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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Luminescent sensing and formation of mixed f-d metal ion complexes between a Eu(III)-cyclen-phen conjugate and Cu(II), Fe(II), and Co(II) in buffered aqueous solution
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Luminescent sensing and formation of mixed f-d metal ion complexes between a Eu(III)-cyclen-phen conjugate and Cu(II), Fe(II), and Co(II) in buffered aqueous solution

机译：Eu（III）-cycln-phen共轭物与Cu（II），Fe（II）和Co（II）在缓冲水溶液中的发光传感和混合f-d金属离子配合物的形成

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摘要

The synthesis and photophysical properties of the Eu(III) complex 1.Eu, based on the use of 1,10-phenanthroline (phen) as a combined sensitizing antenna and a transition metal ion coordinating ligand, is described. The long-wavelength Eu(III) emission from this complex was found to be highly pH sensitive, giving rise to a 'off-on-off' pH profile with maximum emission occurring within the physiological pH range. This allowed for the use of 1.Eu as a luminescent sensor for transition metal ions, where the titration with ions such as Cu(II), Co(II) and Fe(II) gave rise to the formation of mixed f-d nuclear complexes, with concomitant changes in the photophysical properties of 1.Eu. Here, changes in both the ground and the singlet excited state properties of the phen antenna were observed, but the largest changes were observed for the delayed Eu emission, which was fully quenched upon titration with these ions in aqueous pH 7.4 buffered solutions. In comparison, no changes were observed in the Eu(III) emission upon titration with ions such as Zn(II) or group I and II ions. From these changes, we were able to demonstrate the binding stoichiometry and the binding constant for the formation of novel supramolecular complexes between 1.Eu and Cu(II), Co(II) and Fe(II), which showed that either two or three equivalents of 1.Eu complexed to each of these transition metal ions, giving rise to the formation either linear f-d-f or branched f(3) d based mixed nuclear complexes in solution.
机译：描述了Eu（III）配合物1.Eu的合成和光物理性质，基于使用1,10-菲咯啉（phen）作为组合的敏化天线和过渡金属离子配位配体。发现该复合物的长波长Eu（III）发射对pH高度敏感，从而产生了“ off-on-off” pH曲线，并且在生理pH范围内出现了最大发射。这样就可以将1.Eu用作过渡金属离子的发光传感器，其中用诸如Cu（II），Co（II）和Fe（II）的离子进行滴定会形成混合的fd核络合物，伴随着1.Eu的光物理性质的变化。在这里，观察到了phen天线的基态和单线激发态特性的变化，但是观察到最大的变化，即Eu延迟发射，当在pH 7.4缓冲水溶液中用这些离子滴定时，Eu发射完全淬灭。相比之下，用离子（例如Zn（II）或I和II组离子）滴定后，Eu（III）的发射量没有变化。从这些变化，我们能够证明在1.Eu和Cu（II），Co（II）和Fe（II）之间形成新型超分子复合物的结合化学计量和结合常数，表明有两个或三个当量的1.Eu当量与这些过渡金属离子络合，在溶液中形成基于线性fdf或支化f（3）d的混合核络合物。

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