Polyoxometalates as chemically and structurally versatile components in self-assembled materials

Polyoxometalates (POMs) are anionic molecular metal oxides with expansive diversity in terms of their composition, structure, nuclearity and charge. Within this vast collection of compounds are dominant structural motifs (POM platforms), that are amenable to significant chemical tuning with minimal perturbation of the inorganic oxide molecular structure. Consequently, this enables the systematic investigation of these compounds as inorganic additives within materials whereby structure and charge can be tuned independently i.e. [PW(12)O(40)](3−)vs. [SiW(12)O(40)](4−) while also investigating the impact of varying the charge balancing cations on self-assembly. The rich surface chemistry of POMs also supports their functionalisation by organic components to yield so-called inorganic–organic hybrids which will be the key focus of this perspective. We will introduce the modifications possible for each POM platform, as well as discussing the range of nanoparticles, microparticles and surfaces that have been developed using both surfactant and polymer building blocks. We will also illustrate important examples of POM-hybrids alongside their potential utility in applications such as imaging, therapeutic delivery and energy storage.