A Highly Optical Anisotropic Hybrid Perovskite for Efficient Manipulation of Light Polarization

Abstract Optical anisotropic (e.g., birefringent) crystals can manipulate the polarization of light and thus are widely applied in modern optical fields. Common birefringent crystals are almost exclusively limited to inorganic oxides with small birefringence. Here, a new 1D hybrid halide perovskite PZPbCl 3 (PZ = phenazine) is reported, which consists of perfectly parallel Pb–Cl chains and PZ cations. Remarkably, polarized optical observations show that even a PZPbCl 3 crystal with micrometer thickness can modulate the polarized light efficiently. Furthermore, PZPbCl 3 exhibits exceptional birefringence up to 0.65@546 nm, which is significantly larger than that of commercial oxide crystals. According to first‐principles calculations and polarizability anisotropy analyses, it is found that this birefringence is mainly ascribed to the linear polymerization of π ‐conjugated rings in PZ cations. Due to the rich physical properties and structural diversity of hybrid perovskites, it is believed that the introduction of excellent birefringence into the hybrid perovskites will bring unprecedented opportunities to the future explorations of polarization‐dependent functional materials.