摘要
通过高温固相合成技术,成功合成了一种新型含银簇卤化硼酸盐Ag_(3)B_(6)O_(10)I。该晶体属正交晶系,空间群为Pnma(No.62)。结构分析表明,该晶体结构中BO4四面体和BO3三角形连接形成[B_(6)O_(10)]^(2-)并最终相互连接形成三维孔洞结构,Ag3I三角锥位于孔洞中。这种基于B6O10基元的含银簇三维孔洞结构为首次报道。热稳定性分析表明Ag_(3)B_(6)O_(10)I为非同成分熔融化合物,熔融分解温度为963 K。紫外-可见-近红外漫反射光谱分析显示该晶体光学带隙约为3.1 eV。值得关注的是,Ag_(3)B_(6)O_(10)I晶体具有较大的双折射率(0.031@550 nm)。第一性原理理论计算揭示了该晶体的光学特性来源。
Birefringent crystals that can modulate the polarization of light play a significant role in modern optical devices including polarizing microscopes,optical isolators,and achromatic quarter-wave plates.Here we report a new silver cluster compound,Ag_(3)B_(6)O_(10)I,which features a three-dimensional pore structure formed by the connection of[B_(6)O_(10)]^(2-)fundamental structural units,with the Ag3I triangular pyramidal located in the pores.This structure with[B_(6)O_(10)]^(2-)as the basic unit is reported in silver cluster borate for the first time.This compound crystallizes in the Pnma(No.62)space group with a=1.2741(3)nm,b=0.97378(19)nm,c=0.83971(17)nm.It is a non-congruent melting compound and can be stable below 963 K.Notably,Ag_(3)B_(6)O_(10)I has a wide band gap(>3.1 eV),and exhibits a large linear optical response,that is,birefringence ofΔn=0.031 at the wavelength of 550 nm.Moreover,the structure-property relationships in Ag_(3)B_(6)O_(10)I are analyzed by first-principles calculations.This work suggests new possibilities for the design and fabrication of advanced birefringent crystals using the silver cluster.
作者
杜志鹏
周洋
赵三根
DU Zhi-Peng;ZHOU Yang;ZHAO San-Gen(State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China)
出处
《应用化学》
CAS
CSCD
北大核心
2023年第2期229-235,共7页
Chinese Journal of Applied Chemistry
基金
国家自然科学基金(Nos.22122507,61975207)
中国科学院前沿科学重点研究计划(No.ZDBS-LY-SLH024)
国家重点研发计划(No.2019YFA0210400)资助。
关键词
硼酸盐
银簇化合物
晶体结构
双折射率
第一性原理计算
Borates
Silver cluster
Crystal structure
Birefringence
First-principles calculations
