Hetero- and Homointerlocked Metal–Organic Cages

作者：Yingguo Li, Hong Jiang, Wenqiang Zhang, Xiangxiang Zhao, Meng Sun, Yong Cui, Yan Liu · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.3c10734 · 被引用次数：40 · 研究领域：Supramolecular Chemistry and Complexes、Metal-Organic Frameworks: Synthesis and Applications、Crystallography and molecular interactions

Interlocked molecular assemblies constitute a captivating ensemble of chemical topologies, comprising two or more separate components that exhibit remarkably intricate structures. The interlocked molecular assemblies are typically identical, and heterointerlocked systems that comprise structurally distinct assemblies remain unexplored. Here, we demonstrate that metal-templated synthesis can be exploited to afford not only a homointerlocked cage but also a heterointerlocked cage. Treatment of a carboxylated 2,9-dimethyl-1,10-phenanthroline (dmp) or Cu(I) bis-dmp linker with a Ni 4 - p - tert -butylsulfonylcalix[4]arene cluster affords noninterlocked octahedron and quadruply interlocked double cages consisting of two identical tetragonal pyramids, respectively. In contrast, when a mixture of dmp and Cu(I) bis-dmp linkers is used, a quadruply heterointerlocked cage is produced, consisting of a tetragonal pyramid and an octahedron. With photoredox-active [Cu(dmp) 2 ] + in the structures, both interlocked cages exhibit remarkable performance as photocatalysts for atom transfer radical addition (ATRA) reactions of trifluoromethanesulfonyl chloride with alkenes or oxo-azidations of vinyl arenes. These interlocked structures serve the dual purpose of stabilizing photocatalytically active components against deactivation and encapsulating substrates within the cavity, resulting in yields comparable to or even surpassing those of their molecular counterparts. This work thus provides a n...