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Computer-aided design of short-lived phosphorescent Ru(II) polarity probes
Dyes and Pigments ( IF 4.5 ) Pub Date : 2018-10-11 , DOI: 10.1016/j.dyepig.2018.10.015
Guido Ielasi , Gerard Alcover , Josep Casellas , Coen de Graaf , Guillermo Orellana , Mar Reguero

Fluorescent polarity probes are usually based on intramolecular charge transfer excited states of selected dyes, the behavior of which in different solvents is traditionally rationalized by the well-known Lippert-Mataga treatment of the “general solvents effect”. Less often transition metal coordination complexes are used as luminescent probes, even though the spectroscopic properties of these dyes are usually dependent on the environment. This is the case of Ru(II) polypyridyls, which are good candidates to develop robust sensitive polarity probes because of their lowest-lying metal-to-ligand charge transfer triplet emissive state, provided their chelating ligands structure is judiciously tuned. The aim of this work has been to design a computational strategy to forecast the behavior of polarity-sensitive Ru(II) complexes without the need to prepare a large set of candidates. In particular, we have analysed a number of complexes derived from [Ru(bpy)3]2+ by introducing different pairs of substituents in the 4,4′ positions of one of the three equivalent 2,2′-bipyridine (bpy) moieties. In this way, we have investigated if a direct relationship may be established between the electronic features of the substituent and the Stokes shift sensitivity to the solvent polarity. Our computational data satisfactorily agree with our experimental results, but they demonstrate that only by explicitly performing the calculation of the Stokes shift in different media for each candidate, it is possible to select the best Ru(II) dyes to be used as polarity probes.



中文翻译:

短寿命磷光Ru(II)极性探针的计算机辅助设计

荧光极性探针通常基于选定染料的分子内电荷转移激发态,传统上通过众所周知的“一般溶剂效应”的Lippert-Mataga处理可以合理化其在不同溶剂中的行为。过渡金属配位络合物很少用作发光探针,即使这些染料的光谱性质通常取决于环境。Ru(II)聚吡啶就是这种情况,由于明智地调整了它们的螯合配体结构,由于它们最低的金属到配体电荷转移三重态发射态,它们是开发鲁棒的敏感极性探针的良好候选者。这项工作的目的是设计一种计算策略,以预测极性敏感的Ru(II)配合物的行为,而无需准备大量的候选物。特别是,我们分析了许多衍生自[Ru(bpy)3 ] 2+通过在三个等效的2,2'-联吡啶(bpy)部分之一的4,4'位置引入不同的取代基对。这样,我们研究了是否可以在取代基的电子特征与斯托克斯位移对溶剂极性的敏感性之间建立直接关系。我们的计算数据与我们的实验结果令人满意,但是它们表明,只有通过针对每种候选人明确地在不同介质中进行斯托克斯频移的计算,才有可能选择最佳的Ru(II)染料用作极性探针。

更新日期:2018-10-11
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