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A highly sensitive ‘turn-on’ phosphorescence probe based on iridium(III) complex with polyether segment subunits for rapid detection of thiophenol
Journal of Organometallic Chemistry ( IF 2.1 ) Pub Date : 2020-10-02 , DOI: 10.1016/j.jorganchem.2020.121551
Daobin Zhang , Yaqian Guo , Lin Xiao , Shouzhi Pu

A red-emitting cyclometalated Ir(III) complex-based phosphorescent probe 1 was designed and synthesized to selectively and sensitively detect thiophenol in 90% DMSO/PBS (0.01 M, pH = 7.4) solution with a low detection limited (LOD = 8.68 × 10−7 mol L−1). For probe 1, cyclometalated [Ir(ppy)2Phen]+ moiety acted as phosphor, 2,4-dinitrobenzenesulfonyl (DNBS) group was regarded as recognition site and phosphorescent quencher, and polyether (1-ethoxy-2-(2-methoxyethoxy)ethane) units in the C^N ligands was introduced to improve the water solubility of complex. Due to strong electro-withdrawing DNBS moiety, probe 1 exhibited very week phosphorescence at 600 nm. Upon addition with thiophenol to probe 1 and DNBS moiety left due to the cleavage of sulfonamide bond though nucleophilic elimination reaction, an obvious phosphorescence at 600 nm belong to complex 2 could be observed and the solution displayed red phosphorescent color. Meanwhile, the probe possessed a large Stokes shift (180 nm) and a relatively larger phosphorescence lifetime (τ = 5.265 μs). At the same time, the probe could be used for quantitative detection of thiophenol in actual water samples with high recovery, and detect thiophenol in human serum (100-fold dilution by PBS).



中文翻译:

基于铱(III)配合物与聚醚链段亚基的高灵敏“开启”磷光探针,可快速检测苯硫酚

设计并合成了一种发射红色的基于环金属化的Ir(III)配合物的磷光探针1,以选择性和灵敏的方式检测90%DMSO / PBS(0.01 M,pH = 7.4)溶液中的硫酚,且检测限低(LOD = 8.68× 10 -7  mol L -1)。对于探针1,环金属化的[Ir(ppy)2 Phen] +部分充当磷光体,2,4-二硝基苯磺酰基(DNBS)基团被视为识别位点和磷光猝灭剂,以及聚醚(1-乙氧基-2-(2-甲氧基乙氧基)引入C ^ N配体中的)乙烷单元以改善配合物的水溶性。由于具有强大的吸电DNBS部分,探针1在600 nm处表现出非常一周的磷光。在通过亲核消除反应将磺酰胺键裂解后,向探针1和残留的DNBS部分添加硫酚后,在600 nm处可见明显的磷光,属于配合物2,溶液呈红色磷光。同时,该探针具有较大的斯托克斯位移(180 nm)和相对较大的磷光寿命(τ= 5.265μs)。同时,该探针可用于定量回收高回收率的实际水样中的苯酚,并检测人血清中的苯酚(用PBS稀释100倍)。

更新日期:2020-10-07
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