Nanostructured molecular clusters and solids from heavier group 15 cyanate analogues: A novel route to metal pnictides

金属镍（含氮、磷、砷、锑和/或铋的化合物）是一种具有丰富结构和化学计量的多种固体。在它们的许多应用中，它们被用作熏蒸剂、杀虫剂、照明弹，也许最值得注意的是，作为半导体。它们的物理和化学性质的多样性使得这些化合物在一系列技术应用中很有趣。然而，虽然许多这类物质可以很容易地用各种方法合成，但它们往往需要很高的能量成本。此外，获得定义良好的纳米级材料或细观结构固体的能力仍然受到现有技术方法的严重限制。这就是我要解决的挑战。目标是研究使用替代含烟原试剂来合成新的簇，纳米颗粒和结构固体。该提案的重点是氰酸阴离子的较重的含氧原类似物PnCO - (Pn = P-Bi)与过渡和后过渡金属盐的反应性，因为这些化合物用于合成固体和分子簇的使用在很大程度上尚未探索。第一个目标是将较重的15基团氰酸盐类似物的化学性质扩展到SbCO -和BiCO -的合成。然后，重15族氰酸类似物（PnCO -）与各种过渡和过渡后金属盐之间的溶液相复分解反应将进行，目的是开发一种新的自下而上的金属nictides方法。在这里，主要焦点是建立对固体形成的控制，特别关注产生定义良好的纳米颗粒和结构固体，因为尺寸减小的半导体结构，如纳米颗粒和量子点正在影响各种科学和技术领域（例如生物测定或光电器件）。最后，氰酸盐类似物应该是合成魔术大小的分子簇和量子点（QDs）的合适前体。这种团簇的热处理也可用于III/V族量子点的单分散样品的成核，这类化合物迄今为止被证明是非常具有挑战性的合成。

Metal pnictides (compounds containing nitrogen, phosphorus, arsenic, antimony and/or bismuth) are a varied family of solids that adopt a wealth of structures and stoichiometries. Amongst their many applications they have been employed as fumigants, pesticides, flares and, perhaps most notably, as semiconductors. The diversity of their physical and chemical properties makes such compounds interesting for a range of technological applications. However, while many such species can be readily synthesized using a variety of methods, these often come at a high energetic cost. Moreover, the ability to access well defined nanoscale materials or mesostructured solids is still significantly limited by existing technological methods. This is the challenge I propose to address. The goal is to study the use of alternative pnictogen-containing reagents for the synthesis of novel clusters, nanoparticles and structured solids. The proposal focuses on the reactivity of heavier pnictogen-containing analogues of the cyanate anion, PnCO– (Pn = P–Bi) with transition- and post-transition metal salts, as the use of these compounds for the synthesis of solids and molecular clusters is largely unexplored. The first objective is to extend the chemistry of the heavier group 15 analogues of cyanate to target the synthesis of SbCO– and BiCO–. Then, solution-phase metathesis reactions between heavier group 15 cyanate analogues (PnCO–) with a variety of transition- and post-transition metal salts will be conducted, with the aim of developing a novel bottom-up approach to metal pnictides. Herein, the main focus is establishing control over solid formation, with a particular focus on generating well-defined nanoparticles and structured solids as dimensionally reduced semiconductor structures such as nanoparticles and quantum dots are impacting a diverse set of scientific and technological fields (e.g. bioassaying or optoelectronic devices). Finally, the cyanate analogues should be suitable precursors for the synthesis of magic-sized molecular clusters and quantum dots (QDs). The thermal treatment of such clusters may also be used for the nucleation of monodisperse samples of group III/V QDs, a family of compounds that have thus far proven very challenging synthetically.