A Copper Iodide Cluster‐Based Metal–Organic Polyhedra for Photocatalytic Click Chemistry

Self‐assembly from versatile inorganic secondary building units (SBUs) is an important strategy for constructing metal–organic compounds with sophisticated structures and desired functionality. Herein, a copper(I) iodide cluster‐based metal–organic polyhedra (MOP) (Cu₃I₃)₄L¹ ₄ (1) (L ¹ = 1,3,5‐trispyridylsulfanylethyl)‐2,4,6‐triethylbenzene, 2‐mercaptopyridine) is synthesized. Due to the abnormal geometry of [Cu₃I₃] SBUs, MOP 1 exhibits a half‐truncated cube topology, which is rarely observed up to date. Compared with commonly used metal ion or clusters, the coordination bond between the [Cu₃I₃] SBU and the ligand are rather labile in solution evidenced by the theoretical calculations and experimental results. Interestingly, the liable [Cu₃I₃] SBU endows MOP 1 to photocatalyze the azide–alkyne cycloaddition reaction in aqueous solution with high efficiency, excellent tolerance (>80% isolated yield for 18 examples), and good recyclability. The mechanistic studies reveal a photoinduced electron transfer from the MOP to azide, which is unusual in copper‐catalyzed click reactions.