Hetero- and Homointerlocked Metal-Organic Cages
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY(2024)
摘要
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 new strategy that combines metal templating and nontemplating approaches to design new types of interlocked assemblies with intriguing architectures and properties.
更多查看译文
AI 理解论文
溯源树
样例
![](https://originalfileserver.aminer.cn/sys/aminer/pubs/mrt_preview.jpeg)
生成溯源树,研究论文发展脉络
Chat Paper
正在生成论文摘要