An unprecedented 2-fold interpenetrated lvt open framework built from Zn6 ring seamed trivacant polyoxotungstates used for photocatalytic synthesis of pyridine derivatives

Solar-driven straightforward one-step synthesis of pyridine derivatives in the absence of photosensitizer is of considerable interest but greatly challenging in synthetic and medicinal chemistry. Herein, an unprecedented 2-fold interpenetrated lvt polyoxometalate-based open framework (POM-OF), LCU-22 ([Zn(1-ipIM)3]2[Zn6(AsW9O33)2(1-ipIM)6]·2(1-HipIM), 1-ipIM = 1-isopropyl imidazole) has been synthesized in gram-scale quantities using one-pot reaction and structurally characterized by X-ray crystallography. The cluster node in LCU-22 is a Zn6 ring seamed trivacant polyoxotungstate cluster ([Zn6(AsW9O33)2]), which is quadruply extended by [Zn(1-ipIM)3]2+ units to form the final 3D open framework. Remarkably, LCU-22 is highly stable over wide pH range and in various solvents, and dramatically boosted the white light-powered heterogeneous photocatalysis for synthesis of pyridine derivatives in good yields after three times recycles utilization. This work not only builds a novel POM-OF but also underscores the unique advantages of transition metal cluster substituted polyoxotungstates frameworks used for selective photocatalytic formation of value-added organic molecules.