College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou, Jiangsu 215123, China.
Department of Chemistry and Biochemistry, California State University , Long Beach, California 90840, United States.
J Am Chem Soc. 2018 Jan 24;140(3):888-891. doi: 10.1021/jacs.7b12092. Epub 2018 Jan 16.
The cubic ZnS structure type and the size-dependent properties of related nanoparticles are of both fundamental and technological importance. Yet, it remains a challenge to synthesize large atom-precise clusters of this structure type. Currently, only supertetrahedral clusters with 4, 10, 20, and 35 metal sites (denoted as T2, T3, T4, and T5, respectively) are known. Because the synthesis of T5 in 2002, numerous synthetic efforts targeting larger clusters only resulted in T2-T5 clusters in various compositions and intercluster connectivity, with T6 (56 metal and 84 anion sites) being elusive. Here, we report the so-far largest supertetrahedral cluster (T6, [ZnInS]). New T6 clusters can serve as the host matrix for optically active centers. Mn-doped variants of T4 and T6 have also been made, allowing the investigation of site-dependent Mn emission. The results lead to the elucidation of the mechanism regulating Mn emission via size-dependent crystal lattice strain and provide new insight into Mn-doping chemistry in cluster-based chalcogenides at the atomic level.
立方 ZnS 结构类型和相关纳米粒子的尺寸依赖性性质具有基础和技术重要性。然而，合成这种结构类型的大原子精确团簇仍然是一个挑战。目前，仅已知具有 4、10、20 和 35 个金属位点的超四面体团簇（分别表示为 T2、T3、T4 和 T5）。自 2002 年合成 T5 以来，针对更大团簇的大量合成努力仅导致具有各种组成和团簇间连接性的 T2-T5 团簇，而 elusive 的 T6（56 个金属和 84 个阴离子位点）则难以实现。在这里，我们报告了迄今为止最大的超四面体团簇（T6，[ZnInS]）。新的 T6 团簇可用作光学活性中心的宿主基质。还制备了 T4 和 T6 的 Mn 掺杂变体，允许研究依赖于位置的 Mn 发射。这些结果阐明了通过尺寸相关的晶格应变调节 Mn 发射的机制，并在原子水平上为基于团簇的硫属化物中的 Mn 掺杂化学提供了新的见解。
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