High-conductivity oxide ion electrolytes are needed to reduce the operating temperature of solid-oxide fuel cells. Oxide mobility in solids is associated with defects. Although anion vacancies are the charge carriers in most cases, excess (interstitial) oxide anions give high conductivities in isolated polyhedral anion structures such as the apatites. The development of new families of interstitial oxide conductors with less restrictive structural constraints requires an understanding of the mechanisms enabling both incorporation and mobility of the excess oxide. Here, we show how the two-dimensionally connected tetrahedral gallium oxide network in the melilite structure La(1.54)Sr(0.46)Ga(3)O(7.27) stabilizes oxygen interstitials by local relaxation around them, affording an oxide ion conductivity of 0.02-0.1 S cm(-1) over the 600-900 degrees C temperature range. Polyhedral frameworks with central elements exhibiting variable coordination number can have the flexibility needed to accommodate mobile interstitial oxide ions if non-bridging oxides are present to favour cooperative network distortions.

Scientific and technological interest in porous materials with molecule-sized channels and cavities has led to an intense search for controlled chemical routes to systems with specific properties. This Account details our work on directing the assembly of open-framework structures based on molecules and investigating how the response of nanoporous examples of such materials to guests differs from classical rigid porous systems. The stabilization of chiral nanoporosity by a hierarchy of interactions that both direct and maintain a helical open-framework structure exemplifies the approach.

Porous materials find widespread application in storage, separation, and catalytic technologies. We report a crystalline porous solid with adaptable porosity, in which a simple dipeptide linker is arranged in a regular array by coordination to metal centers. Experiments reinforced by molecular dynamics simulations showed that low-energy torsions and displacements of the peptides enabled the available pore volume to evolve smoothly from zero as the guest loading increased. The observed cooperative feedback in sorption isotherms resembled the response of proteins undergoing conformational selection, suggesting an energy landscape similar to that required for protein folding. The flexible peptide linker was shown to play the pivotal role in changing the pore conformation

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