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

作　　者：Die Zhang Qiang Wang Ting Zheng Liling Cao Kang Min Ok Daojiang Gao Jian Bi Ling Huang Guohong Zou 张喋;王强;郑婷;曹礼玲;玉康民;高道江;毕剑;黄玲;邹国红(College of Chemistry and Materials Science,Sichuan Normal University,Chengdu 610066,China;Department of Chemistry,Sogang University,Seoul 04107,Republic of Korea;College of Chemistry,Sichuan University,Chengdu 610065,China)

机构地区：[1]College of Chemistry and Materials Science,Sichuan Normal University,Chengdu 610066,China [2]Department of Chemistry,Sogang University,Seoul 04107,Republic of Korea [3]College of Chemistry,Sichuan University,Chengdu 610065,China

出　　处：《Science China Materials》2022年第11期3115-3124,共10页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(22122106,22071158,21971171,and21875146);National Research Foundation of Korea(NRF)funded by the Ministry of Science and International Cooperation of Technology(2019R1A2C3005530)。

摘　　要：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,Na_(2)Sb_(2)(C_(2)O_(4))F_(6),K_(2)Sb_(2)(C_(2)O_(4))F_(6),and Cs_(2)Sb_(2)-(C_(2)O_(4))_(2)F_(4)·H_(2)O,were successfully synthesized through a rational combination ofπ-conjugated C_(2)O_(4)^(2-)anions and Sb^(3+)cations with stereochemically active lone pairs.These oxalates feature unique quasi-one-dimensional chain structures that induce large optical anisotropy.Remarkably,Cs_(2)Sb_(2)(C_(2)O_(4))_(2)-F_(4)·H_(2)O 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.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C_(2)O_(4)2-阴离子和含具有立体化学活性孤对电子的Sb^(3+)阳离子相结合,成功地合成了三例氟化草酸锑盐,分别为Na_(2)Sb_(2)(C_(2)O_(4))F_(6)、K_(2)Sb_(2)-((C_(2)O_(4))F_(6)和Cs_(2)Sb_(2)(C_(2)O_(4))_(2)F_(4)·H_(2)O.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Cs_(2)Sb_(2)(C_(2)O_(4))_(2)F_(4)·H_(2)O表现出巨大的双折射率(0.325@546 nm),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.

关 键 词：birefringent materials optical anisotropy antimony(Ⅲ)fluoride oxalates synergetic interactions 

分 类 号：TB34[一般工业技术—材料科学与工程]