A New Family of SO_(4)^(2–)-Templated 3d-4f High-Nuclearity Clusters:Syntheses,Structures,and Magnetic Properties  

作　　者：Caihong Fan Kaipeng Bai Qiancheng Luo Tian Han Chang Huang Yanzhen Zheng Weipeng Chen 

机构地区：[1]Frontier Institute of Science and Technology,State Key Laboratory of Electrical Insulation and Power Equipment,Xi'an Key Laboratory of ElectronicDevicesandMaterials Chemistry,Schoolof Chemistry,InstrumentAnalysis Center,Xi'an JiaotongUniversity,Xi'an Shaanxi 710049,China

出　　处：《Chinese Journal of Chemistry》2024年第20期2438-2444,共7页中国化学（英文版）

基　　金：support of National Natural Science Foundation of China(22375157 and 22271228);Special Support Plan of Shaanxi Province for Young Top-notch Talent,State Key Laboratory of Electrical Insulation and Power Equipment(No.EIPE23402);"Scientists+Engineers"Team Building Project of Qin Chuang Yuan(2022KXJ-088);the Medical-Engineering Cross Project of the First Affiliated Hospital of XJTU(QYJCO2).

摘　　要：The precise syntheses of transition-rare-earth metal clusters with desired structures remain a great challenge.Herein,by utilizing SO_(4)^(2-)anion released by in-situ decomposition of sodium dodecyl sulfate(SDS)as a template,a series of novel high-nuclearity 3d-4f clusters,formulated as[Ni_(24)Pr_(22)(μ_(3)-OH)_(31)(pida)_(24)(SO_(4))_(4)(NO_(3))_(9)(CH_(3)COO)_(3)]·Br_(4)·(NO_(3))_(11)·_(16)H_(2)O·25CH_(3)OH(1,H_(2)pida=N-phenyliminodiacetic acid),[Ni_(24)Nd_(22)(μ3-OH)_(31)(pida)_(24)(SO_(4))_(4)(NO_(3))_(9)(CH_(3)COO)_(3)]·Br_(4)·(NO_(3))_(11)·14H_(2)O·24CH_(3)OH(2)and[Ni_(24)Gd_(22)(μ3-OH)_(36)(bida)_(24)(SO_(4))_(7)(NO_(3))_(3)(CH_(3)COO)_(3)]·(SO_(4))·Br_(4)·(NO_(3))_(4)·31H_(2)O·32CH_(3)OH(3,H_(2)bida=N-benzyliminodiacetic acid),have been successfully isolated.X-ray crystal structure analyses reveal that all the cationic{Ni_(24)RE_(22)}cores in 1-3 possess a ball-like structure with C_(3v)symmetry,and can be viewed as consisting of an inner{RE_(22)}core and an outer{Ni_(24)}shell.From 1 and 2 to 3,due to the lanthanide contraction effect,the coordination numbers for rare-earth metal centers in{RE_(22)}are different,resulting in different number of SO_(4)^(2-)and NO_(3)^(-)anions to support and stabilize the skeleton structures.Meanwhile,the magnetic properties of complexes 1-3 were also studied.The result revealed that complexes 1-3 show antiferromagnetic/ferrimagnetic interactions,and 3 exhibits magneto-caloric effect at ultralow temperatures with a maximum-ΔSm(magnetic entropy change)value of 33.03 J·kg^(−1)·K^(−1)at 3.0 K and 7 T.

关 键 词：Transition-Rare-earth metal Cluster Anionic template Magnetic exchange Magnetic refrigeration 

分 类 号：O62[理学—有机化学]