Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials , Shandong University , Jinan 250100 , People's Republic of China.
State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , People's Republic of China.
J Am Chem Soc. 2019 Nov 6;141(44):17884-17890. doi: 10.1021/jacs.9b09460. Epub 2019 Oct 23.
Control over core structure is much more challenging than that over shell structure in core-shell silver nanoclusters. Herein, two isostructural chalcogen-mediated [AgZ@Ag] (Z = S or Se) nanoclusters ( and ) caging tetrahedral [AgZ] as cores were synthesized by introducing PhCSH or PhPSe as slow-release source of S or Se, respectively, and characterized by single-crystal X-ray diffraction (SCXRD). As compared to the previously reported [AgS@Ag] cluster (), we found that introducing additional S or Se ions can effectively enlarge the inner core from tetrahedral AgS to AgZ, which is a regular octahedron of silver with four Z capping on one tetrahedral set of four faces. More interestingly, the molecular enantiomers of and segregate into different crystals (222), while those of form racemic crystals (4/). The larger AgZ core in Ag clusters also extends their emission to the near-infrared region (∼760 nm). The study confirms that chalcogenide can enlarge the nuclearity of nanoclusters by altering the inner core structure and affords a new strategy to synthesize chiral core-shell silver nanoclusters of higher-order in controlled fashion.
在核壳型银纳米簇中，对核结构的控制比壳结构的控制更具挑战性。在此，通过分别引入 PhCSH 或 PhPSe 作为 S 或 Se 的缓释放源，合成了两种等结构的硫属元素介导的 [AgZ@Ag]（Z = S 或 Se）纳米簇（和），并通过单晶 X 射线衍射（SCXRD）进行了表征。与之前报道的 [AgS@Ag] 团簇（）相比，我们发现引入额外的 S 或 Se 离子可以有效地将内核从四面体 AgS 扩大到 AgZ，AgZ 是一种具有四个 Z 帽在一个四面体的四个面上的银的正八面体。更有趣的是，和的分子对映异构体分离成不同的晶体（222），而的对映异构体则形成外消旋晶体（4/）。Ag 簇中较大的 AgZ 核也将其发射扩展到近红外区域（约 760nm）。该研究证实，通过改变内核结构，硫属元素可以增大纳米簇的核性，并提供了一种以可控方式合成高阶手性核壳型银纳米簇的新策略。
