[Sn3OF]PO4与[Sn3F3]PO4：通过打破R3对称性和重新排列孤对来增强双折射性

IF 6.4 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers Pub Date : 2024-07-09 DOI:10.1039/D4QI01203H

Yuhan Hu, Xi Xu, Ruixi Wang, Jingyun Han, Shunsong Zhang, Shuhui Zhan, Jingyu Guo, Li-Ming Wu and Ling Chen

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引用次数: 0

摘要

含锡（II）的磷酸盐是设计和寻找具有增强双折射的材料的理想候选材料。在此，我们展示了一种新型[Sn3OF]PO4化合物，与近 40 年前发现的相关化合物[Sn3F3]PO4 相比，该化合物表现出显著的双折射（546 纳米波长处 ∆nobv = 0.117），提高了五倍。双折射的显著增强主要归功于各向同性的[SnO3F]5-结构构建单元。通过简单地调节 F/O 比，[Sn3F3]PO4 中不理想的 R3 对称性被打破。这种调节还能重新排列孤对，从而产生巨大的光学各向异性。

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[Sn3OF]PO4vs. [Sn3F3]PO4: enhancing birefringence by breaking the R3 symmetry and realigning lone pairs†

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[Sn3OF]PO4vs. [Sn3F3]PO4: enhancing birefringence by breaking the R3 symmetry and realigning lone pairs†

Tin(II)-containing phosphates are promising candidates for designing and studying materials with enhanced birefringence. Herein, we present a novel compound [Sn₃OF]PO₄ that exhibits significant birefringence (Δn_obv. = 0.117 at 546 nm), a five-fold improvement compared to that of the related compound [Sn₃F₃]PO₄ discovered nearly 40 years ago. The remarkable enhancement in birefringence is primarily attributed to the anisotropic [SnO₃F]⁵⁻ structure building unit. By simple regulation of the F/O ratio, the undesirable R3 symmetry in [Sn₃F₃]PO₄ is disrupted. This regulation also realigns the lone pairs, resulting in substantial optical anisotropy.