稀土铽超分子纳米功能材料的荧光性质比较  

Luminescent Comparison of RE Supramolecular Functional Nanosized Materials

作　　者：尹伟[1] 张迈生[1] 康北笙[1] 

机构地区：[1]中山大学化学与化学工程学院,广东广州510275

出　　处：《中国稀土学报》2003年第5期504-507,共4页Journal of the Chinese Society of Rare Earths

基　　金：广州市科委重点攻关计划项目(2000 Z 076 01)资助项目;广东省自然科学基金项目(960078);中科院长春应用化学研究所稀土化学与物理实验室资助项目(R050002K);教育部重点实验室吉林大学无机合成与制备化学开放实验室基金项目(2000 19)

摘　　要：稀土配合物Tb(Phen)x(Bipy)(4-x)(NO3)3(x=4,3,2,1,0)(1×10-3mol·L)溶液中,当配体邻菲罗琳(Phen)和2,2′ 联吡啶(Bipy)共存同一铽的配合物中时,Tb3+的特征发光被敏化,其中Tb(Phen)3(Bipy)(NO3)3的荧光强度是最强,Tb(Bipy)4(NO3)3的荧光强度是最弱。Tb3+在(CH3)3Si MCM 41 Tb(Bipy)4(NO3)3中的特征发光强度最强,而在MCM 41 Tb(Phen)3(Bipy)(NO3)3和(CH3)3Si MCM 41 Tb(Phen)3(Bipy)(NO3)3中的发光变得很弱。当客体分子Tb(Phen)4(NO3)3和Tb(Bipy)4(NO3)3被组装到疏水的主体分子筛(CH3)3Si MCM 41孔道里要比组装到亲水的分子筛MCM 41孔道里的发光要强;当客体分子是Tb(Phen)3(Bipy)(NO3)3和Tb(Phen)2(Bipy)2(NO3)3时,它们的发光情况与前一种情况刚好相反即亲水的极性内腔环境有利于客体分子的发光;平行的荧光寿命试验的结论也是一致的。说明在不同的超分子体系中,疏水和亲水的环境都有可能利于客体分子的发光。在(CH3)3Si MCM 41 Tb(Phen)(Bipy)3(NO3)3中的配体的荧光强度要比在MCM 41 Tb(Phen)(Bipy)3(NO3)3中的强;而Tb3+的特征荧光强度的情况刚好相反。MCM 41 Tb(Phen)(Bipy)3(NO3)3和(CH3)3Si MCM 41 Tb(Phen)(Bipy)3(NO3)3有明显的双指数衰减,双指数衰减拟合所得荧光寿命分别为168.8,641.1μs和73.2。Rare earth complexes Tb(Phen)_x(Bipy)_((4-x))(NO_3)_3 (x=4,3,2,1,0) were prepared in solution. The fluorescent intensity of Tb^(3+) in (Tb(Phen)_3)(Bipy)(NO_3)_3 is the strongest and that of Tb^(3+) in (Tb(Bipy)_4(NO_3)_3) is the weakest. The fluorescent intensity of Tb^(3+) in (CH_3)_3Si-MCM-41-Tb(Bipy)_4(NO_3)_3 is the strongest and that of Tb^(3+) in MCM-41-Tb(Phen)_3(Bipy)(NO_3)_3 or (CH_3)_3Si-MCM-41-Tb(Phen)_3(Bipy)(NO_3)_3 becomes very weak. Supramolecular nanostructured materials, the guests Tb(Phen)_4(NO_3)_3 and Tb(Bipy)_4(NO_3)_3, which were encapsulated in the non-polar channels of (CH_3)_3Si-MCM-41 are stronger than that encapsulated in the polar channels of MCM-41 in luminescence. When the guests are Tb(Phen)_3(Bipy)(NO_3)_3 and Tb(Phen)_2(Bipy)_2(NO_3)_3, it shows an opposite result. The results were proved by fluorescent lifetime experiments. MCM-41-Tb(Phen)(Bipy)_3(NO_3)_3 has two distinct exponential decays. The two decay time constants are 168.8 and 641.1 μs and its amplitude ratio is 0.96∶1; while the two decay time constants of (CH_3)_3Si-MCM-41-Tb(Phen)(Bipy)_3(NO_3)_3 are 73.2 and 5904 μs and the amplitude ratio is 2.3∶1. The ratios of decay time and luminescence intensity of the both supramolecular systems are 2.5∶1, 1∶2.5 and 1.1∶1, 0.96∶1, respectively. These results indicate that interaction and selectivity between host and guest take great effect on luminescent properties of supramolecular system.

关 键 词：发光学 MCM-41 (CH3)3Si-MCM-41 超分子纳米功能材料 指数衰减 稀土 

分 类 号：O641.4[理学—物理化学] O614.33[理学—化学]