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Cation-anion synergetic interactions achieving tunable birefringence in quasi-one-dimensional antimony(III) fluoride oxalates

阴阳离子协同作用在系列准一维氟化草酸锑中实现双折射调控

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Abstract

Birefringent materials with large optical anisotropy, which can be used to modulate the polarization of light, play a key role in laser techniques and science. However, the exploration studies of new, superior birefringent materials develop extremely slowly due to the lack of effective guidelines for rational design. Herein, three antimony(III) fluoride oxalates, namely, Na2Sb2(C2O4)F6, K2Sb2(C2O4)F6, and Cs2Sb2-(C2O4)2F4·H2O, were successfully synthesized through a rational combination of π-conjugated C2O42− anions and Sb3+ cations with stereochemically active lone pairs. These oxalates feature unique quasi-one-dimensional chain structures that induce large optical anisotropy. Remarkably, Cs2Sb2(C2O4)2-F4·H2O exhibits the largest birefringence (0.325@546 nm) among all reported antimony(III)-based oxysalts. Detailed structural analysis and theoretical calculations confirmed that the optical anisotropy of these oxalates could be tuned through the synergetic interactions of templated cations and anionic functional groups. This work may open the door to efficiently designing excellent birefringent materials and guide the further discovery of other novel structure-driven functional materials.

摘要

具有较大光学各向异性的双折射材料可以用来调制光的偏振,在激光科学与技术中发挥着关键作用. 然而, 由于缺乏理性设计的有效策略, 新型高性能双折射材料的探索研究进展极其缓慢. 本文通过采用π共轭C2O42−阴离子和含具有立体化学活性孤对电子的Sb3+阳离子相结合, 成功地合成了三例氟化草酸锑盐, 分别为Na2Sb2(C2O4)F6、K2Sb2-(C2O4)F6和Cs2Sb2(C2O4)2F4·H2O.它们都具有独特的准一维链状结构,并表现出大的光学各向异性. 尤其是Cs2Sb2(C2O4)2F4·H2O表现出巨大的双折射率(0.325@546nm), 在所有已报道的锑(III)基含氧酸盐中最大. 详细的结构分析和理论计算证实, 阳离子模版剂和阴离子功能基团的协同作用可以调节化合物的光学各向异性. 这项工作为高效设计优良的双折射材料打开了一扇大门, 并为新型结构驱动功能材料的进一步发现提供了指导.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22122106, 22071158, 21971171, and 21875146). Ok KM thanks the National Research Foundation of Korea (NRF) funded by the Ministry of Science and International Cooperation of Technology (2019R1A2C3005530).

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Authors and Affiliations

  1. College of Chemistry and Materials Science, Sichuan Normal University, Chengdu, 610066, China

    Die Zhang  (张喋), Qiang Wang  (王强), Ting Zheng  (郑婷), Liling Cao  (曹礼玲), Daojiang Gao  (高道江), Jian Bi  (毕剑) & Ling Huang  (黄玲)

  2. Department of Chemistry, Sogang University, Seoul, 04107, Korea

    Kang Min Ok  (玉康民)

  3. College of Chemistry, Sichuan University, Chengdu, 610065, China

    Guohong Zou  (邹国红)

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  1. Die Zhang  (张喋)
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  2. Qiang Wang  (王强)
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  4. Liling Cao  (曹礼玲)
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  8. Ling Huang  (黄玲)
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  9. Guohong Zou  (邹国红)
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Contributions

Zhang D carried out the experiments, performed the data processing, and wrote the manuscript. Wang Q performed the theoretical calculation of the crystals. Ok KM revised the manuscript. Zheng T, Cao L, Gao D, and Bi J offered help in analyzing the experimental data. Huang L designed the organization of the manuscript and revised the manuscript. Zou G guided and designed the experiment. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Ling Huang  (黄玲) or Guohong Zou  (邹国红).

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Conflict of interest

The authors declare that they have no conflict of interest.

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Supporting data are available in the online version of the paper.

Die Zhang is currently a master student at the School of Chemistry and Materials Science, Sichuan Normal University. She received a bachelor degree in chemistry from Leshan Normal University in 2016. Her research focuses on exploring new nonlinear optical materials.

Ling Huang graduated with a bachelor of science degree from the School of Chemistry, Northeast Normal University in 2008 and a doctor of science degree from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, in 2013. From 2013 to 2016, she worked at the New Materials Research Center of the Institute of Chemical Materials, Chinese Academy of Engineering Physics, and joined the School of Chemistry and Materials Science, Sichuan Normal University, in March 2016. She is engaged in designing new nonlinear optical crystal materials.

Guohong Zou graduated from the Central South University with a bachelor’s degree in 2008 and graduated from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, with a doctoral degree in 2013. From 2015 to 2017, he was engaged in postdoctoral research at Chung-Ang University. In November 2017, he joined Sichuan University as a professor. In 2021, he obtained the support of the National Science Fund for Excellent Young Scholars. He focuses on the structural design and controllable synthesis of new inorganic solid photoelectric crystal materials.

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Cation-anion synergetic interactions achieving tunable birefringence in quasi-one-dimensional antimony(III) fluoride oxalates

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Zhang, D., Wang, Q., Zheng, T. et al. Cation-anion synergetic interactions achieving tunable birefringence in quasi-one-dimensional antimony(III) fluoride oxalates. Sci. China Mater. 65, 3115–3124 (2022). https://doi.org/10.1007/s40843-022-2088-0

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