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

The precise syntheses of transition–rare-earth metal clusters with desired structures remain a great challenge. Herein, by utilizing SO 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 [NiPr(μ3-OH)(pida)(SO) (NO)(CH COO)]·Br·(NO)· 16H O·25CHOH (1, Hpida = N-phenyliminodiacetic acid), [NiNd(μ3-OH)(pida)(SO)(NO)(CHCOO) ]·Br·(NO)·14HO· 24CHOH·(2)·and [NiGd (μ3-OH)(bida)(SO)(NO)(CH COO) ]·(SO)·Br ·(NO)·31HO 32CHOH (3, H bida = N-benzyliminodiacetic acid), have been successfully isolated. X-ray crystal structure analyses reveal that all the cationic {Ni RE}cores in 1–3 possess a ball-like structure with C3v symmetry, and can be viewed as consisting of an inner {RE} core and an outer {Ni} shell. From 1 and 2 to 3, due to the lanthanide contraction effect, the coordina -tion numbers for rare-earth metal centers in {RE} are different, resulting in differ-ent number of SO and NO 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 ·K at 3.0 K and 7 T.