Face-directed self-assembly of an electronically active Archimedean polyoxometalate architecture

Abstract

The convergent assembly of metal-organic frameworks has enabled the design of porous materials using a structural building unit approach, but functional systems incorporating pre-assembled structural building unit 'pore' openings are rare. Here, we show that the face-directed assembly of a ring-shaped macrocyclic polyoxometalate structural building unit, {P(8)W(48)O(184)}(40-) with an integrated 1-nm pore as an 'aperture synthon', with manganese linkers yields a vast three-dimensional extended framework architecture based on a truncated cuboctahedron. The 1-nm-diameter entrance pores of the {P(8)W(48)O(184)}(40-) structural building unit lead to approximately spherical 7.24-nm(3) cavities containing exchangeable alkali-metal cations that can be replaced by transition-metal ions through a cation exchange process. Control over this process can be exerted by either electrochemically switching the overall framework charge by manipulating the oxidation state of the manganese linker ions, or by physically gating the pores with large organic cations, thus demonstrating how metal-organic framework-like structures with integrated pores and new physical properties can be assembled.

Self-Assembly in Polyoxometalate and Metal Coordination-Based Systems: Synthetic Approaches and Developments

“…Another set of representative examples are the all-inorganic POM-OF compounds reported by Cronin et al [71] where the connectivity between the POM-based building blocks was served exclusively by transitions metals.…”

Building Block Libraries and Structural Considerations in the Self-assembly of Polyoxometalate and Polyoxothiometalate Systems

“…A representative example of this effort is the utilization of the [P8W48O184] 40 ring-shaped macrocyclic POM cluster as building unit, with an integrated 1-nm pore as an 'aperture synthon', with manganese linkers yielding a vast three-dimensional extended framework architecture (Fig. 13) [35]. The 1-nm-diameter entrance pores of the {P8W48} structural building unit lead to approximately spherical 7.24 nm 3 cavities containing exchangeable alkali-metal cations that can be replaced by transition-metal ions through a cation exchange process (Fig.…”

Photocatalytic reactivity tuning by heterometal and addenda metal variation in Lindqvist polyoxometalates

“…POMs have been extensively used as functional molecular materials in catalysis, 12,13 photocatalysis, 14,15 redox-active functional materials, 16 and energy conversion and storage. [17][18][19][20] The chemical and structural modifications of POMs can be achieved by tuning the secondary reaction parameters (e.g.…”