Shanghai Key Laboratory of Green Chemistry and Chemical Processes, College of Chemistry and Molecular Engineering , East China Normal University , Shanghai 200062 , P. R. China.
ACS Appl Mater Interfaces. 2018 Apr 4;10(13):11056-11062. doi: 10.1021/acsami.8b01314. Epub 2018 Mar 26.
The development of selective sensing materials for amine detection has received considerable attentions because amines have high toxicity and exist widely. In this article, we demonstrate for the first time that a degree of discriminative detection of alkylamines can be achieved by a metal-organic coordination material. The material is derived from Cd and 4,4'-bipyridinium-1,1'-bis(phenylene-3-carboxylate), shows 1D channels lined with electron-deficient viologen chromophores, and exhibits different colors upon contact with amine vapors of different molecular sizes and types (primary, secondary, and tertiary). The vapochromism is attributable to electron transfer from the amine group to viologen. The discrimination between amines is because the analyte-receptor interactions, which either directly mediate or indirectly affect electron transfer, are influenced by the number of the N-H bonds in the amine molecule, the size of the amine molecule relative to the receptor channel and the steric hindrance for the electron donor-acceptor contacts. The material also shows reversible photo- and hydrochromism owing to stimuli-induced reversible electron transfer. The compound can be deposited in paper simply by spraying the mixture solution of the starting metal salt and the ligand. The paper can be used as portable test strips for visual and differentiable detection of amines and as erasable inkless printing medium.
由于胺类具有高毒性且广泛存在，因此用于胺类检测的选择性传感材料的开发受到了相当多的关注。本文首次证明，通过金属有机配位材料可以实现对烷基胺的一定程度的区分检测。该材料由 Cd 和 4,4'-联吡啶-1,1'-双(苯-3-羧酸)衍生而来，具有一维通道，通道内排列有缺电子的紫罗精发色团，与不同分子大小和类型（伯、仲和叔）的胺蒸气接触时会呈现不同的颜色。蒸气致变色归因于胺基团向紫罗精的电子转移。胺的区分是因为分析物-受体相互作用，无论是直接介导还是间接影响电子转移，都受到胺分子中 N-H 键的数量、胺分子相对于受体通道的大小以及电子给体-受体接触的空间位阻的影响。该材料还由于刺激诱导的可逆电子转移而表现出可逆的光致变色和水致变色。该化合物可以通过简单地喷涂起始金属盐和配体的混合物溶液沉积在纸上。该纸可用作便携式测试条，用于对胺类进行可视和可区分的检测，也可用作可擦除的无墨打印介质。
