The post-functionalizable hybrid-polyoxometalate platforms offer an opportunity to covalently link redox responsive POM cores with virtually any organic molecule or metal cation, generating a wide range of materials with tailored properties.

Working under the supervisor of William Lawrence Bragg at the University of Manchester and being under the direct personal and scientific influence by Linus Pauling, Dr. James Fargher Keggin some 85 years ago published a highly unique discovery—the structure of phosphotungstic acid (Nature 1933, 131, 908–909). This structure sparked the reports of other related polyanions from Keggin's contemporaries, marking the true beginnings of structural polyoxometalate chemistry. In this perspective article, we unveil some aspects and applications of Keggin's structure and discuss how it has shaped the course of our understanding of polyoxometalate chemistry and nanomolecular metal oxides/hydroxides in general.

This Concept article provides insights into the molecular design and construction aspects of polyoxocuprates (POCus), an emerging class of polyoxometalate (POM)‐like architectures featuring low‐to‐high nuclearity copper(II)–oxo/hydroxo skeletons. POCus have been identified to adopt the structural principles of classical POMs consisting of early transition metals. Their potential to afford motifs of the noble‐metal‐based POMs is exploited. “Cross‐structural topological transformation” is introduced to generalize skeletal relationships between POCus and POMs. The study opens up strategies toward the brand‐new structural chemistry of POCus with relevance to homogeneous photocatalysis, medicinal chemistry, molecular magnetism, and quantum computing.

Metal-organic polyhedra (MOPs) are hybrid organic-inorganic nanomolecules, whose rational design depends on harmonious consideration of chemical complementarity and spatial compatibility between two or more types of chemical building units (CBUs). In this work, we apply knowledge engineering technology to automate the derivation of MOP formulations based on existing knowledge. For this purpose we have (i) curated relevant MOP and CBU data; (ii) developed an assembly model concept that embeds rules in the MOP construction; (iii) developed an OntoMOPs ontology that defines MOPs and their key properties; (iv) input agents that populate The World Avatar (TWA) knowledge graph; and (v) input agents that, using information from TWA, derive a list of new constructible MOPs. Our result provides rapid and automated instantiation of MOPs in TWA and unveils the immediate chemical space of known MOPs, thus shedding light on new MOP targets for future investigations.