首页|A New Family of SO42--Templated 3d-4f High-Nuclearity Clusters:Syntheses,Structures,and Magnetic Properties
A New Family of SO42--Templated 3d-4f High-Nuclearity Clusters:Syntheses,Structures,and Magnetic Properties
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The precise syntheses of transition-rare-earth metal clusters with desired structures remain a great challenge.Herein,by utilizing SO42-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[Ni24Pr22(μ3-OH)31(pida)24(SO4)4(NO3)9(CH3COO)3]·Br4·(NO3)11·16H2O·25CH3OH(1,H2pida=N-phenyliminodi-acetic acid),[Ni24Nd22(μ3-OH)31(pida)24(SO4)4(NO3)g(CH3COO)3]·Br4·(NO3)11·14H2O·24CH3OH(2)and[Ni24Gd22(μ3-OH)36(bida)24(SO4)7-(NO3)3(CH3COO)3]·(SO4)·Br4·(NO3)4·31H2O·32CH3OH(3,H2bida=N-benzyliminodiacetic acid),have been successfully isolated.X-ray crystal structure analyses reveal that all the cationic {Ni24RE22} cores in 1-3 possess a ball-like structure with C3v symmetry,and can be viewed as consisting of an inner {RE22} core and an outer {Ni24} shell.From 1 and 2 to 3,due to the lanthanide contraction effect,the coordination numbers for rare-earth metal centers in {RE22} are different,resulting in different number of SO42-and NO3-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.
Frontier Institute of Science and Technology,State Key Laboratory of Electrical Insulation and Power Equipment,Xi'an Key Laboratory of Electronic Devices and Materials Chemistry,School of Chemistry,Instrument Analysis Center,Xi'an Jiaotong University,Xi'an,Shaanxi 710049,China
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