Mishra Shashank
Université Claude Bernard Lyon 1, CNRS, UMR 5256, Institut de Recherches sur la Catalyse et l'Environnement de Lyon (IRCELYON), 2 Avenue Albert Einstein, 69626 Villeurbanne, France.
Chem Commun (Camb). 2022 Sep 13;58(73):10136-10153. doi: 10.1039/d2cc03458a.
Bis(trialkylsilyl) monochalcogenides and diorganyl dichalcogenides, (RSi)E and RE (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 (E) 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 RE 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 RE, leading to interesting materials including metastable ones for new applications.
双（三烷基硅基）单硫属化物和二有机基二硫属化物，(RSi)E 和 RE（E = S、Se 或 Te，R = 烷基、芳基或烯丙基），在过去十年中已成为合成金属硫属化物纳米颗粒（NPs）和团簇的优良试剂，这是由于它们能够在超温和条件下转移硫属化物阴离子（E），并且即使与非常规金属试剂反应或用于各种合成方法时也具有通用性。相比之下，相关的非硅基化二有机基单硫属化物 RE 直到最近才受到用于金属硫属化物 NPs 溶液相合成的关注。尽管有许多相似之处，但这三类有机硫属化物在配位能力和分解行为上有所不同，因此对金属试剂的反应性也不同。这篇专题文章简要概述了这三类化合物作为超低温合成金属硫属化物纳米材料的合成子的用途，探讨了它们不同的分解机制，并批判性地评估了它们在某些应用中的优势。更具体地说，它讨论了它们在以下方面的用途：（i）提供具有不同动力学和热稳定性的分子前体，（ii）分离反应中间体以理解分子到纳米颗粒的转化机制，从而实现对合成的精细控制，（iii）稳定可分离的亚稳相或难以实现的相，以及（iv）生成具有可控化学计量的复杂三元纳米颗粒或与敏感材料的复合材料而不改变后者的特性。除了提供纳米材料低温合成的观点外，这一概述有望促进进一步的进展，特别是在 RE 领域，从而产生包括用于新应用的亚稳材料在内的有趣材料。
