A cationic tetrahedral Zn(ii) cluster based on a new salicylamide imine multidentate ligand: synthesis, structure and fluorescence sensing study
A cationic tetrahedral Zn(ii) cluster based on a new salicylamide imine multidentate ligand: synthesis, structure and fluorescence sensing study
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基于新型水杨酰胺亚胺多齿配体的阳离子四面体 Zn(ii) 簇：合成、结构和荧光传感研究
DOI：
10.1039/c9dt01376h
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发表时间：
2019
影响因子：
4
通讯作者：
Wang Li
中科院分区：
文献类型：
--
作者：
Meng Huan Huan;Wang Cai Yun;Xi Wei;Song Xue Qin;Wang Li
合成了一种新的水杨酰胺亚胺配体H_2L，H_2L=1-(2-hydroxy-3-methoxy-benzamido)-3-(2-hydroxy-3-methoxy-benzylideneamino)-propane，的单阳离子锌四面体簇合物[Zn_4L_3(μ_3-OH)]·NO_3·1.25H_2O。单晶X-射线分析表明，三个去质子化的配体L2-与三个锌(II)中心及其水杨酰胺基团以这样的方式结合在一起，即连接在三个螯合物另一侧的三个水杨胺基团聚集在一起，与另一个锌(II)中心结合在一起，形成一个具有相同配体L2的两个苯基的四面体簇合物--足够接近，从而呈现出很强的分子内π⋯π堆积效应。荧光研究表明，在HEPES缓冲溶液(pH=7.4)+DMSO(V ： V=1 ： 9)中，锌在水中稳定，对其他常见阴离子，包括CO32-、HCO3-、NO3-、F−、Cl−、Br−、I−、HSO4-、SO42-、OAc−、BF4-、ClO4-和CF3SO3-表现出高度灵敏和选择性的识别作用。对于其他常见阴离子，锌锂对磷酸盐具有良好的传感能力，其低检测下限为0.15μM，是一种检测磷酸盐的候选探针。此外，观察到的锌对磷酸盐的荧光猝灭反应是高度可逆的。用核磁共振氢谱、紫外-可见光谱和高分辨电喷雾质谱研究了锌盐对磷酸盐的敏感机理，结果表明，在HEPES缓冲溶液(pH=7.4)+二甲基亚砜(V ： V=1 ： 9)中，磷酸盐能专属地分解锌盐而释放出H 2L。
A monocationic ZnII tetrahedral cluster, [Zn4L3(μ3-OH)]·NO3·1.25H2O (Zn4L3) based on a new salicylamide imine ligand H2L, H2L = 1-(2-hydroxy-3-methoxy-benzamido)-3-(2-hydroxy-3-methoxy-benzylideneamino)-propane, has been prepared. Single crystal X-ray analysis reveals that three deprotonated ligands L2– chelate three Zn(II) centres with their salicylamide moiety in such a way that the three salicylimine groups attached to the other side of the three chelates are converged to bind another Zn(II) centre to provide a tetrahedral cluster with two phenyl groups of the same ligand L2– being close enough to present a strong intramolecular π⋯π stacking effect. Fluorescence studies indicate that Zn4L3 is stable in water and exhibits highly sensitive and selective recognition of phosphates against other common anions including CO32–, HCO3–, NO3–, F−, Cl−, Br−, I−, HSO4–, SO42–, OAc−, BF4–, ClO4– and CF3SO3– in HEPES buffer solution (pH = 7.4) + DMSO (V : V = 1 : 9). The excellent sensing capability of Zn4L3 for phosphate against other common anions with a low detection limit of 0.15 μM renders it a candidate probe for phosphate detection. Furthermore, the observed fluorescence quenching responses of Zn4L3 towards phosphates were highly reversible. The possible sensing mechanisms for phosphate detection by Zn4L3 was investigated by means of 1H NMR, UV-Vis spectra and high-resolution ESI-MS spectra and the results indicate that phosphates could exclusively decompose Zn4L3 to release H2L in HEPES buffer solution (pH = 7.4) + DMSO (V : V = 1 : 9).