Effect of lanthanide contraction on a series of “sulfate-templated” transition-rare-earth metal clusters: Synthesis, structures and magnetic properties

Kaipeng Bai; Pengfei Sun; Mohamed Saber Lassoued; Caihong Fan; Chang Huang; Yanzhen Zheng; Weipeng Chen

doi:10.1016/j.jre.2023.09.005

Effect of lanthanide contraction on a series of “sulfate-templated” transition-rare-earth metal clusters: Synthesis, structures and magnetic properties

Kaipeng Bai
, Pengfei Sun
, Mohamed Saber Lassoued
, Caihong Fan
, Chang Huang
, Yanzhen Zheng
, Weipeng Chen

School of Materials Science and Engineering

Xi'an Jiaotong University

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Twelve novel transition-rare-earth metal clusters, formulated as [Ni₁₈Pr₁₄(μ₃OH)₁₄ (dmpa)₁₀ (mmt)₁₀(SO₄)₄(CH₃COO)₁₆]·9CH₃OH·5H₂O (1, H₃dmpa = dimethylolpropionic acid, and Hmmt = 2-mercapto-5-methyl-1,3,4-thiadiazole) [Ni₃₆RE₁₀₂(OH)₁₃₈ (mmt)₁₈(Hdmpa)₃₀(H₂dmpa)₁₂(CH₃COO)₇₂(NO₃)₃₆(SO₄)₁₈(H₂O)₃₀]·Br₆ (RE = Nd (2), Sm (3), Eu (4) and Gd (5)) [Ni₁₂RE₁₀(μ₃-OH)₁₀ (dmpa)₈ (mmt)₈(SO₄)₂(CH₃COO)₈(H₂O)₄]·8CH₃OH·7H₂O (RE = Tb (6), Dy (7), Ho (8), Er (9) and Y (10)) [Ni₈Pr₈(μ₃-OH)₈ (mmt)₈(Hdpga)₁₆(CH₃COO)₈]·8CH₃OH (11, H₂dpga = diphenyl-glycolic acid), and [Ni₁₆Tb₆(μ₃-OH)₂₄ (mmt)₈(Hdpga)₄ (dpga)₄(CH₃COO)₂(NO₃)₄(H₂O)₂]·12CH₃OH·5H₂O (12), were synthesized solvothermally by using different ligand combinations and rare earth nitrates. X-ray crystal structure analyses reveal that complexes 1 and 12 possess sandwich-like structure. Compounds 2–5 are isostructural and feature a hexagonal structure, shaped like a “Star of David”. Isostructural 6–10 present ring-like structure, as well as the cluster 11. The structural variations of these complexes can be attributed to the effect of lanthanide contraction. Moreover, the template effect of SO₄²⁻ anion derived from the slow decomposition of Hmmt ligand also plays a significant role in the formation of cluster skeletons. The in-situ mechanism for the generation of sulfate anion is briefly discussed. Meanwhile, the magnetic properties of complexes 2–11 were studied which show typical antiferromagnetic interactions.

Original language	English
Pages (from-to)	2150-2155
Number of pages	6
Journal	Journal of Rare Earths
Volume	42
Issue number	11
DOIs	https://doi.org/10.1016/j.jre.2023.09.005
State	Published - Nov 2024

Keywords

Exchange coupling
Lanthanide contraction
Mixed-ligand strategy
Rare earths
Sulfate-templated
Transition-rare-earth metal clusters

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10.1016/j.jre.2023.09.005

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@article{7e97a12647fc4c79878bd85ac519c689,

title = "Effect of lanthanide contraction on a series of “sulfate-templated” transition-rare-earth metal clusters: Synthesis, structures and magnetic properties",

abstract = "Twelve novel transition-rare-earth metal clusters, formulated as [Ni18Pr14(μ3OH)14 (dmpa)10 (mmt)10(SO4)4(CH3COO)16]·9CH3OH·5H2O (1, H3dmpa = dimethylolpropionic acid, and Hmmt = 2-mercapto-5-methyl-1,3,4-thiadiazole) [Ni36RE102(OH)138 (mmt)18(Hdmpa)30(H2dmpa)12(CH3COO)72(NO3)36(SO4)18(H2O)30]·Br6 (RE = Nd (2), Sm (3), Eu (4) and Gd (5)) [Ni12RE10(μ3-OH)10 (dmpa)8 (mmt)8(SO4)2(CH3COO)8(H2O)4]·8CH3OH·7H2O (RE = Tb (6), Dy (7), Ho (8), Er (9) and Y (10)) [Ni8Pr8(μ3-OH)8 (mmt)8(Hdpga)16(CH3COO)8]·8CH3OH (11, H2dpga = diphenyl-glycolic acid), and [Ni16Tb6(μ3-OH)24 (mmt)8(Hdpga)4 (dpga)4(CH3COO)2(NO3)4(H2O)2]·12CH3OH·5H2O (12), were synthesized solvothermally by using different ligand combinations and rare earth nitrates. X-ray crystal structure analyses reveal that complexes 1 and 12 possess sandwich-like structure. Compounds 2–5 are isostructural and feature a hexagonal structure, shaped like a “Star of David”. Isostructural 6–10 present ring-like structure, as well as the cluster 11. The structural variations of these complexes can be attributed to the effect of lanthanide contraction. Moreover, the template effect of SO42− anion derived from the slow decomposition of Hmmt ligand also plays a significant role in the formation of cluster skeletons. The in-situ mechanism for the generation of sulfate anion is briefly discussed. Meanwhile, the magnetic properties of complexes 2–11 were studied which show typical antiferromagnetic interactions.",

keywords = "Exchange coupling, Lanthanide contraction, Mixed-ligand strategy, Rare earths, Sulfate-templated, Transition-rare-earth metal clusters",

author = "Kaipeng Bai and Pengfei Sun and Lassoued, \{Mohamed Saber\} and Caihong Fan and Chang Huang and Yanzhen Zheng and Weipeng Chen",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors",

year = "2024",

month = nov,

doi = "10.1016/j.jre.2023.09.005",

language = "英语",

volume = "42",

pages = "2150--2155",

journal = "Journal of Rare Earths",

issn = "1002-0721",

publisher = "Editorial Office of Chinese Rare Earths",

number = "11",

}

TY - JOUR

T1 - Effect of lanthanide contraction on a series of “sulfate-templated” transition-rare-earth metal clusters

T2 - Synthesis, structures and magnetic properties

AU - Bai, Kaipeng

AU - Sun, Pengfei

AU - Lassoued, Mohamed Saber

AU - Fan, Caihong

AU - Huang, Chang

AU - Zheng, Yanzhen

AU - Chen, Weipeng

PY - 2024/11

Y1 - 2024/11

N2 - Twelve novel transition-rare-earth metal clusters, formulated as [Ni18Pr14(μ3OH)14 (dmpa)10 (mmt)10(SO4)4(CH3COO)16]·9CH3OH·5H2O (1, H3dmpa = dimethylolpropionic acid, and Hmmt = 2-mercapto-5-methyl-1,3,4-thiadiazole) [Ni36RE102(OH)138 (mmt)18(Hdmpa)30(H2dmpa)12(CH3COO)72(NO3)36(SO4)18(H2O)30]·Br6 (RE = Nd (2), Sm (3), Eu (4) and Gd (5)) [Ni12RE10(μ3-OH)10 (dmpa)8 (mmt)8(SO4)2(CH3COO)8(H2O)4]·8CH3OH·7H2O (RE = Tb (6), Dy (7), Ho (8), Er (9) and Y (10)) [Ni8Pr8(μ3-OH)8 (mmt)8(Hdpga)16(CH3COO)8]·8CH3OH (11, H2dpga = diphenyl-glycolic acid), and [Ni16Tb6(μ3-OH)24 (mmt)8(Hdpga)4 (dpga)4(CH3COO)2(NO3)4(H2O)2]·12CH3OH·5H2O (12), were synthesized solvothermally by using different ligand combinations and rare earth nitrates. X-ray crystal structure analyses reveal that complexes 1 and 12 possess sandwich-like structure. Compounds 2–5 are isostructural and feature a hexagonal structure, shaped like a “Star of David”. Isostructural 6–10 present ring-like structure, as well as the cluster 11. The structural variations of these complexes can be attributed to the effect of lanthanide contraction. Moreover, the template effect of SO42− anion derived from the slow decomposition of Hmmt ligand also plays a significant role in the formation of cluster skeletons. The in-situ mechanism for the generation of sulfate anion is briefly discussed. Meanwhile, the magnetic properties of complexes 2–11 were studied which show typical antiferromagnetic interactions.

AB - Twelve novel transition-rare-earth metal clusters, formulated as [Ni18Pr14(μ3OH)14 (dmpa)10 (mmt)10(SO4)4(CH3COO)16]·9CH3OH·5H2O (1, H3dmpa = dimethylolpropionic acid, and Hmmt = 2-mercapto-5-methyl-1,3,4-thiadiazole) [Ni36RE102(OH)138 (mmt)18(Hdmpa)30(H2dmpa)12(CH3COO)72(NO3)36(SO4)18(H2O)30]·Br6 (RE = Nd (2), Sm (3), Eu (4) and Gd (5)) [Ni12RE10(μ3-OH)10 (dmpa)8 (mmt)8(SO4)2(CH3COO)8(H2O)4]·8CH3OH·7H2O (RE = Tb (6), Dy (7), Ho (8), Er (9) and Y (10)) [Ni8Pr8(μ3-OH)8 (mmt)8(Hdpga)16(CH3COO)8]·8CH3OH (11, H2dpga = diphenyl-glycolic acid), and [Ni16Tb6(μ3-OH)24 (mmt)8(Hdpga)4 (dpga)4(CH3COO)2(NO3)4(H2O)2]·12CH3OH·5H2O (12), were synthesized solvothermally by using different ligand combinations and rare earth nitrates. X-ray crystal structure analyses reveal that complexes 1 and 12 possess sandwich-like structure. Compounds 2–5 are isostructural and feature a hexagonal structure, shaped like a “Star of David”. Isostructural 6–10 present ring-like structure, as well as the cluster 11. The structural variations of these complexes can be attributed to the effect of lanthanide contraction. Moreover, the template effect of SO42− anion derived from the slow decomposition of Hmmt ligand also plays a significant role in the formation of cluster skeletons. The in-situ mechanism for the generation of sulfate anion is briefly discussed. Meanwhile, the magnetic properties of complexes 2–11 were studied which show typical antiferromagnetic interactions.

KW - Exchange coupling

KW - Lanthanide contraction

KW - Mixed-ligand strategy

KW - Rare earths

KW - Sulfate-templated

KW - Transition-rare-earth metal clusters

UR - https://www.scopus.com/pages/publications/85195109736

U2 - 10.1016/j.jre.2023.09.005

DO - 10.1016/j.jre.2023.09.005

M3 - 文章

AN - SCOPUS:85195109736

SN - 1002-0721

VL - 42

SP - 2150

EP - 2155

JO - Journal of Rare Earths

JF - Journal of Rare Earths

IS - 11

ER -

Effect of lanthanide contraction on a series of “sulfate-templated” transition-rare-earth metal clusters: Synthesis, structures and magnetic properties

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Keywords

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