杯[4]芳烃修饰的钌(Ⅱ)配合物的合成与性质
Synthesis and Properties of a Calix[4]arene-Based Ruthenium(Ⅱ) Complex
作者单位E-mail
黄秋颖 河南工业职业技术学院化学工程系, 南阳 473009 huangqy72@163.com 
韩银锋 泰山学院化学化工学院, 泰安 271021  
郑泽宝 泰山学院化学化工学院, 泰安 271021 zhengzebao@163.com 
摘要: 合成了一种新颖的杯[4]芳烃修饰的钌(Ⅱ)配合物[Ru2(bpy)4(H2L)](ClO441)(bpy=2,2'-联吡啶,H2L=11,23-双(2-咪唑[4,5-f]-1,10-菲啰啉)-25,27-二羟基-26,28-二乙酯基丙基-5,17-二-对叔丁基-杯[4]芳烃),并通过红外光谱、核磁共振氢谱和碳谱、电喷雾质谱和元素分析对该配合物进行了表征。在乙腈/Britton-Robinson缓冲溶液(1:100,V/V)中研究了配合物1的pH光开关性质。发现随着溶液pH值的变化,配合物1经历两步质子化/去质子化过程,是一个很好的"off-on-off"型pH诱导的分子光开关,其开关比分别为1.42和96.0。通过加入不同阴离子引起配合物1溶液的吸收光谱、发射光谱和核磁共振氢谱的变化研究了其对阴离子的传感性能,发现该配合物可以通过荧光淬灭来识别F-和OAc-。另外初步细胞成像实验显示配合物1可以在短时间内穿过细胞膜对细胞质进行染色,而且在成像浓度范围内对Hela细胞体现出低毒性。
关键词: 钌(Ⅱ)配合物  杯[4]芳烃  pH光开关  阴离子传感  细胞成像
基金项目: 国家自然科学基金(No.21571137)、河南省科技攻关计划项目(No.172102210128)、山东省自然科学基金(No.ZR2015BL002)、泰安市科技计划项目(No.2015GX2048)和泰山学院引进人才项目(No.Y-01-2014017)资助。
Abstract: A new calix[4]arene-based ruthenium(Ⅱ) complex of[Ru2(bpy)4(H2L)](ClO4)4 (1) (bpy=2,2'-bipyridine and H2L=11,23-bis(2-imidazo[4,5-f]-1,10-phenanthroline)-25,27-dihydroxy-26,28-diethoxycarbonylpropyl-5,17-di-p-t-butyl-calix[4]arene) was synthesized and characterized using an assortment of spectroscopic techniques such as IR, 1H NMR, 13C NMR, ESI-MS, and elementary analysis. The pH luminescence switching property of 1 was studied by means of spectrofluorimetric titrations in CH3CN/Britton-Robinson buffer solution (1:100, V/V). The complex exhibited two-step separate protonation/deprotonation processes, and acting as a pH-induced "off-on-off" luminescence switch (Ion/Ioff=1.42 and 96.0). The anion sensing properties of complex 1 were thoroughly investigated in solution using absorption, emission, and 1H NMR spectral studies, which revealed that 1 acted as an efficient "turn off" emission sensor for F- and OAc-. Importantly, cellular imaging and cytotoxicity experiments demonstrated that 1 rapidly penetrate through the HeLa cells membrane, and showed low cytotoxicity at the imaging concentration.
Keywords: ruthenium(Ⅱ) complex  calix[4]arene  pH switch  anion sensing  cell imaging
投稿时间:2017-07-19 修订日期:2017-10-22
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黄秋颖,韩银锋,郑泽宝.杯[4]芳烃修饰的钌(Ⅱ)配合物的合成与性质[J].无机化学学报,2018,34(2):217-229.
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