RbPb₈O₄Cl₉: the first alkali metal lead oxyhalide with distorted [PbO₃Cl₃] and [PbOCl₅] mixed-anion groups

A new heavy metal oxychloride, RbPb₈O₄Cl₉, has been synthesized by a high-temperature solution method. The compound crystallizes in the centrosymmetric space group P4/n (no. 85) and exhibits a three-dimensional (3D) framework constructed from [PbO₃Cl₃], [PbOCl₅] and [RbCl₈] polyhedra. RbPb₈O₄Cl₉ is an indirect band gap compound with an experimental band gap of 3.66 eV. The first-principles calculations indicate that the band gap mainly originated from the interaction of Pb 6p, O 2p and Cl 2p states. Meanwhile, the calculated birefringence of RbPb₈O₄Cl₉ is about 0.012 at 1064 nm. The compound is the first alkali metal lead oxyhalide, which enriches the structural diversity of oxyhalides and provides an insight for the exploration of new functional materials.