A New Family of SO42–‐Templated 3d‐4f High‐Nuclearity Clusters: Syntheses, Structures, and Magnetic Properties

• Published in: Chinese journal of chemistry 2024-10, Vol.42 (20), p.2438-2444
• Main Authors: Fan, Caihong, Bai, Kaipeng, Luo, Qiancheng, Han, Tian, Huang, Chang, Zheng, Yanzhen, Chen, Weipeng
• Format: Article
• Language: English
• Subjects: Anionic template; Anions; Antiferromagnetism; Cluster; Coordination numbers; Crystal structure; Low temperature; Magnetic exchange; Magnetic properties; Magnetic refrigeration; Metal clusters; Sodium dodecyl sulfate; Sodium lauryl sulfate; Transition−Rare‐earth metal
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.202400262

Comprehensive Summary 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‐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(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. A new family of 3d‐4f clusters {Ni24RE22} (RE = Pr, Nd, and Gd) with excellent stability were isolated by utilizing the SO42– anion from the in‐situ decomposition of sodium dodecyl sulfonate as a template agent, which provides an effective method for the synthesis of novel high‐nuclearity nanoclusters.