Nakatani Riki, Sakai Jin, Saha Aishik, Kondo Ayumu, Tomioka Rina, Kawawaki Tokuhisa, Das Saikat, Negishi Yuichi
Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai 400 076, India.
Nanoscale. 2025 Jan 2;17(2):813-822. doi: 10.1039/d4nr03992k.
Silver cluster-assembled materials (SCAMs) are well-defined crystalline extended materials hallmarked by their unique geometric structures, atomically precise designability and functional modularity. In this study, we report for the first time the synthesis of a (3,6)-connected three-dimensional (3D) SCAM, [Ag(SBu)(CFCOO)(TPMA)] (designated as TUS 6), TPMA = tris(pyridine-4-ylmethyl)amine, by assembling Ag cluster nodes with the help of a tritopic linker TPMA. Besides, we also prepared a two-dimensional (2D) SCAM, [Ag(SBu)(CFCOO)(TPEB)] (described as TUS 7), TPEB = 1,3,5-tris(pyridine-4-ylethynyl)benzene, by reticulating Ag nodes with a tritopic linker TPEB. Characterized by microscopic and diffraction analyses, the SCAMs revealed distinct morphologies, structural robustness, and phase purity. This paper elucidates how the binding with the organic linkers alters the symmetry of the silver nanoclusters (NCs). Changes in the symmetry of discrete NCs to assembled structures have not been reported yet. This study provides an atomic-level explanation of the transformation of symmetry from NCs to extended structures.
银簇组装材料（SCAMs）是定义明确的晶体扩展材料，其特点是具有独特的几何结构、原子精确的可设计性和功能模块化。在本研究中，我们首次报告了通过三齿连接体TPMA（三（吡啶-4-基甲基）胺）辅助组装银簇节点，合成了一种（3,6）连接的三维（3D）SCAM，即[Ag(SBu)(CFCOO)(TPMA)]（命名为TUS 6）。此外，我们还通过用三齿连接体TPEB（1,3,5-三（吡啶-4-基乙炔基）苯）使银节点网状化，制备了一种二维（2D）SCAM，即[Ag(SBu)(CFCOO)(TPEB)]（称为TUS 7）。通过显微镜和衍射分析表征，这些SCAMs显示出独特的形态、结构稳健性和相纯度。本文阐明了与有机连接体的结合如何改变银纳米簇（NCs）的对称性。离散NCs到组装结构的对称性变化尚未见报道。本研究为从NCs到扩展结构的对称性转变提供了原子水平的解释。
