Reversible Interconversion of a Divalent Vanadium Bronze between δ and β Quasi-1D Structures

Abstract

Charge fluctuations along the quasi-1D frameworks of M(x)V(2)O(5) bronzes have evinced much recent interest owing to the manifestation of colossal metal-insulator transitions and superconductivity. Depending upon the nature of the intercalating cation (M), distinctive geometries of the V(2)O(5) framework are accessible. Herein, we demonstrate an unprecedented reversible transformation between double-layered (δ) and tunnel (β) quasi-1D geometries for nanowires of a divalent vanadium bronze, Ca(x)V(2)O(5) (x ≈ 0.23), upon annealing-induced dehydration and hydrothermally induced hydration. Such a facile hydration/dehydration-induced interconversion between two prominent quasi-1D structures (accompanied by a change in charge-ordering motifs) has not been observed in the bulk and is posited to result from the ease of propagation of crystallographic slip processes across the confined nanowire widths for the δ → β conversion and the facile diffusion of water molecules within the tunnel geometries for the β → δ reversion.