Ajayakumar Gopalakrishnan, Sreenath Kesavapillai, Gopidas Karical R
Photosciences and Photonics, Chemical Sciences and Technology Division, National Institute for Interdisciplinary Science and Technology, Council of Scientific and Industrial Research (CSIR), Trivandrum 695 019, India.
Dalton Trans. 2009 Feb 21(7):1180-6. doi: 10.1039/b813765j. Epub 2008 Dec 22.
The design of a highly selective "turn-ON" luminescence chemodosimeter for Cu(2+) is reported. The design strategy made use of the ability of Cu(2+) ions to oxidize aromatic amines in acetonitrile solution. The aromatic amine employed here is a phenothiazine moiety which is covalently linked to one of the bipyridine units of Ru(bpy)(3)(2+). Excitation of the Ru(bpy)(3)(2+) leads to electron transfer from the phenothiazine moiety to the MLCT excited state of Ru(bpy)(3)(2+) which resulted in efficient quenching of the luminescence. In the presence of excess Cu(2+), phenothiazine moiety is oxidized to a stable entity which is incapable of electron donation to the MLCT excited state of Ru(bpy)(3)(2+). The emission of the Ru(bpy)(3)(2+) moiety is thus restored and we show that this strategy can be used as the basis for sensing micromolar amounts of Cu(2+). Only Cu(2+) is capable of this reaction, making this an interesting, hitherto unexplored strategy for the selective detection of micromolar amounts of Cu(2+).
报道了一种用于铜离子(Cu(2+))的高选择性“开启”发光化学传感器的设计。该设计策略利用了Cu(2+)离子在乙腈溶液中氧化芳香胺的能力。这里使用的芳香胺是一个吩噻嗪部分,它与钌联吡啶配合物(Ru(bpy)(3)(2+))的一个联吡啶单元共价连接。Ru(bpy)(3)(2+)的激发导致电子从吩噻嗪部分转移到Ru(bpy)(3)(2+)的金属-配体电荷转移(MLCT)激发态,从而导致发光的有效猝灭。在过量Cu(2+)存在下,吩噻嗪部分被氧化成一个稳定的实体,该实体不能向Ru(bpy)(3)(2+)的MLCT激发态提供电子。因此,Ru(bpy)(3)(2+)部分的发射得以恢复,并且我们表明该策略可作为检测微摩尔量Cu(2+)的基础。只有Cu(2+)能够发生这种反应,这使得这成为一种用于选择性检测微摩尔量Cu(2+)的有趣的、迄今未被探索的策略。