稀土有机螯合物发光研究进展

Progress on Study of Luminescence of Rare Earth Organic Chelates

总结了稀土有机螯合物结构与发光性能的关系 :配体最低三重态能级与稀土离子激发态能级的匹配是中心稀土离子能否发光的主要因素 ;螯合物结构的平面性和刚性是中心离子发光效率高低的重要因素 ;适宜的第二配体的加入一般导致螯合物分子刚性和稳定性增高 ,因而有利于能量的传递 ,致使中心离子发光效率增高 ,但也不能忽视第二配体加入所引起光能的吸收和能量传递过程的竞争 ;配体的耐热 ,耐辐射性是配合物能否作为材料的必要因素。自行设计、合成了 5类 2 5种新的有机配体及其相应的二元、三元稀土螯合物 ,研究了这些螯合物的配位性质、发光性能、发光与结构关系及发光机制 ;提出并发展了稀土离子发光和电子振动光谱作为配合物和生物分子结构探针的两种新的方法。将稀土 β 二酮的发光螯合物与树脂制成荧光塑料 ;利用铕和铽螯合物的发光和免疫反应 ,检测了体液中生物活性物质的含量 ,证实以稀土离子替代放射性同位素作为标记物 ,有希望替代放射免疫分析方法 ,成为常规的临床检验方法 ;利用Tb3+ 荧光检测了植物中生长激素的含量。

Based on the investigation of the luminescence of a series of rare earth organic chelates, some relationships between the luminescence and the structure of the chelates were proposed. The intensity of sensitized luminescence of central lanthanide ions (Ln 3+ ) in a rare earth organic chelate depends on (1) the suitability of the energy gap between the excited triplet energy level of the ligands and the lowest excited energy level of Ln 3+ ions; (2) the rigidity and planarity of the structure of the chelate molecule; (3) the existence of a suitable π conjugated system in the chelate molecule and (4) the existence of a suitable secondary ligand which may increase the rigidity and the stability of the chelate molecule. According to the above relationships, 25 novel organic ligands were designed and synthesized, and their lanthanide chelates were prepared. Investigation of the photoluminescence for the new chelates shows that some of the chelates were strongly luminescent, and these chelates are applied to fluoroimmunoassay for determination of human immunoglobulin (IgG), to preparation of fluorescent plastics, and to determination of growth hormone for plants. Two novel spectroscopy probe technologies for structure of coordination compounds and biological molecules have been proposed and developed based on vibronic spectra of Tb 3+ complexes and fluorescence of Ce 3+ ions.