Copper (I)-Organic Frameworks for Catalysis: Networking Metal Clusters with Dynamic Covalent Chemistry

Metal clusters exhibit diverse structures, emerging functions, and applications; thus, incorporating clusters into metal-organic frameworks (MOFs) brings tremendous merits. Although the construction of cluster-based MOFs is sophisticated, the reticular materials constructed from a combination of the chemistry of metal clusters and covalent organic frameworks (COFs) remain unexplored. Herein, we prepared two Cu(I) cluster-based MOFs with cyclic trinuclear units (CTUs), termed JNM-1 and JNM-2, either by a stepwise synthetic approach or by a one-pot reaction, for networking clusters with dynamic covalent chemistry, rarely utilized in MOF synthesis. The generated JNMs exhibited excellent stability and could be used as recyclable catalysts for palladium-free Sonogashira coupling reactions with high efficiency and tolerance (>90% yield for nine examples), without loss of performance for at least five cycle runs. In addition, conjugated single molecular wires with lengths ranging from 1.6 to 2.7 nm were synthesized feasibly using the JNM-1 catalyst. [GRAPHICS] .