稀土离子与苯并咪唑二羧酸和邻菲啰啉配合物:晶体结构、荧光及对有机小分子的荧光传感  

Lanthanum Coordination Polymer Based on Benzimidazole-Dicarboxylic Acid and Phenanthroline:Crystal Structure,Fluorescence and Fluorescent Sensing for Organic Small Molecules

作　　者：董高云[1] 马雪[1] 李佳佳[1] 李夏[1] 

机构地区：[1]首都师范大学化学系,北京100048

出　　处：《光谱学与光谱分析》2015年第8期2208-2211,共4页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(21471104)资助

摘　　要：合成了两种新的配合物{[Eu3(bidc)4(phen)2(NO3)]·2H2O}n(1)和[Tb2(bidc)3(H2O)2](2)(bidc=苯并咪唑二羧酸根,phen=1,10-邻菲啰啉)。配合物1是链状结构,含有三种不同的金属离子配位环境:Eu(1)O6N2,Eu(2)O8和Eu(3)O6N2。配合物2是二维网状结构,含有两种配位环境相似的金属离子:Tb(1)O8和Tb(2)O8。配合物1在581,593,615,654和702nm处出现发射峰,为Eu3+的5 D0→7 FJ(J=0-4)跃迁产生的特征荧光。最强发射峰位于615nm,对应于5 D0→7 F2跃迁,为红光。跃迁强度I(5 D0→7 F2)∶I(5 D0→7 F1)约为2.5,说明Eu3+不处于反演中心。配合物2在490,545,584和622nm出现发射峰,归属为中心Tb3+的5 D4→7 FJ(J=6-3)跃迁产生的特征荧光。在545nm的发射最强,对应于5 D4→7 F5跃迁,为绿光。探讨了不同溶剂对配合物1和2荧光的影响。实验结果表明硝基苯对配合物1和2具有显著的荧光猝灭作用,因此配合物1和2可用于环境污染物硝基苯的检测。Two new complexes,{[Eu3（bidc）4（phen）2（NO3）]·2H2O}n（1）and[Tb2（bidc）3（H2O）2]（2）（bidc=benzimidazoledicarboxylate,phen=1,10-phenanthrolIne）were synthesized.Complex 1shows 1Dchain structure.The asymmetric unit of 1contains three crystallographically different Eu^3＋,Eu（1）O6N2,Eu（2）O8and Eu（3）O6N2.Complex 2reveals 2Dstructure.It contains two crystallographically similar Tb^3＋,Tb（1）O8and Tb（2）O8.Complex 1displays the emission peaks at 581,593,615,654 and 702nm,corresponding to the ^5 D0→^7 FJ（J=0-4）transitions of Eu^3＋.The most intense emission at 615 nm is attributed to the 5 D0→7 F2 transition,implies a red emission light of 1.The intensity rations I（^5 D0/^7 F2）/I（^5 D0/^7 F1）is about 2.5,indicating the chemical environment around Eu^3＋does not have an inversion center.Complex 2exhibits four emission peaks at492,545,584 and 622nm,corresponding to the ^5 D4→^7 FJ（J=6-3）transitions of Tb^3＋.The emission band at 545 nm corresponds to the ^5 D4→^7 F5 transition of the Tb^3＋,which gives an intense green luminescence output for the solid sample.Notably,the solvent-dependent luminescence behavior of complexes 1and 2was discussed.They show highly selective for nitrobenzene via a fluorescence quenching mechanism.The highly selective and sensitive sensing nitrobenzene leads to its application in environmental system.

关 键 词：稀土配合物 苯并咪唑二羧酸 荧光 

分 类 号：O76[理学—晶体学]