Designed construction of two new atom-precise three-dimensional and two-dimensional Ag12 cluster-assembled materials

Silver cluster-assembled materials (SCAMs) are well-defined crystalline extended materials hallmarked by their unique geometric structures, atomically precise designability and functional modularity. The precise structural features of SCAMs are intrinsically linked to their unique functionalities, and understanding this correlation helps in optimizing their performance and predicting their behavior. In this study, we report for the first time the synthesis of a (3,6)-connected three-dimensional (3D) SCAM, [Ag12(StBu)6(CF3COO)6(TPMA)6]n (designated as TUS 6), TPMA=tris(pyridine-4-ylmethyl)amine by assembling Ag12 cluster nodes with the help of a tridentate linker TPMA. Besides, we also prepared a two-dimensional (2D) SCAM, [Ag12(StBu)6(CF3COO)6(TPEB)6]n (described as TUS 7), TPEB = 1,3,5-tris(pyridine-4-ylethynyl)benzene by reticulating Ag12 nodes with tridentate linker TPEB. This work highlights the influence of flexibility of organic linkers in dictating the spatially extended structures of SCAMs and the properties arising thereof. Characterized by microscopic and diffraction analyses, the SCAMs revealed distinct morphologies, structural robustness, and phase purity.