Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension-Reduced Zn-Based Crystals.

ABSTRACT

Birefringent crystals have essential applications in optical communication areas. Low-dimensional structures with inherited structural anisotropy are potential systems for investigating birefringent materials with large birefringence. In this work, the zero-dimensional (0D) [(o-C5H5NO)2ZnCl2] (1) and [o-C5H6NO]2[ZnCl4] (2) were obtained by introducing the π-conjugated o-C5H5NO (4HP) into the three-dimensional (3D) ZnCl2. Remarkably, 1 exhibits a giant birefringence of 0.482@546 nm, which is the largest among Zn-based ultraviolet (UV) compounds and 160 times that of ZnCl2. According to structural and theoretical calculation analyses, the large optical polarizability, high spatial density, ideal distribution of the [(4HP)2ZnCl2]0 cluster, and the low dimension of 1 result in the dramatically increased birefringence compared to ZnCl2. This work will provide a valid route for accelerating the design and synthesis of compounds with excellent birefringence in low-dimensional systems.