各向异性
双折射
极化率
材料科学
共轭体系
四面体
结晶学
化学物理
光学
化学
聚合物
有机化学
分子
物理
复合材料
作者
Zhiyong Bai,Kang Min Ok
标识
DOI:10.1002/anie.202315311
摘要
Abstract Sulfate crystals typically exhibit minimal optical anisotropy due to the near‐zero polarizability anisotropy (δ) of [SO 4 ] 2− tetrahedra, arising from highly symmetrical electron clouds. Recent research sought to enhance δ via chemical modifications, such as fluorination. However, the resultant crystals often maintain subpar optical anisotropy, frequently with birefringence values below 0.1. In this study, we have uncovered that δ can be significantly strengthened by chemically tailoring the tetrahedral [SO 4 ] 2− with anisotropic π‐conjugated modules. This has been demonstrated by several newly proposed S−O‐Org (Org: π‐conjugated organic species) moieties, which show a sharp increase in δ based on theoretical computations. To further validate this experimentally, we synthesized and characterized six new 3‐pyridinesulfonate crystals with the formula A(3‐C 5 H 4 NSO 3 ) ⋅ x H 2 O (A=Li, Ag, K, Rb, Cs, and NH 4 ; x =0 and 1). Notably, these materials exhibit strong optical anisotropy, with birefringence values ranging from 0.240 to 0.312 at 546 nm. These values are approximately 23 to 145.5 times greater than those of corresponding sulfates, and they outperform a vast number of sulfate‐related optical materials, thus verifying the effectiveness of the proposed strategy. Furthermore, the title compounds exhibit diverse microstructure peculiarities influenced by the size and binding natures of the counter cations.
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