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A highly selective turn-on colorimetric and luminescence sensor based on a triphenylamine-appended ruthenium(Ⅱ) dye for detecting mercury ion
作者姓名:Su-Hua Fan  Jie Shen  Hai Wu  Ke-Zhi Wangb  An-Guo Zhang
作者单位:a School of Chemical and Materials Engineering, Fuyang Normal College, Fuyang 236037, China; b College of Chemistry, Beijing Normal University, Beijing 100875, China; c College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China
摘    要:A dual colorimetric and luminescent sensor based on a heteroleptic ruthenium dyeRu(Hipdpa)(Hdcbpy)(NCS)_2]~-·0.5H~+ 0.5N(C_4H_9)_4]~+ Ru(Hipdpa) {where Hdcbpy = monodeprotonted-4,4'-dicarboxy-2.2'-bipyridineand Hipdpa = 4-(1H-imidazo4,5-f]l,10]phenanthroIin-2-yl)-N,N-diphenylaniIine} for selective detection of Hg~(2+) is presented.The results of spectrophotometric titrations revealed an evident luminescence intensity enhancement(I/I_0 =11) and a considerable blue shift in visible absorption and luminescence maxima with the addition of Hg~(2+).The sensitive response of the optical sensor on Hg~(2+) was attributed to the binding of the electron-deficient Hg~(2+) to the electron-rich sulfur atom of the thiocyanate(NCS) ligand in the Ru(Hipdpa).which led to an increase in the energy gap between the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO).Accordingly,the blue shift in the absorption spectrum of Ru(Hipdpa) due to the binding of Hg~(2+) was obtained.Ru(Hipdpa) was found to have decreased Hg~(2+) detection limit and improved linear region as compared to di(tetrabutylammonium) ris-bis(isothiocyanato)bis(2,2'-bipyridine-4-carboxylic acid-4'-carboxylate)ruthenium(Ⅱ) N719.Moreover,a dramatic color change from pink to yellow was observed,which allowed simple monitoring of Hg~(2+) by either naked eyes or a simple colorimetric reader.Therefore,the proposed sensor can provide potential applications for Hg~(2+) detection.

收稿时间:2014-09-15
修稿时间:2014-11-17

A highly selective turn-on colorimetric and luminescence sensor based on a triphenylamine-appended ruthenium(II) dye for detecting mercury ion
Su-Hua Fan,Jie Shen,Hai Wu,Ke-Zhi Wangb,An-Guo Zhang.A highly selective turn-on colorimetric and luminescence sensor based on a triphenylamine-appended ruthenium(II) dye for detecting mercury ion[J].Chinese Chemical Letters,2015,26(5):580-584.
Authors:Su-Hua Fan  Jie Shen  Hai Wu  Ke-Zhi Wangb  An-Guo Zhang
Institution:a School of Chemical and Materials Engineering, Fuyang Normal College, Fuyang 236037, China; b College of Chemistry, Beijing Normal University, Beijing 100875, China; c College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China
Abstract:A dual colorimetric and luminescent sensor based on a heteroleptic ruthenium dye Ru(Hipdpa)(Hdcbpy)(NCS)2]-·0.5H+0.5N(C4H9)4]+ Ru(Hipdpa) {where Hdcbpy = monodeprotonted-4,4''-dicarboxy-2,2''- bipyridine and Hipdpa = 4-(1H-imidazo4,5-f]1,10]phenanthrolin-2-yl)-N,N-diphenylaniline} for selective detection of Hg2+ is presented. The results of spectrophotometric titrations revealed an evident luminescence intensity enhancement (I/I0 = 11) and a considerable blue shift in visible absorption and luminescence maxima with the addition of Hg2+. The sensitive response of the optical sensor on Hg2+ was attributed to the binding of the electron-deficient Hg2+ to the electron-rich sulfur atom of the thiocyanate (NCS) ligand in the Ru(Hipdpa), which led to an increase in the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Accordingly, the blue shift in the absorption spectrum of Ru(Hipdpa) due to the binding of Hg2+ was obtained. Ru(Hipdpa) was found to have decreased Hg2+ detection limit and improved linear region as compared to di(tetrabutylammonium) cis-bis(isothiocyanato)bis(2,2''-bipyridine-4-carboxylic acid-4''- carboxylate)ruthenium(II) N719. Moreover, a dramatic color change from pink to yellow was observed, which allowed simple monitoring of Hg2+ by either naked eyes or a simple colorimetric reader. Therefore, the proposed sensor can provide potential applications for Hg2+ detection.
Keywords:Ruthenium dye  Mercury  Colorimetric sensor  Luminescence sensor
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