Assembly of Chiral Cluster-Based Metal–Organic Frameworks and the Chirality Memory Effect during their Disassembly

Many metal clusters are intrinsically chiral but are often synthesized as a racemic mixture. By taking chiral Ag₁₄(SPh­(CF₃)₂)₁₂(PPh₃)₄(DMF)₄ (Ag₁₄) clusters with bulky thiolate ligands as an example, we demonstrate herein an interesting assembly disassembly (ASDS) strategy to obtain the corresponding, optically pure crystals of both homochiral enantiomers, R-Ag_14m and S-Ag_14m. The ASDS strategy makes use of two bidentate linkers with different chiral configurations, namely, (1R,2R,N¹E,N²E)-N¹,N²-bis­(pyridin-3-ylmethylene)­cyclohexane-1,2-diamine (LR) and the corresponding chiral analogue LS. For comparison, we also use the racemic mixture of equimolar of LR and LS (LRS). Three three-dimensional (3D) Ag₁₄-based metal–organic frameworks (MOFs) were characterized by X-ray crystallography to be [Ag₁₄(SPh­(CF₃)₂)₁₂(PPh₃)₄(LR)₂]_n (Ag₁₄-LR), [Ag₁₄(SPh­(CF₃)₂)₁₂(PPh₃)₄(LS)₂]_n (Ag₁₄-LS), and [Ag₁₄(SPh­(CF₃)₂)₁₂(PPh₃)₄(LRS)₂]_n (Ag₁₄-LRS), respectively. As expected, the building blocks in Ag₁₄-LR or Ag₁₄-LS are homochiral R-Ag₁₄ or S-Ag₁₄, respectively. In contrast, Ag₁₄-LRS is achiral and crystallizes with a diamond-like structure containing alternate R-Ag₁₄ and S-Ag₁₄ clusters. During the assembly process, the racemic Ag₁₄ clusters were converted to homochiral building blocks, namely, R-Ag₁₄ for Ag₁₄-LR and S-Ag₁₄ for Ag₁₄-LS. Subsequently, the chiral linkers were removed from the crystals of Ag₁₄-LR and Ag₁₄-LS via hydrolysis with water, and from the disassembled solid material Ag₁₄-DR and Ag₁₄-DS, optically pure enantiomers R-Ag_14m and S-Ag_14m were obtained. It is hoped that this simple assembly strategy can be used to construct cluster-based chiral assemblage materials and that the subsequent disassembly protocol can be used to obtain optically pure chiral cluster molecules from as-prepared racemic mixtures.