Spontaneous Electronic Band Formation and Switchable Behaviors in a Phase-Rich Superatomic Crystal

Structural phase transitions run in families of crystalline solids. Perovskites, for example, feature a remarkable number of structural transformations that produce a wealth of exotic behaviors, including ferroelectricity, magnetoresistance, metal–insulator transitions and superconductivity. In superatomic crystals and other such materials assembled from programmable building blocks, phase transitions offer pathways to new properties that are both tunable and switchable. Here we describe [Co6Te8(PEt3)6][C70]2, a novel superatomic crystal with two separate phase transitions that drastically transform the collective material properties. A coupled structural-electronic phase transition triggers the emergence of a new electronic band in the fullerene sublattice of the crystal, increasing its electrical conductivity by 2 orders of magnitude, while narrowing its optical gap and increasing its spin density. Independently, an order–disorder transition transforms [Co6Te8(PEt3)6][C70]2 from a phonon crystal to a ph...