Versatile Superatom Complex Nanocluster for the Construction of Framework Materials.

Accurately controlling the assembly of nanometer-sized building blocks presents an important but significant challenge for the construction of functional framework materials, which requires the development of highly stable versatile nanosized assembly modules with multiple coordination sites. In this study, [Ag23(SAdm)12]3+ (Ag23, in which SAdm = 1-adamantanethiol, i.e., C10H15S), a chiral superatom complex nanocluster, was synthesized and assembled into various topologies. We constructed two kinds of framework materials, i.e., superatom complex inorganic framework (SCIF) and superatom complex organic framework (SCOF) materials, including [Ag23(SAdm)12](SbF6)2X (Ag23-1; X = Cl-/SbF6-, a SCIF), [Ag23(SAdm)12](SbF6)3 (Ag23-2, a SCIF), [Ag23(SAdm)12](SbF6)3(bpy)3 (Ag23-bpy, a SCOF, in which bpy = 4,4'-bipyridine, i.e., C10H8N2), and [Ag23(SAdm)12](SbF6)3(dpbz)3 (Ag23-dpbz, a SCOF, in which dpbz = 1,4-bis(4-pyridyl)benzene, i.e., C16H12N2), owing to strong interactions between the versatile Ag23 and the inorganic and organic linkers. Ag23-1, Ag23-2, and Ag23-bpy exhibit two superstructures with interpenetrating frameworks and adamantane-like, hexagonal, and cubic topologies, while Ag23-dpbz displays three superstructures with interpenetrating frameworks and cubic topologies. Ag23-dpbz exhibits the largest specific surface area as well as the strongest photoluminescence and electrochemiluminescence signals owing to its dense network arrangement. This work contributes to the construction of nanocluster-based framework materials and helps to elucidate the effect of the assembly mode on the material properties and functionalities.