亚磺酰基杯[4]芳烃和1,10-菲罗啉双配体修饰的双核稀土配合物合成,晶体结构及发光性质研究  

Synthesis,crystal structure,and luminescence properties of binuclear lanthanide ion coordination clusters modified with butylsulfinylcalix[4]arene and 1,10-phenanthrene

作　　者：徐林猛 毛东骜 毕研峰 XU Linmeng;MAO Dongao;BI Yanfeng(School of Petrochemical Engineering,Liaoning Petrochemical University,Fushun 113001,China)

机构地区：[1]辽宁石油化工大学石油化工学院,辽宁抚顺113001

出　　处：《渤海大学学报(自然科学版)》2024年第3期184-194,共11页Journal of Bohai University:Natural Science Edition

基　　金：国家自然科学基金项目(No:91961110)。

摘　　要：在溶剂热条件下以对叔丁基亚磺酰基杯[4]芳烃(H_(4)TC4A-SO)和1,10-菲啰啉(phen)为配体,合成两个双核镧离子配位团簇,[Ln_(2)(HTC4A-SO)_(2)(phen)_(2)](+Solvents)(Ln_(2)=Tb_(2),Eu_(2)),并通过X-射线单晶衍射表征了化合物的结构.在双核结构中,每个镧系离子通过HTC4A-SO四个酚羟基氧配位形成Ln-HTC4A-SO单元,两个单元之间通过亚磺酰氧和μ2-酚羟基氧配位.phen配体螯合配位占据八配位稀土离子的两个配位点.在370 nm波长激发下,Tb_(2)表现了典型的绿光发射(λ_(em)=548 nm),而相同条件下,Eu_(2)并不能发光.此外,在N,N-二甲基甲酰胺溶液中,配合物Tb_(2)表现出聚集诱导发光性能,在Tb2浓度为3×10^(-5) mol/L时有最佳发射强度.结合配合物发光光谱和和DFT计算,讨论了Tb_(2)与Eu_(2)不同的发光性质.Two binuclear lanthanide ion coordination clusters,[Ln_(2)(HTC4A-SO)_(2)(phen)_(2)](+Solvents)(Ln_(2)=Tb_(2),Eu_(2)),were synthesized under solvothermal conditions using p-tert-butylsulfinylcalix[4]arene(H_(4)TC4A-SO)and 1,10-phenanthrene(phen)as ligands.The two clusters were structurally characterized by single-crystal X-ray diffraction.In the binuclear structure,each lanthanide ion forms the Ln-HTC4A-SO unit through coordination of the four phenolic oxygens from HTC4A-SO;Two Ln-HTC4A-SO units are further linked by the sulfonyl and μ2-phenolic oxygens to form the binuclear coordination clusters.The phen ligand with chelate coordination mode occupies two coordination sites of the octa-coordinated lanthanide ions.Upon excitation at 370 nm,Tb_(2) exhibits typical green emission(λ_(em)=548 nm),while Eu_(2) does not emit under the same conditions.In addition,in N,N-dimethylformamide solution,the Tb_(2) showed aggregation-induced luminescence,and the best emission intensity was found with the concentration of 3×10^(-5) mol/L.The different luminescence properties of Tb_(2) and Eu_(2) were analyzed by combining the luminescence spectra and the DFT calculation.

关 键 词：镧系离子 芳烃 构象变化 发光性质 

分 类 号：R373.9[医药卫生—病原生物学]