Shen Honglei, Wang Pu, Xu Jiawei, Fu Ziwei, Kang Xi, Pei Yong, Zhu Manzhou
Department of Chemistry, Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University Hefei Anhui 230601 China
Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University Xiangtan Hunan 411105 P. R. China
Chem Sci. 2025 Jan 7;16(5):2373-2381. doi: 10.1039/d4sc06847e. eCollection 2025 Jan 29.
Controlling symmetrical or asymmetrical growth has allowed a series of novel nanomaterials with prominent physicochemical properties to be produced. However, precise and continuous size growth based on a preserved template has long been a challenging pursuit, yet little has been achieved in terms of manipulation at the atomic level. Here, a correlated silver cluster series has been established, enabling atomically precise manipulation of symmetrical and asymmetrical surface structure expansions of metal nanoclusters. Specifically, the -axisymmetric Ag(BDTA)(PPh) nanocluster underwent symmetrical and asymmetrical surface structure expansions an acid-mediated synthetic procedure, giving rise to -axisymmetric Ag(BDTA)(PPh) and -axisymmetric Ag(BDTA)(PPh), respectively. In addition, structural transformations, including structural degradation from Ag to Ag and asymmetrical structural expansion from Ag to Ag, were rationalized theoretically. More importantly, the asymmetrically structured Ag nanoclusters followed a chiral crystallization mode, and their crystals displayed high optical activity, derived from CD and CPL characterization. This work not only provides an important model for unlocking the symmetrical/asymmetrical size growth mechanism at the atomic level but also pioneers a promising approach to activate the optical activity of cluster-based nanomaterials.
控制对称或不对称生长使得一系列具有突出物理化学性质的新型纳米材料得以制备。然而，基于保留模板进行精确且连续的尺寸生长长期以来一直是一项具有挑战性的追求，而在原子水平上的操控方面几乎没有取得什么成果。在此，已建立了一个相关的银簇系列，能够对金属纳米簇的对称和不对称表面结构扩展进行原子精确操控。具体而言，轴对称的Ag(BDTA)(PPh)纳米簇在酸介导的合成过程中经历了对称和不对称的表面结构扩展，分别产生了轴对称的Ag(BDTA)(PPh)和轴对称的Ag(BDTA)(PPh)。此外，从理论上对包括从Ag到Ag的结构降解以及从Ag到Ag的不对称结构扩展等结构转变进行了合理化解释。更重要的是，具有不对称结构的Ag纳米簇遵循手性结晶模式，并且它们的晶体表现出高光学活性，这是通过圆二色性（CD）和圆偏振发光（CPL）表征得出的。这项工作不仅为揭示原子水平上的对称/不对称尺寸生长机制提供了一个重要模型，还开创了一种激活基于簇的纳米材料光学活性的有前景的方法。
