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

We report the observation of an antipolar phase in cubic GaNb4S8 driven by an unconventional microscopic mechanism, the cooperative Jahn-Teller effect of Nb4S4 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 GaNb4S8 may be transformable to a ferroelectric state, which would further classify the observed antipolar phase as antiferroelectric.