Le Natur François, Calvez Guillaume, Guégan Jean-Paul, Le Pollès Laurent, Trivelli Xavier, Bernot Kevin, Daiguebonne Carole, Neaime Chrystelle, Costuas Karine, Grasset Fabien, Guillou Olivier
∥Université Lille 1-Sciences et Technologies, UMR CNRS 8576 UGSF, IFR 147-FRE 3637, F-59655 Villeneuve d'Ascq, France.
Inorg Chem. 2015 Jun 15;54(12):6043-54. doi: 10.1021/acs.inorgchem.5b00947. Epub 2015 May 29.
For the first time, hexanuclear complexes with general chemical formula Ln6O(OH)8(NO3)6(H2O)n with n = 12 for Ln = Sm-Lu and Y and n = 14 for Ln = Pr and Nd were stabilized as nanoaggregates in ethylene glycol (EG). These unprecedented nanoaggregates were structurally characterized by (89)Y and (1)H NMR spectroscopy, UV-vis absorption and luminescence spectroscopies, electrospray ionization mass spectrometry, diffusion ordered spectroscopy, transmission electron microscopy, and dynamic light scattering. These nanoaggregates present a 200 nm mean solvodynamic diameter. In these nanoaggregates, hexanuclear complexes are isolated and solvated by EG molecules. The replacement of ethylene glycol by 2-hydroxybenzyl alcohol provides new nanoaggregates that present an antenna effect toward lanthanide ions. This results in a significant enhancement of the luminescence properties of the aggregates and demonstrates the suitability of the strategy for obtaining highly tunable luminescent solutions.
首次将通式为Ln₆O(OH)₈(NO₃)₆(H₂O)ₙ(Ln = Sm - Lu、Y时n = 12,Ln = Pr和Nd时n = 14)的六核配合物以纳米聚集体的形式稳定在乙二醇(EG)中。通过⁸⁹Y和¹H核磁共振光谱、紫外 - 可见吸收光谱和发光光谱、电喷雾电离质谱、扩散有序光谱、透射电子显微镜和动态光散射对这些前所未有的纳米聚集体进行了结构表征。这些纳米聚集体的平均溶剂动力学直径为200 nm。在这些纳米聚集体中,六核配合物被EG分子隔离并溶剂化。用2 - 羟基苄醇取代乙二醇可提供对镧系离子具有天线效应的新纳米聚集体。这导致聚集体发光性能显著增强,并证明了该策略对于获得高度可调谐发光溶液的适用性。