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Trinuclear copper (I) pyrazolate complexes for vapochromic sensing of aromatic volatile organic compounds

机译:三核吡唑酸铜(I)络合物用于芳香族挥发性有机化合物的气相致变色传感

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摘要

Vapochromism using optical chemosensors of d10 group metal complexes have a great potential for sensing different kinds of volatile organic compounds (VOCs) by vapor-triggered color and luminescence changes. Since organic aromatic vapors are mainly hazardous and carcinogenic to human health and environment, it is interesting challenge to develop the low-cost vapochromic chemosensors with high sensing capability. On the other hands, inorganic complexes and materials have been found to change their color and luminescence properties by modifying molecular structures. However, there is no study on, the relationship of molecular structures for chemosensors of VOCs such as aromatic vapors. Therefore, we report systematic study on by using supramolecular assembly of a weak metal-metal interaction, optical response of trinuclear copper(I) pyrazolate complexes ([Cu3Pz3]) for vapochromic chemosensors of benzene, toluene and hexafluorobenzene. The [Cu3Pz3] complexes have been successfully synthesized from 3,5-dimethyl (complex A), 3,5-trifluoromethyl (complex B), 3,5-diphenyl (complex C) and 4-(3,5-dimethoxybenzyl)-3,5-dimethyl (complex D) pyrazole ligands as a solid powder. The resulting complexes showed color emission in the range from red to green upon exposure to a UV hand lamp (254 nm) in dark room, which were in good agreement with emission spectra upon excitation at 280 nm; 590 nm (complex A), 570 nm (complex B), 614 nm (complex D) and upon excitation at 321 nm for emission at 642 nm (complex C). The sensing capability of all [Cu3Pz3] complexes with different molecular side-chains showed different phenomena depending on the types of aromatic solvents. In contrast to no response of complex A upon exposure to VOCs, complexes B and C showed gradually quenching of the intensity due to cleavage of Cu(I)-Cu(I) interaction. Interestingly, complex D showed blue shifting of its emission center due to enhancement of the metal-metal distance.
机译:使用d10类金属配合物的光学化学传感器进行气相致变色具有巨大潜力,可通过气相触发的颜色和发光变化来检测不同种类的挥发性有机化合物(VOC)。由于有机芳香蒸气主要危害人类健康和环境,并致癌,因此开发具有高传感能力的低成本气相致变色化学传感器是一个有趣的挑战。另一方面,已经发现无机配合物和材料通过改变分子结构来改变其颜色和发光性质。但是,关于芳香族蒸气等VOC的化学传感器的分子结构的关系,尚无研究。因此,我们报告了通过使用超分子组装的弱金属与金属的相互作用,系统研究三核吡唑酸铜(I)吡唑酸酯络合物([Cu3Pz3])对苯,甲苯和六氟苯的变色化学传感器的光学响应。 [Cu3Pz3]配合物已成功地由3,5-二甲基(配合物A),3,5-三氟甲基(配合物B),3,5-二苯基(配合物C)和4-(3,5-二甲氧基苄基)- 3,5-二甲基(复合物D)吡唑配体为固体粉末。暴露于暗室中的紫外线手灯(254 nm)下,所得配合物显示出从红色到绿色的颜色发射,这与在280 nm激发时的发射光谱非常吻合。 590 nm(复合物A),570 nm(复合物B),614 nm(复合物D),并在321 nm激发后在642 nm(复合物C)发射。具有不同分子侧链的所有[Cu3Pz3]配合物的传感能力根据芳族溶剂的类型显示出不同的现象。与复合物A暴露于VOC时无反应相反,复合物B和C由于裂解Cu(I)-Cu(I)相互作用而显示出强度的逐渐淬灭。有趣的是,由于金属间距离的增加,复合物D的发射中心呈现出蓝移。

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