Unidade de Ciências Químicas e Radiofarmacêuticas, Instituto Superior Técnico, Instituto Tecnológico e Nuclear, Estrada Nacional 10, 2686-953 Sacavém, Portugal.
Inorg Chem. 2013 Apr 1;52(7):3755-64. doi: 10.1021/ic3023024. Epub 2013 Mar 11.
An intrinsic photoluminescent ionic liquid based on europium(III) tetrakis(β-diketonate) complex with a tetraalkylphosphonium as counterion was synthesized. Calorimetric measurements showed a melting point at 63 °C, which allows the ionic liquid classification. When cooling the material from the liquid state, metastable supercooled ionic liquid is obtained, as seen from NMR spectroscopy as well. Eu(III) photoluminescence is clearly observed while the absorption spectra of the ligand is dominant, showing the antenna effect. This was confirmed with submicrosecond time scale luminescence spectroscopy, where a rise of Eu(III) emission is observed with the correspondent decay of the ligand excited state. Temperature effects in the photoluminescence are also shown, being prominent above the melting point where the intensity decreases with Arrhenius behavior. Eu(III) luminescence decays also show features characteristic of energy migration between homologue Eu(III) species. Solvent effects were also studied by NMR and Luminescence spectroscopies, highlighting that the nucleophilicity of organic solvents such as n-alcohols leads to a coordination with Eu(III), which ultimately compromises the stability of the complex.
合成了一种基于镧系元素铕(III)四(β-二酮)配合物与四烷基鏻作为抗衡离子的固有光致发光离子液体。量热测量显示熔点为 63°C,允许对离子液体进行分类。从液态冷却材料时,从 NMR 光谱中可以看出,获得了亚稳过冷离子液体。观察到 Eu(III)光致发光,而配体的吸收光谱占主导地位,显示出天线效应。这通过亚微秒时间尺度的发光光谱得到了证实,其中观察到 Eu(III)发射的上升,同时配体激发态的相应衰减。还显示了光致发光中的温度效应,在高于熔点时尤为明显,此时强度随 Arrhenius 行为下降。Eu(III)发光衰减也显示出同种 Eu(III)物种之间能量迁移的特征。通过 NMR 和发光光谱也研究了溶剂效应,突出了亲核性有机溶剂(如正醇)与 Eu(III)的配位作用,最终破坏了配合物的稳定性。