新型两亲性混配钌配合物的合成及其对Hg^(2+)的选择性“肉眼”识别  

Synthesis of New Mixed-ligands Amphiphilic Ruthenium Complex and Its Naked-eye Detectable Recognition of Hg^(2+)

作　　者：李襄宏[1] 段新方[2] 李富友[1] 黄春辉[1] 

机构地区：[1]复旦大学先进材料实验室,上海200433 [2]北京师范大学化学系,北京100875

出　　处：《高等学校化学学报》2006年第3期419-423,共5页Chemical Journal of Chinese Universities

基　　金：国家"八六三"计划(批准号:2002AA302403);国家自然科学基金(批准号:20490210);上海市科委基金(批准号:03QB14006;03DZ12031)资助.

摘　　要：采用与文献不同的路线合成了4,4′二(p甲基苯基)2,2′二联吡啶,与文献结果相比,总收率由4.0%提高至15.3%.该化合物和4,4′二羧基2,2′二联吡啶组成混合配体与金属钌配位,合成了两亲性、混配型配合物cisN,N4,4′二(p甲基)苯基2,2′二联吡啶N,N4,4′二羧基2,2′二联吡啶N,N二异硫氰钌配合物,并用IR,UVVis,NMR和MaldiTOF等手段进行表征.将该两亲性混配钌配合物首次用于对Hg2+的识别中,发现此配合物对Hg2+表现出灵敏的选择性“肉眼”识别:在DMF/乙醇溶液(体积比1∶9)中加入Hg2+后,MLCT态吸收由530nm蓝移到485nm.该配合物与Hg2+以1∶1(摩尔比)结合,检测限可低至0.5×10-6mol/L.4,4＇-Di （p-methylphenyl）-2,2＇-bipyridine was synthesized via modified routine with a high yield of 15.3%, and was used as a ligand to form a new mixed-ligand amphiphilic ruthenium complex, cis-N,N-4 ,4＇- di （p-methylphenyl）-2, 2＇-bipyridine-N, N-4, g＇-dicarboxy-2, 2＇-bipyridine-N, N-dithiocyanato ruthenium （ H ）. This new mixed-ligands amphiphilic ruthenium complex was characterized by IR, UV-Vis, ^1H NMR and Maldi-TOF MS spectra and firstly used to detect Hg^2＋. Its MLCT absorption（530 nm） was blue-shifted to 485 nm when Hg^2＋ was added to DMF-ethanol（volume ratio 1： 9） solution of the complex. The complex was combined quantitatively with Hg^2＋ not with other metal cations by the molar ratio of 1 ： 1, indicating that it can be used as a selective naked-eye sensor for Hg^2 ＋. Its detective limit is 0. 5×10^-6 mol/L.

关 键 词：两亲性混配钌配合物 MLCT谱 Hg^2+离子识别 “肉眼”识别 

分 类 号：O621.3[理学—有机化学] O557.3[理学—化学]