Li_(4)AAl(SO_(4))_(2)F_(4)(A=Cs,Rb):两例具有特殊基元[AlS_(2)O_(8)F_(4)]的深紫外氟铝硫酸盐  

Li_(4)AAl(SO_(4))_(2)F_(4)(A=Cs,Rb):two deep-UV fluoroaluminosulfates with special motif[AlS_(2)O_(8)F_(4)]

作　　者：江豹 闫玉臣 刘醒龙 张博宣 陈兆慧 Bao Jiang;Yuchen Yan;Xinglong Liu;Boxuan Zhang;Zhaohui Chen(Key Laboratory of Oil&Gas Fine Chemicals,Ministry of Education and Xinjiang Uyghur Autonomous Region,School of Chemical Engineering and Technology,Xinjiang University,Urumqi 830017,China;School of Physics and Technology,Xinjiang University,Urumqi 830046,China)

机构地区：[1]石油天然气精细化工教育部暨自治区重点实验室,新疆大学化工学院,乌鲁木齐830017 [2]新疆大学物理与技术学院,乌鲁木齐830017

出　　处：《中国科学：化学》2023年第8期1559-1567,共9页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:51962033);国家重点实验室新疆高效专项(编号:KF2203)资助项目。

摘　　要：将氟引入含氧酸盐获得结构新颖及性能优异的无机新材料是当前无机功能晶体材料领域的热点.在氟铝硫酸盐体系,目前只报道了一例天然矿物晶体结构,因此,在该体系进行新结构的设计合成,对于探索硫酸盐晶体材料及丰富结构化学具有重要的意义.本工作中,通过高温固相法在封闭体系合成了两例氟铝硫酸盐晶体:Li_(4)CsAl(SO_(4))_(2)F_(4)和Li_(4)RbAl(SO_(4))_(2)F_(4),它们是首次通过人工合成的氟铝硫酸盐晶体.通过结构的研究,我们发现两个化合物属于同构,均由两个[SO_(4)]2−四面体和一个[AlO_(2)F_(4)]^(5−)八面体连接形成的独特孤立的[AlS_(2)O_(8)F_(4)]^(5−)阴离子,这种零维[AlS_(2)O_(8)F_(4)]^(5−)基元是首次报道.光学性能测试表明,它们的截止边都低于190 nm,达到了深紫外区,表明两种化合物具有深紫外波段应用的潜力,我们利用第一性原理计算分析了结构和光学性能之间的关系.The introduction of fluorine into oxysalts to obtain new inorganic materials with novel structures and excellent properties is a current hot topic in the field of inorganic functional crystal materials.In the fluoroaluminosulfates,only one case of natural mineral crystal structure has been reported,so it is extremely significant to be designed and synthesized for sulphates,which is beneficial to exploration and structural diversity of sulphate materials.In this work,two cases of fluoroaluminosulfate crystals,Li_(4)CsAl(SO_(4))2F4 and Li_(4)RbAl(SO_(4))2F4,are firstly synthesized artificially in a closed system by a high-temperature solid-phase method.Structural investigations manifested that isolated anion[AlS_(2)O_(8)F_(4)]^(5−)is formed by two[SO_(4)]2−tetrahedra and an[AlO_(2)F_(4)]^(5−)octahedron and the zero-dimensional motif[AlS_(2)O_(8)F_(4)]^(5−)is first reported.Their optical characterizations showed that the cut-off edges of both compounds can reach the deep UV region(<190 nm),which indicated that two compounds have the potential for deep UV band applications.Besides,the relationship of the two compounds between structure and optical performance was analyzed by employing first-principle calculations.

关 键 词：无机功能晶体 氟铝硫酸盐 人工合成 深紫外 

分 类 号：O743.3[理学—晶体学]