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

Abstract

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.