Dual Chemical Scissors Strategy Enables 1D Antimony Selenates with Ultraviolet Nonlinear Optical Properties
Xuehua Dong, Ling Huang, Hongmei Zeng, Zhien Lin, Kang Min Ok, Guohong Zou
Abstract
Abstract The rational, function‐driven design of advanced inorganic functional materials remains a significant challenge, primarily attributed to their inherently complex and highly connected 3D frameworks of most oxide‐based systems. Herein, we report a “dual chemical scissors” strategy that synergistically combines the effects of fluoride ions and stereochemically active lone pairs to precisely modulate local coordination environments and enable controlled dimensional reduction. Using this approach, we successfully synthesized the first series of non‐centrosymmetric 1D antimony selenates—RbSbF 2 SeO 4 (I), Rb 2 Sb 2 F 6 SeO 4 (II), and Rb 2 Sb 3 F 9 SeO 4 (III). These compounds feature well‐defined helical chain structures constructed from SbO x F y polyhedra and SeO 4 tetrahedra, resulting in pronounced optical anisotropy and robust nonlinear optical (NLO) properties. Among the series, RbSbF 2 SeO 4 (I) stands out with an exceptional combination of a broad optical transparency window (0.26–10 µm), a strong second‐harmonic generation response (5.4 × KDP), and moderate birefringence (0.12 at 546 nm), positioning it as a highly promising candidate for ultraviolet NLO applications. This work establishes a powerful and generalizable structural design paradigm for constructing polar low‐dimensional architectures and underscores the effectiveness of targeted coordination modulation in advancing high‐performance optical materials.