钕配位聚合物的合成、结构、电化学和荧光性质研究

摘要

A neodymium coordination polymer with succinic acid in deionized water was synthesized and characterized by IR,UV,fluorescence,TG-DTA,electrochemistry and X-ray single-crystal diffraction. The crystal belongs to the triclinic system,a=0.784 5(3) nm,b=0.811 4(3) nm,c=1.422 7(5) nm,α=96.933(5)°,β=97.023(5)° ,γ =103.513(5)° ,Z =2 and V =0.863 4(5)nm3,with a nine-coordinated of the neodymium forming a distorted tetradecahedral. The polymer emits yellow-green luminescence at 367 nm (λex=326 nm). which may be assigned to theπ*→n transition. The TG result shows a three-step weight loss for the complex, and the Nd2O3 is the last remaining.Cyclic voltammetric measurement of the compound reveals that the compound has a couple of irreversible redox peak at 0.024 V and-0.07 V in the potential range-0.4 0.3 V. According to|Ep-Ep/2|=47.7/αn(α=0.5),the electron transfer number involved in the processes could be calculated to be two. Thus,it indicates that the electrochemistry of the polymer is corresponded to the unusual Nd(Ⅲ)/Nd(Ⅴ) transformation.%合成一种新的钕和丁二酸的配位聚合物，通过红外、紫外、荧光、热重、电化学和X线单晶衍射对其进行表征.晶体结构检测结果表明：中心离子钕（III）以九配位形成变形十四面体，该晶体属于三斜晶系，其中a =0.7845(3) nm， b=0.8114(3) nm，c=1.4227(5) nm，α=96.933(5)°，β=97.023(5)°，γ=103.513(5)°，Z=2，V=0.8634(5) nm3.荧光光谱显示，配位聚合物在367 nm处有一个较强的发射峰(λex=326 nm)，归因于配体的π*→n跃迁；热重分析表明，配位聚合物分3步失重，最后剩余Nd2O3.电化学结果表明，在-0.4~0.3 V电势范围内，配位聚合物在0.024 V和-0.07 V处有一对不可逆的氧化还原峰，通过峰电位和半峰电位的计算公式|Ep-Ep/2|=47.7/αn(α=0.5)，可以计算出转移电子数为2，由此可见，Nd（III）和Nd（V）之间的转换导致该配位聚合物具有电化学活性.