Two Oxime‐Based {LnIII3NiII3} Clusters with Triangular {Ln3(μ3‐Ο2)}7+ Core: Solvothermal Syntheses,Crystal Structures,and Magnetic Properties |
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| Authors: | Xiao‐Ting Wang Hui‐Ming Dong Xiu‐Guang Wang En‐Cui Yang Xiao‐Jun Zhao |
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| Institution: | 1. College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic‐Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Normal University, Tianjin, P. R. China;2. Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin, P. R. China |
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| Abstract: | Two isostructural heterometallic complexes, {Dy3Ni3(H2O)3(mpko)9(O2)(NO3)3](ClO4) · 3CH3OH · 3CH3CN} ( 1 ) and {Gd3Ni3(H2O)3(mpko)9(O2)(NO3)3](NO3) · 10.75CH3OH} ( 2 ) mpkoH = 1‐(pyrazin‐2‐yl)ethanone oxime], were solvothermally synthesized by varying lanthanide ions with different magnetic anisotropy. Structural analyses revealed that both complexes contain a peroxide anion‐aggregated triangular {Ln3(μ3‐Ο2)}7+ core, which is surrounded by three NiII octahedra through threefold oxime linkages into a heterometallic hexanuclear cluster. Apparent antiferromagnetic interactions are observed between the adjacent spin carriers of 1 and 2 with the coupling constant JLn ··· Ni ≈ 12JLn ··· Ln. Additionally, 1 with highly anisotropic DyIII site shows slow magnetization relaxation under zero dc field and 2 constructed from isotropic GdIII ion displays significant cryogenic magnetocaloric effect with a maximum entropy change of 24.8 J · kg–1 · K–1 at 3.0 K and 70 kOe. |
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| Keywords: | Heterometallic 3d‐4f complex 1‐(Pyrazin‐2‐yl)ethanone oxime Magnetic entropy Anisotropy energy barrier Lanthanide |
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