Methanol-induced luminescence vapochromism based on a Sb^(3+)-doped organic indium halide hybrid  

基于锑(Ⅲ)掺杂的氯化铟杂化材料通过甲醇诱导实现的蒸汽变色

作　　者：Cui-Mi Shi Jin-Long Li Liang-Jin Xu Yue Wu Hong-Li Xuan Jin-Yun Wang Zhong-Ning Chen 石翠密;李金龙;徐亮金;吴越;宣宏丽;王金云;陈忠宁(College of Chemistry,Fuzhou University,Fuzhou 350108,China;State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China;Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou 350108,China)

机构地区：[1]College of Chemistry,Fuzhou University,Fuzhou 350108,China [2]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [3]Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou 350108,China

出　　处：《Science China Materials》2022年第7期1876-1881,共6页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(22175181,92061202,and 21531008);Fujian Science and Technology Project(2020L3022);the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)。

摘　　要：Ion doping has been demonstrated as a practical approach to achieving highly efficient luminescence in both inorganic phosphors and organic-inorganic hybrids.The asformed doping species show great potential in optoelectronic applications due to their high photoluminescence quantum yield(PLQY)and excellent stability.Herein,we report highly emissive Sb^(3+)-doped indium halides(C_(6)H_(18)N_(2))InCl_(5)·H_(2)O:Sb(C_(6)H_(18)N_(2)^(2+)=N,N,N',N'-tetramethylethane-1,2-diammonium)prepared by solution evaporation methods with an emission that peaked at 565 nm and a PLQY of 74.6%.Photophysical characterizations and density functional theory computational studies verify the broadband emission originating from a self-trapped exciton.Interestingly,a drastic red shift of the emission peak from 565 to 663 nm with yellow luminescence turning to red is observed once the(C_(6)H_(18)N_(2))InCl_(5)·H_(2)O:Sb hybrid is exposed to methanol vapor.Moreover,when the methanol-exposed hybrid is put in air,the emission reverts to 565 nm in several minutes.Single-crystal X-ray diffraction studies show a subsequent structure distortion upon the coordination of methanol to the Sb(III)center,which is responsible for the drastic red shift of the emission.Encouragingly,we found that(C_(6)H_(18)N_(2))InCl_(5)·H_(2)O:Sb exhibits a specific response to methanol vapor after screening a series of volatile organic compounds with different polarities.Besides,a negligible change of the emission intensity is observed after several cycles of uptaking and releasing methanol.The high fatigue resistance and specific solvent response of the Sb^(3+)-doped indium halide make it a very promising methanol detector.离子掺杂已被证明是在无机荧光粉和有机-无机杂化材料中实现高效发光的一种有效方法.掺杂体系大多具有较高的光致发光量子产率(PLQY)和优异的稳定性,因此在光电器件领域有着潜在的应用前景.本论文采用同价离子掺杂的策略,通过溶液蒸发方法制备了高效发光的Sb^(3+)掺杂的铟基卤化物(C_(6)H_(18)N_(2))InCl_(5)·H_(2)O:Sb(C_(6)H_(18)N_(2)^(2+)=N,N,N',N'-四甲基乙烷-1,2-二铵),其发射峰值为565 nm,PLQY为74.6%.光物理性质表征和密度泛函理论(DFT)计算研究证明了该宽带发射起源于自陷激子.当(C_(6)H_(18)N_(2))InCl_(5)·H_(2)O:Sb杂化材料暴露在甲醇蒸气中时,在365 nm的紫外光激发下,其发射峰从565 nm显著红移到663 nm,发光颜色由黄色变为红色;当将暴露于甲醇的杂化材料置于空气中时,几分钟后其发射将恢复到原来的565 nm的黄光发射.单晶X射线衍射研究表明,甲醇与Sb(Ⅲ)中心配位后的结构畸变是导致发射红移的原因.在筛选了一系列不同极性的挥发性有机溶剂(VOC)后,我们发现(C_(6)H_(18)N_(2))InCl_(5)·H_(2)O:Sb对甲醇蒸汽表现出特定的响应.此外,当材料吸收和释放甲醇的几个循环后,其发射强度未发生明显变化.高抗疲劳性和专一的溶剂响应使这种Sb^(3+)掺杂的铟基卤化物能够成为非常有前景的甲醇检测材料.

关 键 词：organic metal halide hybrid Sb^(3+) doped self-trapped exciton emission luminescence vapochromism 

分 类 号：TQ133.53[化学工程—无机化工]