Research progress in trivalent main group V heteroanion-templated polyoxometalates
Zhigang Tang, Mengyao Tang, Dan Wang, Lijuan Chen, Jun‐Wei Zhao
Abstract
Polyoxometalates (POMs), characterized by their varied elemental compositions, nanoscale dimensions, adjustable electronic structures and versatile physicochemical properties, have garnered significant attention across numerous application domains. However, the rational design and precise synthesis of POMs continue to pose substantial challenges. The electronic configurations and spatial effects of heteroanions (HAs) are pivotal in dictating the coordination patterns and topological arrangements of POM building blocks, thus enabling the regulation of both structural attributes and functional characteristics of POMs. Notably, the stereochemical influence of lone pair electrons and the steric constraints induced by protonated phosphorus in trivalent main group V HAs ([HP III O 3 ] 2− , [As III O 3 ] 3− , [Sb III O 3 ] 3− , [Bi III O 3 ] 3− ) facilitate the formation of diverse lacunary POM species. These species not only augment the structural intricacy and diversity of POMs but also effectively modulate intramolecular electronic interactions, conferring POMs with superior and tunable redox capabilities that significantly enhance their applications in advanced fields. Considering the extensive development of trivalent main group V HA-templated POMs (HPOMs), a systematic review of their historical progression is essential. This review provides an in-depth overview of structural features, synthetic methodologies and representative properties of trivalent main group V HPOMs, aiming to offer meaningful insights and direction for the innovative design and advancement of high-performance HPOMs.