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A New Family of SO42–‑Templated 3d-4f High-Nuclearity Clusters: Syntheses, Structures, and Magnetic Properties
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  • Cai-Hong Fan,
  • Kai-Peng Bai,
  • Qian-Cheng Luo,
  • Tian Han,
  • Chang Huang,
  • Yanzhen Zheng,
  • Wei-Peng Chen
Cai-Hong Fan
Xi'an Jiaotong University
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Kai-Peng Bai
Xi'an Jiaotong University
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Qian-Cheng Luo
Xi'an Jiaotong University
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Tian Han
Xi'an Jiaotong University
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Chang Huang
Xi'an Jiaotong University
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Yanzhen Zheng
Xi'an Jiaotong University
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Wei-Peng Chen
Xi'an Jiaotong University

Corresponding Author:[email protected]

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Abstract

The precise syntheses of transition–rare-earth metal clusters with desired structures remain a great challenge. Herein, by utilizing SO4 2– anion released by in-situ decomposition of sodium dodecyl sulfate (SDS) as a template, a series of novel high-nuclear ity 3d-4f clusters, formulated as [Ni24Pr22(μ3-OH)31(pida)24(SO4)4 (NO3)9(CH3 COO)3]·Br4·(NO3)11· 16H 2O·25CH3OH (1, H2pida = N-phenyliminodiacetic acid), [Ni24Nd22(μ3-OH)31(pida)24(SO4)4(NO3)9(CH3COO)3 ]·Br4·(NO3)11·14H2O· 24CH3OH·(2)·and [Ni24Gd22 (μ3-OH)36(bida)24(SO4)7(NO3)3(CH3 COO) 3]·(SO4)·Br4 ·(NO3)4·31H2O 32CH3OH (3, H 2 bida = N-benzyliminodiacetic acid), have been successfully isolated. X-ray crystal structure analyses reveal that all the cationic {Ni24 RE22}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 coordina -tion numbers for rare-earth metal centers in {RE22} are different, resulting in differ-ent number of SO42– and NO3 anions to support and stabilize the skeleton structures. Meanwhile, the magnetic properties of com-plexes 1–3 were also studied. The result revealed that complexes 1–3 show antiferromagnetic /ferrimagnetic interactions, and 3 ex-hibits 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.
07 Mar 2024Submitted to Chinese Journal of Chemistry
08 Mar 2024Submission Checks Completed
08 Mar 2024Assigned to Editor
08 Mar 2024Review(s) Completed, Editorial Evaluation Pending
14 Mar 2024Reviewer(s) Assigned
09 May 2024Editorial Decision: Revise Minor
15 May 20241st Revision Received