一系列同多钼酸盐-紫精化合物:结构以及光致变色、有机胺传感、双重防伪性能研究  

A series of isopolymolybdate-viologen compounds:structures and photochromic,organic amine sensing,and double anti-counterfeiting properties

作　　者：于爽 应俊[1] 田爱香[1] 王秀丽[1] Shuang Yu;Jun Ying;Aixiang Tian;Xiuli Wang(Colloge of Chemistry and Materials Engineering,Bohai University,Jinzhou 121013,China)

机构地区：[1]渤海大学化学与材料工程学院,锦州121013

出　　处：《中国科学：化学》2023年第9期1711-1723,共13页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:21571023,22271021,21671025);辽宁省“兴辽英才”计划(编号:XLYC1807049,XLYC1902011);辽宁省教育厅一般项目基金(编号:LQ2020010,LJKMZ20221479);辽宁省自然科学基金会(编号:2022-MS-369);渤海大学校内博士启动项目(编号:0523bs004)资助。

摘　　要：在本工作中,我们通过引入[Mo_(8)O_(26)]^(4)–阴离子的两种异构体以及对称紫精配体,在溶剂热条件下合成了化合物1~3,即{ZnⅡ(1,3-bcbpy)1.5(H_(2)O)[H_(2)(β-Mo_(8)O_(26)]}·2H_(2)O·2C_(2)H_(7)N(1)、[Co_(3)Ⅱ(1,3-bcbpy)4(H_(2)O)_(4)(γ-Mo_(8)O_(26))_(2)]·16H_(2)O(2)和{NiⅡ(1,3-bcbpy)(H_(2)O)2[H_(2)(γ-Mo_(8)O_(26))]}·4H_(2)O·2C_(2)H_(7)N(3)(1,3-bcppy·2Cl=1,1′-双(3-羧基苄基-4,4′-联吡啶)二氯化物).化合物1的金属有机单元[Zn4(1,3-bcbpy)_(5)]^(8+)是“蝴蝶结状”的结构,而游离的β-Mo8阴离子通过氢键作用连接在蝴蝶结上.化合物2是典型的ABAB堆叠的2D层超分子结构,而化合物3是由平行的1D链间通过Ni原子与γ-Mo8的O原子配位形成的2D层结构.由于化合物1~3具有可逆的光致变色性能和优异的荧光淬灭效果,我们成功制备了基于1~3的具有柔韧性的紫外检测器.而当2和3暴露于胺气氛下时,2和3对NH3和en表现出明显的颜色变化.基于这一特点,我们制备了胺的检测试纸.此外,1还可以被用作一种新的印刷材料介质,可实际应用于可擦除的无墨打印,也可作为具有双重防伪性能的材料使用.In this article,by introducing two isomers of[Mo_(8)O_(26)]anions and a symmetrical viologen ligand,we synthesized three compounds 1-3 with different structures under solvothermal conditions,namely(Zn(1,3-bcbpy)1.5(H_(2)O)[H_(2)(β-Mo_(8)O_(26)]}·2H_(2)O·2C_(2)H_(7)N(1)、[Co_(3)Ⅱ(1,3-bcbpy)4(H_(2)O)_(4)(γ-Mo_(8)O_(26))_(2)]·16H_(2)O(2)and{NiⅡ(1,3-bcbpy)(H_(2)O)2[H_(2)(γ-Mo_(8)O_(26))]}·4H_(2)O·2C_(2)H_(7)N(3)(1,3-bcppy·2Cl=1,1′-bis(3-carboxybenzyl)-4,4'-bipyridine dichloride).The metal organic unit[Zn4(1,3-bcbpy)s]8+of compound 1 has a“bowknot-like"structure,while the freeβ-Mog anions are connected to the bow by hydrogen bonding.Compound 2 is a typical ABAB stacked 2D layer supramolecular structure,while compound 3 is composed of parallel 1D chains,which are connected to form a 2D layer structure through the coordination of Ni atom and the O atom of y-Mog.Due to the reversible photochromic properties and excellent fluorescence quenching effect of compounds 1-3,we have successfully prepared flexible UV detectors based on 1-3.When 2 and 3 were exposed to amine atmosphere,they exhibited significant color changes for NH and ethanediamine.Based on this characteristic,we prepared amine colorimetric test paper.In addition,1 can also be used as a new printing material medium,which can be practically applied to erasable inkless printing,and can also be used as a material with dual anti-counterfeiting properties.

关 键 词：多金属氧酸盐 对称紫精配体 光致变色 紫外检测器 有机胺检测试纸 

分 类 号：O641.4[理学—物理化学] TB34[理学—化学]