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, [Mo132 Se60 O312 (H2 O)72 (AcO)30 ]42- {Mo132 Se60 } 1 and [W72 Mo60 Se60 O312 (H2 O)72 (AcO)30 ]42- {W72 Mo60 Se60 } 2, that have been synthesised using pentagonal and dimeric ([Mo2 O2 Se2 ]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 {Mo132 Se60 } and previously reported Keplerates {Mo132 O60 }, {Mo132 S60 } based on the ligand exchange rates, revealed the emergence of increased "breathability" that dominates over the pore size as we transition from the {Mo132 S60 } to the "softer" {Mo132 Se60 } molecular nano-container.
Keywords: Host-Guest Systems; Keplerate; Polyoxometalates; Selenium; Self-Assembly.
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