Supramolecular assemblies of organo-functionalised hybrid polyoxometalates: from functional building blocks to hierarchical nanomaterials

Abstract

Organic–inorganic hybrid polyoxometalates are versatile building blocks for the self-assembly of functional supramolecular materials.

Improvement of the Hydrolytic Stability of the Keggin Molybdo- and Tungsto-Phosphate Anions by Cyclodextrins

“…POMs have shown a remarkable ability to interact with organic and hybrid moieties to form supramolecular assemblies with specific physicochemical properties. [17][18][19] For instance, Keggin-type anions are capable of forming non-covalent complexes in aqueous solution with the toroidal cyclodextrin (CD) macrocycles. 16,[20][21][22][23][24][25][26] Some of these CD/Keggin hybrids have shown improved properties in sensor 27 , or in electrochemical energy storage, 28 highlighting the beneficial effects of these supramolecular composites.…”

Recent Achievements on Functionalization within closo‐Decahydrodecaborate [B10H10]2− Clusters

“…POMs are soluble anionic oxides with the general formula [M m O y ] pÀ for isopolyoxometalates or [X x M m O y ] qÀ for heteropolyoxometalates, where X can be a non-metal atom such as P, Si, As, Sb and M is the main transition metal constituent in high oxidation state (usually Mo VI or W VI ). [83] The composition of POMs can be finely tuned at the molecular level and due to their vast diversity in sizes, shapes and compositions, they display and exceptional panel of physicochemical properties in numerous domains such as catalysis, [84] electro-catalysis, [85] optics, [86] magnetism [87] and medicine. [88] POMs can be functionalized with organic or inorganic moieties to obtain several organic-inorganic hybrid complexes.…”

A Mixed‐Addenda Mo/W Organofunctionalised Hybrid Polyoxometalate

“…[5,6] Much of the early work on the modification of lacunary POMs focussed on TM-POMs and found them to exhibit a range of potential applications across the fields of medicine, [7] molecular electronics [8,9] and catalysis. [10] In recent years, however, more consideration has been given to the preparation and characterisation of hybrid POMs, [5,11] owing to their highly tuneable properties, including visible-light photoactivity, [12] supramolecular self-assembly, [13][14][15][16] and redox chemistry. [17,18] The combined benefits of addenda metal ion substitution and organo-functionalisation are likely to offer greater scope to tune the physical properties of the POM cluster, [19] however, the preparation of such systems is synthetically challenging and only a handful of mixed-metal hybrid POMs have been reported.…”