Departament de Química Inorgànica i Orgànica, Universitat de Barcelona, Diagonal 645, 08028 Barcelona, Spain.
Institute of Nanoscience and Nanotechnology of the University of Barcelona (IN2UB), 08028 Barcelona, Spain.
Inorg Chem. 2023 Feb 20;62(7):3106-3115. doi: 10.1021/acs.inorgchem.2c03940. Epub 2023 Feb 8.
Facile access to site-selective hetero-lanthanide molecules will open new avenues in the search of novel photophysical phenomena based on Ln-to-Ln' energy transfer (ET). This challenge demands strategies to segregate efficiently different Ln metal ions among different positions in a molecule. We report here the one-step synthesis and structure of a pure [YbNdYb] () coordination complex featuring short Yb···Nd distances, ideal to investigate a potential distributive (, from one donor to two acceptors) intramolecular ET from one Nd ion to two Yb centers within a well-characterized molecule. The difference in ionic radius is the mechanism allowing to allocate selectively both types of metal ion within the molecular structure, exploited with the simultaneous use of two β-diketone-type ligands. To assist the photophysical investigation of this heterometallic species, the analogues [YbLaYb] () and [LuNdLu] () have also been prepared. Sensitization of Yb and Nd in the last two complexes, respectively, was observed, with remarkably long decay times, facilitating the determination of the Nd-to-Yb ET within the [YbNdYb] composite. This ET was demonstrated by comparing the emission of iso-absorbant solutions of , , and and through lifetime determinations in solution and solid state. The comparatively high efficiency of this process corroborates the facilitating effect of having two acceptors for the nonradiative decay of Nd created within the [YbNdYb] molecule.
易于获得位点选择性的杂镧系分子将为基于镧系元素到镧系元素能量转移(ET)的新型光物理现象的研究开辟新途径。这一挑战需要有效的策略将不同的镧系金属离子分离到分子的不同位置。我们在此报告了一种纯[YbNdYb]()配位化合物的一步合成和结构,其具有短的 Yb···Nd 距离,非常适合研究从一个 Nd 离子到两个 Yb 中心的潜在分布(,从一个供体到两个受体)分子内 ET,该分子具有良好的特征。离子半径的差异是将两种类型的金属离子选择性分配到分子结构中的机制,这是通过同时使用两种β-二酮型配体来实现的。为了辅助对这种杂金属物种的光物理研究,还制备了类似物[YbLaYb]()和[LuNdLu]()。分别在最后两个配合物中观察到 Yb 和 Nd 的敏化,其衰减时间非常长,这有助于确定[YbNdYb]复合物中 Nd 到 Yb 的 ET。通过比较,, 和 的等吸收溶液的发射,并通过在溶液和固态中的寿命测定来证明这种 ET。该过程的相对高效率证实了在[YbNdYb]分子内为非辐射衰减的 Nd 创建两个受体对于这个过程具有促进作用。