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Anion binding and luminescent sensing using cationic ruthenium(II) aminopyridine complexes

机译:使用阳离子钌(II)氨基吡啶配合物进行阴离子键合和发光传感

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摘要

The synthesis of a series of ruthenium(II) based anion sensors of the type [Ru(eta(6)-C6H4MeCHMe2)- Cl(L)(2)][BF4] (2) is reported in which ligand L represents a series of substituted pyridinyhriethyl-arnine derivatives. 'flie carbazole based ligand L-3 exhibits a fluorescent intraligand chargetransfer (ILCT) state that is quenched by ligand-to-metal charge transfer (LMCT) upon coordination to ruthenium in the 1:1 complex [Ru(eta(6)-C6H4MeCHMe2)Cl-2(L-3)] (1c). The 1:2 complex 2c is fluorescent, however, and acts as a fluorescent anion sensor because of the mixing of an anion-dependent charge-transfer component into the excited state. The 1:2 complexes of type 2 all exhibit interesting low symmetry H-1 NMR spectra that also are a useful handle on anion complexation. The electronic structures of L3, 1c and 2c have been probed by time-dependent DFT calculations.
机译:报告了一系列基于钌(II)的[Ru(eta(6)-C6H4MeCHMe2)-Cl(L)(2)] [BF4](2)类型的阴离子传感器,其中配体L代表一系列取代的吡啶二甲基乙基亚胺衍生物。 '基于咔唑的配体L-3表现出荧光配体内电荷转移(ILCT)状态,该配体与配体在1:1络合物中的钌配位后通过配体-金属电荷转移(LMCT)猝灭[Ru(eta(6)-C6H4MeCHMe2 )Cl-2(L-3)](1c)。 1:2络合物2c是荧光的,并且由于将依赖于阴离子的电荷转移成分混合到激发态而用作荧光阴离子传感器。类型2的1:2配合物均显示出有趣的低对称H-1 NMR光谱,这也是处理阴离子配合物的有用方法。 L3、1c和2c的电子结构已通过与时间有关的DFT计算进行了探讨。

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