Long-wave infrared birefringent crystals are essential materials in infrared optical applications, with broad potential in fields such as infrared imaging, laser technology, and optical communications. Due to limitations in birefringence, infrared transmission, and crystal growth, high-performance long-wave infrared birefringent crystals have rarely been reported. While metal halides containing lone-pair electrons are promising candidates for long-wave infrared birefringent materials, the "holodirected" coordination configuration of metal ions, particularly when coordinated with heavy halogens, significantly reduces the activity of the lone-pair electrons, thus lowering the birefringence of the structure.

In a study published inAngewandte Chemie International Edition, the research team led by Prof. Kong Fang from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, discovered a facile route to long-wave infrared birefringent crystal.

The researchers proposed an oxygenation strategy, wherein the monovalent halide ion in the halogen polyhedron can been replaced by a divalent oxygen ion, to activate the lone-pair electrons of the central cations, thus enhancing the birefringence of the crystal.

The research effort in Rb⁺-Sb³⁺-Cl^- system resulted three new structures, namely, Rb₁₃Sb₈Cl₃₇, Rb₃Sb₂OCl₇, and Rb₂Sb₂OCl₆. As the Cl/Sb ratio decreases in the structure, the Sb³⁺ coordination geometry transitions from the "holodirected" octahedron to the "hemidirected " square pyramid. Due to the introduction of oxygen ions, the Sb³⁺ ions in Rb₃Sb₂OCl₇ and Rb₂Sb₂OCl₆ adopt a square pyramidal geometry with steric activity, and these two compounds represent the first examples of alkali metal antimony(III) oxyhalides.

The researchers grew a large crystal of Rb₂Sb₂OCl₆ (6×6×2 mm³). Due to the low oxygen content, the infrared cutoff edge of this crystal reaches 14380 nm and exhibits good transmission performance in the range of 0.4-13.5 μm, which is superior to many reported birefringent crystals. The birefringence of the three new compounds is negatively correlated with the Cl/Sb ratio, and the birefringence of Rb₂Sb₂OCl₆ reaches 0.191 @550 nm, which is 11.2 times that of Rb₁₃Sb₈Cl₃₇ (0.017 @550 nm). So, Rb₂Sb₂OCl₆ is a promising long-wave infrared birefringent crystal.

This study not only opens up a new material system—alkali metal antimony(III) oxyhalides, but also offers a novel strategy for the development of long-wave infrared birefringent crystals. The researchers explored the relationship between the geometric structure, electronic structure, and optical properties of lone-pair electron-containing metal oxyhalides, providing a new strategy for the development of long wave infrared birefringent crystals.

The large crystal and transmission spectrum of Rb₂Sb₂OCl₆, the birefringence and coordination mode of Sb³⁺ of Rb₁₃Sb₈Cl₃₇, Rb₃Sb₂OCl₇, and Rb₂Sb₂OCl₆.（Image by Dr. LI Xinyang）

Contact:

Prof. KONG Fang

Fujian Institute of Research on the Structure of Matter

Chinese Academy of Sciences

Email:kongfang@fjirsm.ac.cn