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首页> 外文期刊>Journal of Materials Chemistry, C. materials for optical and electronic devices >Luminescent sensing profiles based on anionresponsive lanthanide(III) quinolinecarboxylate materials: solid-state structures, photophysical properties, and anionic species recognition
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Luminescent sensing profiles based on anionresponsive lanthanide(III) quinolinecarboxylate materials: solid-state structures, photophysical properties, and anionic species recognition

机译：基于阴离子型镧系元素喹啉羧酸酯材料的发光传感曲线：固态结构，光物理性质和阴离子种类识别

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摘要

Lanthanide complexes based on the quinolinecarboxylate ligand 2-phenyl-4-quinolinecarboxylic acid (PQC), namely, Ln(2)PQC(6) (Ln = La3+, Pr3+, Nd3+, Sm3+ and Eu3+) were synthesized by a convenient solvothermal reaction, and the related crystal structures were determined. These complexes are isostructural and feature a discrete dinuclear moiety, in which solvent molecules act as coligands and the Ln(3+) centre exhibits distorted tricapped trigonal prism geometry. By the introduction of the PQC ligand, the europium sample Eu(2)PQC(6) (5) showing intense red emission in the solid state and solution, with both the replaceable coordination environment and potential hydrogen-bonding-accepting site, can be explored as a luminescent probe for sensing various anions. Among the tested ions (F-, Cl-, Br-, I-, NO3-, ClO4-, SCN-, HCO3-, HSO4- and H2PO4-), HSO4- and H2PO4- possess a strong response in the Eu3+ emitting behaviour leading to a unique quenching with a low detection limit of 15.3 and 8.3 nM, respectively, and a quick response time of less than 30 s. The different recognition mechanisms for two anions, including O-H center dot center dot N hydrogen bonding and metal coordination modes have been proposed, which are supported by UV-vis, fluorescence spectroscopy, nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) measurements. In addition, density functional theory (DFT) calculations were carried out to verify the two recognition mechanisms of Eu(2)PQC(6) in depth. As an extended research, Eu(2)PQC(6) interaction with the nucleoside phosphates adenosine triphosphate (ATP), adenosine diphosphate (ADP) and adenosine monophosphate (AMP) in mixed aqueous solution was investigated, which can act as a special luminescent sensor for all three phosphates. The strong quenching by ADP (99.5%), has been ascribed to the strong bonding affinity (log K-a = 5.99) based on electrostatic attractions and steric effects.
机译：通过方便的溶剂热反应合成了基于喹啉羧酸酯配体2-苯基-4-喹啉羧酸（PQC）的镧系元素络合物，即Ln（2）PQC（6）（Ln = La3 +，Pr3 +，Nd3 +，Sm3 +和Eu3 +），并确定了相关的晶体结构。这些复合物是同构的，具有离散的双核部分，其中溶剂分子充当大分子，Ln（3+）中心呈现扭曲的三棱柱三角几何形状。通过引入PQC配体，the样品Eu（2）PQC（6）（5）可以在固态和溶液中显示出强烈的红色发射，同时具有可替换的配位环境和潜在的氢键接受位点用作探测各种阴离子的发光探针。在测试离子（F-，Cl-，Br-，I-，NO3-，ClO4-，SCN-，HCO3-，HSO4-和H2PO4-）中，HSO4-和H2PO4-在Eu3 +发射行为中具有较强的响应导致独特​​的淬灭，其检测限分别低至15.3和8.3 nM，响应时间短于30 s。提出了对两种阴离子的不同识别机制，包括OH中心点，中心点N氢键和金属配位模式，这些均由紫外可见，荧光光谱，核磁共振（NMR）和X射线光电子能谱（XPS）支持） 测量。此外，进行了密度泛函理论（DFT）计算以验证Eu（2）PQC（6）的两种识别机制的深度。作为扩展研究，研究了Eu（2）PQC（6）与核苷磷酸盐三磷酸腺苷（ATP），二磷酸腺苷（ADP）和单磷酸腺苷（AMP）的相互作用，该溶液可作为特殊的发光传感器所有三种磷酸盐。基于静电引力和空间效应，ADP的强淬灭作用（99.5％）归因于强的键合亲和力（log K-a = 5.99）。

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