基于(E)⁃N,N⁃二甲基⁃4⁃(2⁃(吡啶⁃4⁃基)乙烯基)苯胺的锌/镉有机-无机杂化金属卤化物的结构和发光性质  

Structures and Photoluminescence Properties of Zinc(Ⅱ)/Cadmium(Ⅱ)⁃Based Organic⁃Inorganic Hybrid Metal Halides Derived from(E)⁃N,N⁃Dimethyl⁃4⁃(2⁃(pyridin⁃4⁃yl)vinyl)aniline

作　　者：王申宇 陈典 刘晓莉[2] 王硕文 苑亚南 王振平[2] 杨春[2] WANG Shen‑Yu;CHEN Dian;LIU Xiao‑Li;WANG Shuo‑Wen;YUAN Ya‑Nan;WANG Zhen‑Ping;YANG Chun(College of Chemistry,Jilin University,Changchun 130012,China;School of Chemical Engineering and Technology,Hebei University of Technology,Tianjin 300130,China)

机构地区：[1]吉林大学化学学院,长春130012 [2]河北工业大学化工学院,天津300130

出　　处：《无机化学学报》2021年第9期1659-1664,共6页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21101096);河北省引进留学人员资助项目(No.C20200317)资助。

摘　　要：以(E)‑N,N‑二甲基‑4‑(2‑(吡啶‑4‑基)乙烯基)苯胺(EDPVA)为有机源,以金属卤化物ZnX2和CdX2为无机源,用相应的浓酸HX(X=Cl、Br)提供酸性介质,通过溶剂缓慢挥发法得到了4个离子型单核有机-无机杂化金属卤化物(H_(2)EDPVA)[ZnCl_(4)](1)、(H_(2)EDPVA)[ZnBr_(4)](2)、(H_(2)EDPVA)[CdCl_(4)](3)和(H_(2)EDPVA)[CdBr_(4)](4)。X射线单晶衍射分析表明,交替排列的刚性有机阳离子(H_(2)EDPVA)^(2+)和稍微扭曲的四面体形无机阴离子[MX_(4)]^(2-)(M=Zn、Cd;X=Cl、Br)之间存在静电作用和氢键。发光性质研究表明,化合物1~4的蓝色磷光峰分别位于459、446、440和434 nm,斯托克斯位移分别为79、72、61和55 nm,半峰宽分别为100、88、87和100 nm,发光寿命τ分别为0.47、8.38、18.38和11.62μs。发光机理分析表明:化合物1~4的磷光发射是有机阳离子和无机阴离子协同作用的结果。With(E)‑N,N‑dimethyl‑4‑(2‑(pyridin‑4‑yl)vinyl)aniline(EDPVA)as the organic source,and metal halides ZnX2 and CdX2 as the inorganic source,using the corresponding concentrated HX(X=Cl,Br)to provide acidic medium,four ionic mononuclear organic‑inorganic hybrid metal halides,(H_(2)EDPVA)[ZnCl_(4)](1),(H_(2)EDPVA)[ZnBr_(4)](2),(H_(2)EDPVA)[CdCl_(4)](3)and(H_(2)EDPVA)[CdBr_(4)](4),were obtained by slow evaporation of solvent.Single crystal structure analysis shows that there were electrostatic interactions and hydrogen bonds between the alternative rigid organic cations(H_(2)EDPVA)^(2+)and slightly distorted tetrahedral inorganic anions[MX_(4)]^(2-)(M=Zn,Cd;X=Cl,Br).The photoluminescence properties of compounds 1~4 showed that the blue phosphorescence peaks were at 459,446,440 and 434 nm,respectively;the Stokes shifts were 79,72,61 and 55 nm,respectively;the full widths at halfmaximum were 100,88,87 and 100 nm,respectively;the luminescence lifetimes(τ)were 0.47,8.38,18.38 and 11.62μs,respectively.According to the photoluminescence mechanism analysis,the phosphorescent emission of compounds 1~4 is the result of synergistic action of organic cations(H_(2)EDPVA)^(2+)and inorganic anions[ZnX_(4)]^(2-)or[CdX_(4)]^(2-)(X=Cl,Br),respectively.CCDC:2094237,1;2094238,2;2094239,3;2094240,4.

关 键 词：低维结构 杂化金属卤化物 光致发光 晶体结构 

分 类 号：O614.241[理学—无机化学] O614.242[理学—化学]