Metal–Organic Cages with {SiW₉Ni₄} Polyoxotungstate Nodes

Abstract

A tritopic, Ni‐substituted Keggin cluster, {SiW9Ni4}, assembles with rigid dicarboxylate linkers to give rise to a set of discrete, POM2nL3n‐type structures (POM={SiW9Ni4}) 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.

Coupling Ni3POM with FeOOH on BiVO4 Photoanodes for Efficient Photoelectrochemical Water Splitting

“…Our group has carried out some photocatalytic studies using molecular catalysts, especially polyoxometalates (POMs). − In this study, based on our previous work, a polyoxometalate was used as a cocatalyst to design the photoelectrode. As robust and effective catalysts, POMs are a class of discrete anionic clusters containing oxygen and transition metals, which possess enormous structural diversity (Keggin, Dawson, Anderson, Waugh, Silverton, and Lindqvist) .…”

A Hexadecanuclear Cobalt-Added Tungstogermanate Containing Counter Cobalt Hydrates: Synthesis, Structure and Photocatalytic Properties

“…The lacunary tungsten-oxo clusters can act as multidentate inorganic ligands, incorporating transition metal ions to form transition metal-added POMs (TMAPs) [ 13 , 15 ]. By following the lacunary-directing, synthetic strategy, numerous TMAPs have been reported [ 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 ]. TMAPs have been comprehensively studied due to their integrated advantages, including added transition metal ions and lacunary POM ligands, which result in good structural stability and interesting catalytic properties [ 20 , 21 ].…”

Polyoxometalates tailoring of frustrated Lewis pairs on Ce-doped Bi2O3 for boosting photocatalytic CO2 reduction

“…1 Given that solar energy is a clean and renewable source, photocatalytic CO 2 reduction is a promising strategy for converting CO 2 into value-added products. 2 However, the difficulty of activating the highly stable CO bond of CO 2 poses a significant challenge. 3 Recently, a way to effectively activate CO 2 has been provided by frustrated Lewis pairs (FLPs), which consist of a sterically hindered Lewis acid (LA) and Lewis base (LB).…”