Department of Chemistry, Zhejiang Sci-Tech University, Xiasha Higher Education District, Hangzhou 310018, P. R. China.
Analyst. 2019 Aug 16;144(17):5254-5260. doi: 10.1039/c9an01037h.
In this paper we report a novel probe based on a luminescent 23-membered [1 + 1] Schiff-base macrocyclic mononuclear Sm(iii) complex Sm-2e, originating from the dialdehyde H2Qe and 1,2-bis(2-aminoethoxy)ethane precursors, which is synthesized by the Sm(iii) ion template method. X-ray structural analyses confirm that each ten-coordinate Sm(iii) center with the coordination geometry of a distorted bicapped square antiprism is fully encapsulated by a flexible macrocyclic ligand H2L2e to form a "lasso-type" architecture, and this architecture could enable efficient energy transfer in various solvents confirmed by long lifetimes (33.5-65.2 μs) and high quantum yields (0.23-0.76%) of the Sm(iii) ion. Simultaneously, complex Sm-2e could serve as a probe for sensing organic solvents. Particularly, this complex probe Sm-2e exhibits a highly selective, rapid and sensitive response to tetrahydrofuran (THF), which is easily distinguished by a large absorption shift, even visible to the naked eye, and complete fluorescence quenching. Moreover, the limit of detection for THF is about 0.20% determined by titration experiments, and good selectivity for THF could still be realized in mixture solvents. Consequently, this colorimetric and "turn off" fluorescent probe Sm-2e could be a valuable candidate as a sensor material for sensing THF which has been rarely reported.
本文报道了一种基于发光 23 元[1+1]席夫碱单核 Sm(iii)配合物 Sm-2e 的新型探针,该配合物源于二醛 H2Qe 和 1,2-双(2-氨基乙氧基)乙烷前体,通过 Sm(iii)离子模板法合成。X 射线结构分析证实,每个十配位 Sm(iii)中心采用扭曲的双帽四方反棱柱配位几何形状,被柔性大环配体 H2L2e 完全包裹,形成“套索型”结构,这种结构可以在各种溶剂中实现有效的能量转移,证实了长寿命(33.5-65.2μs)和高量子产率(0.23-0.76%)。同时,配合物 Sm-2e 可用作有机溶剂的探针。特别是,该配合物探针 Sm-2e 对四氢呋喃(THF)表现出高度选择性、快速和灵敏的响应,甚至肉眼可见,通过大的吸收位移和完全的荧光猝灭来区分。此外,通过滴定实验确定 THF 的检测限约为 0.20%,并且在混合溶剂中仍能实现对 THF 的良好选择性。因此,这种比色和“关闭”荧光探针 Sm-2e 可以作为一种很有价值的传感器材料,用于传感 THF,这在以前很少有报道。