A bis(ferrocenyl)phenanthroline iridium(III) complex as a lab-on-a-molecule for cyanide and fluoride in aqueous solution.
A bis(ferrocenyl)phenanthroline iridium(III) complex as a lab-on-a-molecule for cyanide and fluoride in aqueous solution.
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DOI：
10.1021/ic301256g
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发表时间：
2012-11
影响因子：
4.6
通讯作者：
Q. Shu;L. Birlenbach;M. Schmittel
中科院分区：
文献类型：
--
作者：
Q. Shu;L. Birlenbach;M. Schmittel
合成了双（二茂铁基）菲咯啉铱（III）配合物1，并将其作为一个分子实验室用于水溶液中氰化物和氟化物的竞争和定量测定。1表现出很强的关-开光致发光（PL）响应时，添加氰化物与其他阴离子具有良好的选择性。该机制涉及亲核取代的菲咯啉配体，淬灭PL，提供一个强烈的光致发光二氰基铱配合物。相反，在电化学发光（ECL）通道，氰化物进行氧化和观察到不同的选择性。在ECL中首次利用了强的二茂铁-氟化物相互作用，以选择性地监测氟化物，增强>60倍。在PL和ECL通道中，阴离子选择性进一步受到其他阴离子存在下竞争性测定的挑战。在两个通道中实现CN（-）和F（-）的定量测定。
The bis(ferrocenyl)phenanthroline iridium(III) complex 1 is synthesized and elaborated as a lab-on-a-molecule for the competitive and quantitative determination of cyanide and fluoride in aqueous solution. 1 exhibits a strong OFF-ON photoluminescence (PL) response upon addition of cyanide with a good selectivity over other anions. The mechanism involves nucleophilic displacement of the phenanthroline ligand, which quenches PL, to furnish a strongly photoluminescent dicyano iridium complex. In contrast, in the electrochemiluminescence (ECL) channel, cyanide undergoes oxidation and a different selectivity is observed. The strong ferrocenium-fluoride interaction is exploited for the first time in ECL to selectively monitor fluoride by a >60-fold enhancement. In both PL and ECL channels, anion selectivity is further challenged by competitive assays in the presence of other anions. Quantitative determination of CN(-) and F(-) is achieved in both channels.