Hexavanadate Functionalization With Methacrylic Moieties via “Click” Chemistry: An Elegant Route to Metalorganic Vinyl Monomers

The Copper(I)‐catalyzed Azide–Alkyne Cycloaddition reaction was demonstrated as an efficient approach for the construction of Lindqvist‐type hexavanadate‐based organo–inorganic hybrid structures bearing covalently attached vinyl monomer pendant groups. N ‐(4‐ethynylphenyl)methacrylamide, featuring both a terminal alkyne and an acrylamide fragment, was designed and synthetized as a convenient, “easy‐to‐handle” “click” chemistry building block, enabling smooth and selective postfunctionalization of metalorganic species. This building block readily reacts with (NBu 4 ) 2 [V 6 O 13 ((OCH 2 ) 3 CCH 2 −N 3 ) 2 ] to yield the covalent conjugate (NBu 4 ) 2 [V 6 O 13 ((OCH 2 ) 3 CCH 2 (N 3 HC 2 )(C 6 H 4 )NHCOC(CH 3 )=CH 2 ) 2 ]. The smooth conversion of the starting substrate and the high reaction yield—surpassing all previously described protocols for the synthesis of olefin‐functionalized hexavanadates—demonstrate that the “click” chemistry strategy presented here is a powerful and versatile tool for the tailored formation of polyoxometalate‐based vinyl monomers and related metalorganic derivatives. This approach enhances the synthetic accessibility of these challenging metalorganic vinyl monomers and opens new avenues for the design and preparation of advanced (co)polymers, composite materials, and highly ordered polymer‐based assemblies with precisely engineered structure and properties.