Exploring the Magnetism of C_(5)/C_(2)B_(3) Heteroleptic Organolanthanide Sandwiches  

作　　者：Ye-Ye Liu Qian-Cheng Luo Peng-Bo Jin Yan-Zhen Zheng 

机构地区：[1]Frontier Institute of Science and Technology(FIST),State Key Laboratory of Electrical Insulation and Power Equipment,MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter,Xi’an Key Laboratory of Electronic Devices and Material Chemistry and School of Chemistry,Xi’an Jiaotong University,Xi’an,Shaanxi,710054 China [2]Department of Hepatobiliary Surgery and Institute of Advanced Surgical Technology and Engineering,The First Affiliated Hospital of Xi’an Jiaotong University,Xi’an,Shaanxi,710061 China

出　　处：《Chinese Journal of Chemistry》2025年第2期131-138,共8页中国化学(英文版)

基　　金：the assistance of the project supported by the National Natural Science Foundation of China(22375157,22401227);the Programme of Introducing Talents of Discipline to Universities(B23025);State Key Laboratory of Electrical Insulation and Power Equipment(EIPE23402,EIPE23405);the China Postdoctoral Science Foundation(2023M742783,GZB20240599);"Medical-Engineering Cross Project of the First Affiliated Hospital of XJTU(QYJCo2)";Shaanxi Postdoctoral Science Foundation(2023BSHYDZZ12)and the"Scientists+Engineers"Team Building Project of Qin Chuang Yuan(2022KXJ-088).

摘　　要：Two families of cyclopentadienyl(Cp)/carboranyl heteroleptic sandwiched organolanthanide complexes,namely[Ln{η^(5):σ-Me_(2)C(C_(5)H_(4))(C_(2)B_(10)H_(10))}_(2)][Li(DME)_(3)](1Ln,Ln=Tb,Dy,Ho,Er)and[2-THF-2'-(μ^(2)-Cl)Li(THF)_"(3)-2,2'-Ln(nido-1,7-C_(2)B_(9)H_(11))Cp*](2Dy),were synthesized.Family of 1Ln has been proposed based on the mixing-ligands idea by linking Cp and nido-dicarborllide.However,the carborane cage of[Me_(2)C(C_(5)H_(4))(C_(2)B_(10)H_(10))]_(2)−deprotons and forms a mono-C−anion rather than deboron to form dicarborllide dianion.Hence,the family of 1Ln features a dysprosocenium skeleton with extra two coordination of C−anions of carborllides.Such coordination geometry is more like a tetrahedron if abstracting the centroids of two coordinated Cp rings.In this cubic-type geometry,no significant magnetic axiality is presented;only 1Dy and 1Tb show field-induced slow magnetic relaxation behavior below 10 K.Inspired by 1Ln,the free pentamethylcyclopentadienyl(Cp^(*−))and nido-dicarborllide ligands are used to sandwich central Dy3+ion,achieving heteroleptic complex 2Dy.The bending angle by linking the centroid of Cp^(*−),Dy^(3+)and C_(2)B_(3)^(2−)in 2Dy is increased to 132.8(1)°.As such,the effective energy barrier for magnetic reversal(Ueff)and magnetic blocking temperature TB(ZFC)are both increased(Ueff=616(10)K;TB=6 K).The effort of further enhancing Ueff and TB in such heteroleptic organolanthanide sandwiches should rely on keeping increasing the ligand axiality.

关 键 词：Single-molecule magnets Heteroleptic sandwiched complexes nido-Dicarborllide LANTHANIDES CYCLOPENTADIENYL 

分 类 号：O62[理学—有机化学]