稀土配合物与发光离子液体的研制及其性能研究

Nowadays, many attentions have been focused in about the rare earth complex. However, there are little literature reported about the Lanthanide complexes material sol/gel/amorphous, such as long-rang order/short-rang order. Therefore, we would combine the theory with the experimental result to prepare the Y(Ⅲ), La(Ⅲ), Tb(Ⅲ), Eu(Ⅲ) Lanthanide complexes（Abbreviated as M(oct-ala)3, M(oct-phe)3, M(oct-ser)3, etc. M为Y, La, Tb, Eu）. The NMR、EXAFS、SAXS、TEM、FT-IR、TG-DTA、WAXD、UV fluorescence spectrophotometer are used to measure the physical and chemical properties of sol / gel / amorphous (glassy) / liquid crystalline / crystalline of diversification of state. Recently, amorphous (glassy) / liquid crystalline / crystalline of Y(Ⅲ), La(Ⅲ), Tb(Ⅲ), Eu(Ⅲ) based rare earth complex have been prepared by our team. Meanwhile, the strong luminescent properties of Tb(Ⅲ), Eu(Ⅲ) in metal complexes are soluble in ionic liquid, which are beneficial to preparing the rare earth luminescence ionic liquids. This project should reveal the formation mechanism of multiple state of rare earth complex. The glass transition temperature were 50℃for the yttrium and europium complex and 70-75℃for the lanthanum complexes when these complexes are monohydrates prepared by a solvent-cast method, whereas they increase by 10-30 degrees for the hemihydrates which were obtained by an annealing treatment at 110℃ The coordinated water was eliminated from the solid above the glass transition temperature . The glassy state was regarded as a result of the self-aggregation of the metal complex in solution by an entanglement of the methylene chains with one another. SAXS showed the presence of two disordered bilayer structures with 2.2nm and 4.5nm periods in the glassy states. t the same time, it should explore new type rare earth luminescence ionic liquids, which should open a new thought for using rare-earth.

目前，在稀土配合物方面的研究在国内外都比较普遍，但是，稀土配合物材料的溶胶/凝胶/非晶态等集合体的长程有序/短程有序关系的研究很少。因此，我们利用理论和实验结合的方法研究制备出氨基酸系列Y(Ⅲ), La(Ⅲ), Tb(Ⅲ), Eu(Ⅲ)基稀土配合物（简写为M(oct-ala)3, M(oct-phe)3, M(oct-ser)3等; M为Y(Ⅲ), La(Ⅲ), Tb(Ⅲ), Eu(Ⅲ)）,将要做的是通过NMR、EXAFS、SAXS、TEM、FT-IR、TG-DTA、WAXD、分光荧光光度计等来测定和分析这些金属配合物材料的溶胶/凝胶/非晶态（玻璃态）/液晶态/结晶态的多样化状态的物理与化学功能特性。目前，我们研究组已经发现Y(Ⅲ), La(Ⅲ), Tb(Ⅲ), Eu(Ⅲ)基稀土配合物可以形成非晶态（玻璃态）/液晶态/结晶态。另外，还发现了发光性能强烈的Tb, Eu金属配合物溶解于离子液体

已发现氨基酸系列表面活性配体(H(oct-ala), H(oct-ser), H(oct-phe)等)是一种很强烈的金属离子结合的比较稳定的无毒配体，将氨基酸配体所吸收的能量转移给稀土离子(Y3+, La3+, Tb3+, Eu3+等)，进一步增强稀土有机配合物的发光效率。还发现这些溶解性好的稀土氨基酸配合物，随着配合物有机溶液浓度的增加而发光强度增强，并荧光寿命值也跟随着稳定增加。随着配合物溶质含量的增加或配合物溶液的溶剂的不断挥发，这些配合物聚集物逐渐收缩，可以形成透明胶束聚集体，发光强度高，发光寿命值趋于稳定。我们已经掌握了比较成熟的稀土氨基酸配合物的制备工艺，并对配合物的物理化学性能有所了解，可以弥补现有稀土有机配合物材料的不如点，将来可以推动稀土发光材料多领域的发展。具体研究内容如下：.（1）通过溶液内的热化学方法制备出DL型辛酰丙氨酸，DL型辛酰苯丙氨酸以及DL和L型的辛酰丝氨酸等4种氨基酸类配体化合物。4种氨基酸化合物因其良好的溶解性使其具有较好的生理作用和功能特性。并进一步研究了这些氨基酸配体与稀土离子(Y3+, La3+, Eu3+, Tb3+等)结合形成的稀土氨基酸配合物材料的溶胶/凝胶/非晶态（玻璃态）/液晶态/结晶态的多样化状态的物理与化学功能特性。.（2）本项目当中用密度泛函理论(DFT)和分子中的原子(AIM)理论等计算稀土氨基酸配合物分子几何结构，振动模型和化学位移等，并与实验结果进行比较。理论和实验数据的良好一致性确保计算结果的可靠性。DFT方法的研究弥补实验无法观察到分子内部更精细结构的缺点，为稀土配合物的研究提供了新的思路和建议。. 本项目研究共完成 19篇论文，其中，SCI 论文5 篇，EI论文 4篇，核心刊物上 5 篇，省级刊物上 2篇，已接收SCI论文2篇，已接收EI论文1篇。申请当中的发明专利1项。独著《新型氨基酸稀土配合物材料的研究》1部。