Precise Assembly of Polyoxometalates at Single‐cluster Levels

Abstract

Polyoxometalate (POM) clusters with atomic precision structures are promising candidates construct functional nanomaterials via self-assembly. Non-covalent interactions at molecular levels can govern the self-assembly of POM clusters, for which the precise control of POM-based assemblies can be realized at single-cluster levels. This mini-review focuses on the synthesis and properties of POM-based nanostructures, including amphiphilic POM assemblies and coassemblies of POM clusters and other subnanometer building blocks. Several synthetic strategies have been developed for rational control of POM-based assemblies in terms of morphologies, compositions and properties. 1D subnanometer POM assemblies demonstrate remarkable enhanced mechanical properties due to the topological interactions between nanowires and surroundings. The in-depth understanding of POM-based assemblies may help in the design of functional nanomaterials in fundamental perspectives and applications.

Fabrication of Polyoxometalate-Based Metal–Organic Frameworks Integrating Paddlewheel Rh2(OAc)4 for Visible-Light-Driven Oxidative Coupling of Amines

“…They have attracted much interest in the photocatalytic field because of their structural diversity, high negative charge, and remarkable redox ability. 14,15 Particularly, POMs are often used as "electron relays" in photocatalytic organic synthesis reactions because they can achieve structural modifications at the molecular level and enable fast, reversible, and multiple electron transfer. 16−19 However, POMs usually absorb only UV light and have high solubility in the reaction system, making them difficult to recycle and reuse, greatly restricting their usage.…”

A monolayer crystalline covalent network of polyoxometalate clusters

“…Polyoxometalate (POM) is a special class of clusters with a stable structure, a uniform size, and modifiable surface properties. The assembly behavior of POM clusters can be precisely regulated at the molecular scale, which has emerged as promising building units to construct ultrathin nanomaterials (17)(18)(19)(20), such as single-cluster nanowires (18), nanosheets (19), single-walled nanotubes (20), etc. Moreover, when POM clusters are directly connected, the electronic structures of assemblies will be changed and display electron delocalization behavior (21).…”

Multi-CeIII-Inserted Phospho(III)tungstate Containing Three Building Units with Prominent Peroxidase-Mimicking Activity for Detecting l-Cysteine

“…Polyoxometalates (POMs) as a class of excellent metal oxide nanoclusters have drawn significant attention on account of their adjustable compositions, well-defined structures, and excellent redox performances, which afford them potential applications in catalysis, optics, medicine, and so on. − Recently, POMs, especially transition-metal-substituted POMs, have been reported for their excellent peroxidase-mimicking activity and promising application in the biosensing field (Figure S1). − For instance, the introduction of redox-active Fe III centers into a germanotungstate matrix forming a transition-metal-substituted POM, reported by our group, is an example of excellent peroxidase-mimicking activity in colorimetric biosensing, and it was further used for detecting uric acid .…”