Ultra-mild synthesis of nanometric metal chalcogenides using organyl chalcogenide precursors

Abstract

Bis(trialkylsilyl) monochalcogenides and diorganyl dichalcogenides, (R₃Si)₂E and R₂E₂ (E = S, Se or Te and R = alkyl, aryl or allyl group), have emerged in the past decade as excellent reagents for the synthesis of metal chalcogenide nanoparticles (NPs) and clusters owing to their ability to transfer the chalcogenide anion (E²⁻) under ultra-mild conditions and versatility in reacting even with non-conventional metal reagents or being employed in a variety of synthetic methods. In comparison, the related non-silylated diorganyl monochalcogenides R₂E have received attention only recently for the solution phase synthesis of metal chalcogenide NPs. In spite of sharing many similarities, these three families of organyl chalcogenides are different in their coordination ability and decomposition behavior, and therefore in reactivities towards metal reagents. This feature article provides a concise overview on the use of these three families as synthons for the ultralow-temperature synthesis of metal chalcogenide nanomaterials, deliberating their different decomposition mechanisms and critically assessing their advantages for certain applications. More specifically, it discusses their usefulness in (i) affording molecular precursors with different kinetic and thermal stabilities, (ii) isolating reactive intermediates for comprehending the mechanism of molecule-to-nanoparticle transformation and, therefore, achieving fine control over the synthesis, (iii) stabilizing isolable metastable or difficult-to-achieve phases, and (iv) yielding complex ternary nanoparticles with controlled stoichiometry or composites with sensitive materials without modifying the characteristics of the latter. Besides providing a perspective on the low-temperature synthesis of nanomaterials, this overview is expected to assist further progress, particularly in the field of R₂E, leading to interesting materials including metastable ones for new applications.