Gold-Cage Perovskites: A Three-Dimensional AuIII–X Framework Encasing Isolated MX63– Octahedra (MIII = In, Sb, Bi; X = Cl–, Br–, I–)

The Cs8AuIII4MIIIX23 (M = In3+, Sb3+, Bi3+; X = Cl–, Br–, I–) perovskites are composed of corner-sharing Au–X octahedra that trace the edges of a cube containing an isolated M–X octahedron at its body center. This structure, unique within the halide perovskite family, may be derived from the doubled cubic perovskite unit cell by removing the metals at the cube faces. To our knowledge, these are the only halide perovskites where the octahedral sites do not bear an average 2+ charge. Charge compensation in these materials requires a stoichiometric halide vacancy, which is disordered around the Au atom at the unit-cell corner and orders when the crystallization is slowed. Using X-ray crystallography, X-ray absorption spectroscopy, and pair distribution function analysis, we elucidate the structure of this unusual perovskite. Metal-site alloying produces further intricacies in this structure, which our model explains. Compared to other halide perovskites, this class of materials shows unusually low absorption onset energies ranging between ca. 1.0 and 2.4 eV. Partial reduction of Au3+ to Au+ affords an intervalence charge-transfer band, which redshifts the absorption onset of Cs8Au4InCl23 from 2.4 to 1.5 eV. With connected Au–X octahedra and isolated M–X octahedra, this structure type combines zero- and three-dimensional metal-halide sublattices in a single material and stands out among halide perovskites for its ordering of homovalent metals, ordering of halide vacancies, and incorporation of purely trivalent metals at the octahedral sites.