A cationic radical lanthanide organic tetrahedron with remarkable coordination enhanced radical stability  

作　　者：Zhengzhong Zhu Shaojun Hu Zhi Liu Lipeng Zhou Chongbin Tian Qingfu Sun 

机构地区：[1]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [2]University of the Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Chinese Chemical Letters》2025年第2期540-545,共6页中国化学快报(英文版)

基　　金：supported by National Key Research and Development Program of China(Nos.2021YFA1500400 and 2022YFA1503300);the National Natural Science Foundation of China(Nos.21825107,21971237,22171264 and 22301301);the Science Foundation of the Fujian Province(No.2021J02016)。

摘　　要：Rare-earth supramolecular compounds,such as lanthanide organic polyhedrons(LOPs),are of particular interest due to their many possible applications in various fields.Here we report the first syntheses of Ln_(4)(L^(·+))_(4)-type(Ln,lanthanides;L^(·+),radical ligand)radical-bridged lanthanide organic tetrahedrons by self-assembly of face-capping triphenylamine(TPA)-cored radical ligand with different lanthanide ions.Remarkable coordination enhanced radical stability has been observed,with half-life times(t_(1/2))for L_(1)^(·+),La_(4)(L_(1)^(·+))_(4),Eu_(4)(L_(1)^(·+))_(4),Gd_(4)(L_(1)^(·+))_(4),Tb_(4)(L_(1)^(·+))_(4)and Lu_(4)(L_(1)^(·+))_(4)estimated to be 53 min,482 min,624 min,1248 min,822 min and 347 min,respectively.The TPA radical in Ln_(4)(L_(1)^(·+))_(4)containing paramagnetic Ln ions(Ln=Eu^(Ⅲ),Gd^(Ⅲ)and Tb^(Ⅲ))is observed to be more stable than that in Ln_(4)(L_(1)^(·+))_(4)(Ln=La^(Ⅲ)and Lu^(Ⅲ))constructed by diamagnetic Ln ions.This difference in radical stability is possibly due to the magnetic interactions between paramagnetic Ln^(Ⅲ)ions and L_(1)^(·+)ligands,as confirmed by electron paramagnetic resonance(EPR)in La_(4)(L)_(4)(L=L_(1)and L_(1)^(·+))and Tb_(4)(L)_(4)(L=L_(1)and L_(1)^(·+)),and magnetic susceptibility measurements in Tb·_(4)(L)_(4)(L=L_(1)and L_(1)^(·+)).Our study reveals the coordination of radical ligands with lanthanide ions can improve the radical stability,which is crucial for their applications.

关 键 词：Supramolecular chemistry Self-assembly Lanthanide organic polyhedrons RADICAL Enhanced stability 

分 类 号：O641.3[理学—物理化学]