Xuehua Dong,Ying Long,Ling Huang,Liling Cao,Daojiang Gao,Jian Bi,Guohong Zou
Exploring excellent ultraviolet (UV) birefringent crystals is of great significance. Herein, two novel UV organic–inorganic hybrid birefringent materials [C(NH2)3]2Sb3F3(HPO3)4 ((Gu)2Sb3F3(HPO3)4) and [C(NH2)3]SbFPO4·H2O ((Gu)SbFPO4·H2O) have been successfully synthesized by a facile hydrothermal reaction. Interestingly, though both the two title compounds exhibit similar 2D layered structures, and possess the same functional moieties including SbO4F square pyramids and C(NH2)3 planar groups, they exhibit significantly different optical anisotropies. (Gu)2Sb3F3(HPO3)4 exhibits a small birefringence of 0.027@546 nm while (Gu)SbFPO4·H2O exhibits a large birefringence of 0.151@546 nm. Detailed structural analysis along with calculations revealed that the large optical anisotropy differentiation originating from the anion-directing regulation structures affects the [HPO3]2− and [PO4]3− anionic groups. This work opens a new door to explore novel high-performance structure-driven functional materials in the future.
Zichang Wang,Qingyu Liu,Zhihua Yang,Xueling Hou,Minqiang Gai
Exploring excellent UV birefringent crystals is very urgent for use in advanced optical technologies to manipulate light polarization of great significance. Planar π-conjugated groups are of great interest to researchers in the exploration of optical materials with pronounced birefringence (∆ n ). However, the systematic understanding of cation and anion groups-regulated structure–property relationships requires further investigation. Herein, metal cation engineering is applied to achieve controlled synthesis of novel compounds, enabling precise coordination modulation and structure–property correlation studies. In this work, eight new 3-pyridinesulfonate crystals with the formula A(3-C 5 H 4 NSO 3 ) x ·yH 2 O ( A = Li, Na, Mg, Ca, Zn, Sr, and Ba; x = 1 and 2, y = 0, 4, and 6) and Na(3-C 5 H 4 NSO 3 )·2NaBF 4 ·(3-C 5 H 4 NSO 3 H) are synthesized and characterized. Notably, these crystals exhibit strong optical anisotropy, with birefringence (∆ n ) values ranging from 0.106 to 0.345 (measured at 546 nm) and short UV cut-off edges below 280 nm. Specifically, Li(3-pySO 3 ) exhibits an exceptionally large birefringence (∆ n = 0.345 at 546 nm), which represents the highest value within the metal-containing 3-pyridinesulfonate system and surpasses that of most commercially available birefringent crystals. Moreover, this analysis of the eight crystals elucidates a comprehensive cation-structure-birefringence correlation framework, thereby establishing a cation-driven design principle for high-performance birefringent crystals.
Yue Zhao,Chun-Li Hu,Peng-Fei Chen,Ming-Zhi Zhang,Jiang-Gao Mao
Ultraviolet (UV) birefringent crystals have important applications in polarizers, optical isolators and optical information processing. Crystals with large birefringence can enhance the modulation ability of light and realize the miniaturization of devices. However, the birefringence of cyanurates is often limited by the large dihedral angles between anionic groups. In this work, a chiral-driven approach is proposed for the first time to construct cyanurates with large birefringence. We combined racemic or chiral α-methylbenzylamine (α-MBA) molecules with a π-conjugated cyanurate group (CY), which led to the isolation of three organic hybrid cyanurates with wide band gaps >5.10 eV, namely, rac-α-MBACY, R-α-MBACY, and S-α-MBACY. Notably, the presence of chirality leads to a significant reduction of the dihedral angle between the α-MBA cation and (H2C3N3O3)− anion and a threefold increase in birefringence from 0.113@546 nm to 0.344@546 nm and 0.338@546 nm. The birefringence values of R-α-MBACY and S-α-MBACY exceed those of most of the cyanurates and commercial crystals, indicating their potential as UV birefringent crystals. This work provides new insights into the design and syntheses of UV birefringent materials.
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