键长和电子效应共同调控的β⁃二酮Dy(Ⅲ)配合物的合成、结构与磁性  

Syntheses,Structures and Magnetic Properties ofβ⁃diketone Dy(Ⅲ)Complexes Tuned by Bond Length and Electronic Effect

作　　者：董艳萍 李光明[1] DONG Yan‑Ping;LI Guang‑Ming(Key Laboratory of Functional Inorganic Material Chemistry(MOE),Heilongjiang University,Harbin 150080,China;Department of Food and Pharmaceutical Engineering,Suihua University,Suihua,Heilongjiang 152061,China)

机构地区：[1]黑龙江大学,功能无机材料化学教育部重点实验室,哈尔滨150080 [2]绥化学院食品与制药工程学院,绥化152061

出　　处：《无机化学学报》2021年第2期213-220,共8页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金青年科学基金(No.21601132,21471051);黑龙江省教育厅基本科研业务费(No.KYYWF10236180110);绥化学院第四届科研创新团队(No.SIT04B004);2018年绥化学院科研启动基金项目(No.SQ18002)资助。

摘　　要：以N-乙基-3-吲哚三氟甲基β-二酮(EIFD)为主配体,分别以乙二醇单甲醚(EM)、乙二醇二甲醚(EDM)、二缩三乙二醇(TEG)为辅助配体,与DyCl3·6H2O反应合成了一系列Dy(Ⅲ)配合物[Dy(EIFD)3(EM)]·CH2Cl2(1)、[Dy(EIFD)3(EDM)]·CH2Cl2(2)和[Dy(EIFD)3(TEG)](3)。X射线单晶衍射分析表明,3个配合物都是八配位的单核结构,配位构型分别为双帽三棱柱、正十二面体和双帽三棱柱,分别具有C2v、D2d和C2v对称性。磁学性质显示了配合物1~3具有慢弛豫现象,能垒分别为95.1 K (1)、40.5 K (2)、53.8和13.4 K (3),且配合物1和3有明显的蝴蝶状磁滞回线。进一步讨论了配合物中Dy-O键长和含氧辅助配体的电子效应对配合物有效翻转能垒的影响。A series of 1‑(1‑ethyl‑1H‑indol‑3‑yl)‑4,4,4‑trifluorobutane‑1,3‑dione(EIFD)dysprosium complexes,namely[Dy(EIFD)3(EM)]·CH2Cl2(1),[Dy(EIFD)3(EDM)]·CH2Cl2(2)and[Dy(EIFD)3(TEG)](3)(EM=CH3OCH2CH2OH,EDM=CH3OCH2CH2OCH3,TEG=HOCH2CH2OCH2CH2OCH2CH2OH),have been isolated by reactions of EIFD,DyCl3·6H2O and corresponding oxygen‑containing auxiliary ligands,respectively.X‑ray crystallographic analysis reveals that complexes 1~3 are all eight‑coordinated mononuclear structures.The coordination geometry for Dy􀃮ion in complexes 1 and 3 are suggested closer to the biaugmented trigonal prismatic(8‑BTP,C2v),in contrast,it is closer to the triangular dodecahedron(8‑TDH,D2d)for complex 2.Magnetic studies indicate that all complexes 1~3 exhibit slowed magnetic relaxation with anisotropy energy barriers of 95.1 K for 1,40.5 K for 2 as well as 53.8 and 13.4 K for 3,respectively.Complexes 1 and 3 showed butterfly‑loop.In view of theβ‑diketone ligand of EIFD,Dy(Ⅲ)complexes with oxygen‑containing auxiliary ligands displayed higher energy barriers than those of complexes with nitrogen‑containing auxiliary ligands.The Dy—O bond length and electronic effect of oxygen‑containing auxiliary ligands in the complexes have been investigated in terms of their anisotropy energy barriers.CCDC:1893554,1;1893555,2;1893556,3.

关 键 词：β‑二酮 Dy(Ⅲ)配合物 含氧辅助配体 电子效应 键长 

分 类 号：O614.342[理学—无机化学]