TY - JOUR
T1 - A New Family of SO42–-Templated 3d-4f High-Nuclearity Clusters
T2 - Syntheses, Structures, and Magnetic Properties†
AU - Fan, Caihong
AU - Bai, Kaipeng
AU - Luo, Qiancheng
AU - Han, Tian
AU - Huang, Chang
AU - Zheng, Yanzhen
AU - Chen, Weipeng
N1 - Publisher Copyright:
© 2024 SIOC, CAS, Shanghai, & WILEY-VCH GmbH.
PY - 2024/10/15
Y1 - 2024/10/15
N2 - 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.
AB - 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.
KW - Anionic template
KW - Cluster
KW - Magnetic exchange
KW - Magnetic refrigeration
KW - Transition−Rare-earth metal
UR - https://www.scopus.com/pages/publications/85195124383
U2 - 10.1002/cjoc.202400262
DO - 10.1002/cjoc.202400262
M3 - 文章
AN - SCOPUS:85195124383
SN - 1001-604X
VL - 42
SP - 2438
EP - 2444
JO - Chinese Journal of Chemistry
JF - Chinese Journal of Chemistry
IS - 20
ER -