Cooperative Cluster Jahn-Teller Effect as a Possible Route to Antiferroelectricity.

We report the observation of an antipolar phase in cubic GaNb_{4}S_{8} driven by an unconventional microscopic mechanism, the cooperative Jahn-Teller effect of Nb_{4}S_{4} molecular clusters. The assignment of the antipolar nature is based on sudden changes in the crystal structure and a strong drop of the dielectric constant at T_{JT}=31  K, also indicating the first-order nature of the transition. In addition, we found that local symmetry lowering precedes long-range orbital ordering, implying the presence of a dynamic Jahn-Teller effect in the cubic phase above T_{JT}. Based on the variety of structural polymorphs reported in lacunar spinels, also including ferroelectric phases, we argue that GaNb_{4}S_{8} may be transformable to a ferroelectric state, which would further classify the observed antipolar phase as antiferroelectric.