Abstract

Biological macromolecules exhibit emergent functions through hierarchical self-assembly, a concept that is extended to design artificial supramolecular assemblies. Here, the first example of breaking the common parallel arrangement of capsule-shaped zirconium coordination cages is reported by constructing the hierarchical porous framework ZrR-1. ZrR-1 adopts a quaternary structure resembling protein and contains 12-connected chloride clusters, representing the highest connectivity for zirconium-based cages reported thus far. Compared to the parallel framework ZrR-2, ZrR-1 demonstrated enhanced stability in acidic aqueous solutions and a tenfold increase in BET surface area (879m2 g-1 ). ZrR-1 also exhibits excellent proton conductivity, reaching 1.31×10-2 S·cm-1 at 353K and 98% relative humidity, with a low activation energy of 0.143eV. This finding provides insights into controlling the hierarchical self-assembly of metal-organic cages to discover superstructures with emergent properties.

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