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Updated: Jul 9, 2025

Novel Techniques for Observing Structural Dynamics of Photoresponsive Liquid Crystals
Published on: May 29, 2018
The first polyanion-substitution-driven centrosymmetric-to-noncentrosymmetric structural transformation realizing an
Zhi-Xin Qiu1, Zhe-Xiong Zheng1, Xiao-Ming Jiang1,2
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou Fujian 350002 P. R. China bwliu@fjirsm.ac.cn gcguo@fjirsm.ac.cn.
Abstract:
Crystallographically, noncentrosymmetricity (NCS) is an essential precondition and foundation of achieving nonlinear optical (NLO), pyroelectric, ferroelectric, and piezoelectric materials. Herein, structurally, octahedral [SmCl6]3- is substituted by the acentric tetrahedral polyanion [CdBr4]2-, which is employed as a templating agent to induce centrosymmetric (CS)-to-NCS transformation based on the new CS supramolecule [Cd5P2][SmCl6]Cl (1), thereby providing the NCS supramolecule [Cd4P2][CdBr4] (2). Meanwhile, this replacement further results in the host 2D ∞2[Cd5P2]4+ layers converting to yield the twisted 3D ∞3[Cd4P2]2+ framework, which promotes the growth of bulk crystals. Additionally, phase 2 possesses well-balanced NLO properties, enabling considerable second-harmonic generation (SHG) responses (0.8-2.7 × AgGaS2) in broadband spectra, the thermal expansion anisotropy (2.30) together with suitable band gap (2.37 eV) primarily leading to the favorable laser-induced damage threshold (3.33 × AgGaS2), broad transparent window, and sufficient calculated birefringence (0.0433) for phase-matching ability. Furthermore, the first polyanion substitution of the supramolecule plays the role of templating agent to realize the CS-to-NCS transformation, which offers an effective method to rationally design promising NCS-based functional materials.
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