heterostructures integrating noble-metal and copper chalcogenide nanoparticles have attracted a great deal of attention in nonlinear optics, because coupling of their localized surface plasmon resonances (LSPRs) substantially enhances light-matter interactions through local-field effects. Previously, enhanced cascaded third-harmonic generation was demonstrated in Au/CuS heterostructures mediated by harmonically coupled surface plasmon resonances. This suggests a promising approach for extending nonlinear enhancement to higher harmonics by adding an additional nanoparticulate material with higher-frequency harmonic resonances to the hybrid films. Here we report the first observation of enhanced cascaded fourth- and fifth-harmonic generation in Al/Au/CuS driven by coupled LSPRs at the fundamental (1050 nm), second harmonic (525 nm), and third harmonic (350 nm) of the pump frequency. An analytical model based on incoherent dipole-dipole interactions among plasmonic nanoparticles accounts for the observed enhancements. The results suggest a novel design for efficiently generating higher harmonics in resonant plasmonic structures by means of multiple sum-frequency cascades.

Celebrating the 150th anniversary of Vanderbilt University.

An introduction to the Nanoscale Horizons, Nanoscale and Nanoscale Advances themed collection celebrating the 150th anniversary of Vanderbilt University, featuring work from researchers currently affiliated with Vanderbilt University, esteemed alumni, and researchers with strong connections and extensive collaborations with the university.