Metal–Organic Cages with {SiW9Ni4} Polyoxotungstate Nodes. Issue 19 (7th March 2022)

• Record Type: Journal Article
• Authors: Chang, Qing; Meng, Xiangyu; Ruan, Wenjun; Feng, Yeqin; Li, Rui; Zhu, Jiayu; Ding, Yong; Lv, Hongjin; Wang, Wei; Chen, Guanying; Fang, Xikui
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 19(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-07
• Subjects: CO2 Photoreduction -- Metal–Organic Polyhedra -- Nickel -- Polyoxometalates -- Self-Assembly; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202117637
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A tritopic, Ni‐substituted Keggin cluster, {SiW9 Ni4 }, assembles with rigid dicarboxylate linkers to give rise to a set of discrete, POM2 n L3 n ‐type structures (POM={SiW9 Ni4 }) with defined interior voids. The outcome of coordination‐driven self‐assemblies of these polyhedral cages—from fused dimers to trigonal prisms—was found to be sensitive to bend angles of the ditopic ligands, which vary from 122° to 180°. These polyoxotungstate‐based metal–organic polyhedra, when coupled with [Ru(bpy)3 ]Cl2 as a photosensitizer and triethanolamine as the electron donor, serve as highly effective catalysts for CO2 reduction, with turnover numbers up to 328 and CO selectivity as high as 96.2 %. The inner cavities of such cage structures, if functionalized or of sufficient size to encapsulate targeted guest molecules, could present a new strategy towards functional materials for potential applications. Abstract : Discrete metal–organic cages with polyoxotungstate nodes were assembled from a tritopic Keggin cluster, {SiW9 Ni4 }, and rigid dicarboxylates. Varying the bend angles of the linkers from 122° to 180° allows a set of POM2 n L3 n ‐type cages to be realized. The fact they can serve as highly effective photocatalysts for CO2 reduction opens up future opportunities for novel functions and applications by taking advantage of the confinement effect of their void spaces.