Pore “Softening” and Emergence of Breathability Effects of New Keplerate Nano‐Containers

Abstract

The self‐assembly of porous molecular nanocapsules offer unique opportunities to investigate a range of interesting phenomena and applications. However, to design nanocapsules with pre‐defined properties, thorough understanding of their structure‐property relation is required. Here, we report the self‐assembly of two elusive members of the Keplerate family, [Mo132Se60O312(H2O)72(AcO)30]42− {Mo132Se60} 1 and [W72Mo60Se60O312(H2O)72(AcO)30]42− {W72Mo60Se60} 2, that have been synthesised using pentagonal and dimeric ([Mo2O2Se2]2+) building blocks and their structures have been confirmed via single crystal X‐ray diffractions. Our comparative study involving the uptake of organic ions and the related ligand exchange of various ligand sizes by the {Mo132Se60} and previously reported Keplerates {Mo132O60}, {Mo132S60} based on the ligand exchange rates, revealed the emergence of increased “breathability” that dominates over the pore size as we transition from the {Mo132S60} to the “softer” {Mo132Se60} molecular nano‐container.

Synthesis of Isotypic Giant Polymolybdate Cages for Efficient Photocatalytic C–C Coupling Reactions

“…Polyoxometalates (POMs) are a prominent type of discrete early-transition metal-oxo clusters with a diversity of structures and properties. − In the field of POMs, the synthesis of giant hollow POM cages is interesting and important since they not only have fascinating architectures but also combine the benefits of POM cluster and porous cage; thus, they are highly promising for applications in catalysis, guest recognition, and molecular reactors. − To date, although a number of giant hollow POM cages, e.g., “hedgehog-like” Mo 368 , truncated icosahedral Mo 132 and U 60 , pentagonal dodecahedral Mo 240 , have been successfully explored by chemists, there is still a lack of an effective strategy in the synthesis for guiding researchers to explore more derivatives or homologs. From the synthesis experiences of traditional POMs, molecular growth based on some known POMs seems to be a good idea for constructing more POM derivatives. − In particular, it is even possible to synthesize a series of derivatives that possess identical main skeleton with the pristine parent POMs. − Such POM derivatives not only largely enrich the structures and properties of traditional POMs but also provide a unique platform for studying their structural transformation process as well as the structure–property relationships. − In this context, the construction of a series of isotypic giant POM cages that can maintain the pristine parent structure and large opening cavities by a molecular growth approach is very interesting and important, but reports on this breakthrough have not been found so far.…”