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

Twelve novel transition-rare-earth metal clusters, formulated as [Ni18Pr14(mu 3OH)(14) (dmpa) 10 (mmt)(10)(SO4)(4)(CH3COO)(16)]center dot 9CH(3)OH center dot 5H(2)O (1, H(3)dmpa = dimethylolpropionic acid, and Hmmt = 2-mercapto-5-methyl-1,3,4-thiadiazole) [Ni36RE102(OH)(138) (mmt)(18)(Hdmpa)(30)(H(2)dmpa)(12)(CH3COO)(72) (NO3)(36)(SO4)(18)(H2O)(30)]center dot Br-6 (RE = Nd (2), Sm (3), Eu (4) and Gd (5)) [Ni12RE10(mu(3)-OH)(10) (dmpa)(8) (mmt)(8)(SO4)(2)(CH3COO)(8)(H2O)(4)]center dot 8CH(3)OH center dot 7H(2)O (RE = Tb (6), Dy (7), Ho (8), Er (9) and Y (10)) [Ni8Pr8(mu(3)-OH)(8) (mmt)(8)(Hdpga)(16)(CH3COO)(8)]center dot 8CH(3)OH (11, H(2)dpga = diphenyl-glycolic acid), and [Ni16Tb6(mu(3)-OH)(24) (mmt)(8)(Hdpga)(4) (dpga)(4)(CH3COO)(2)(NO3)(4)(H2O)(2)]center dot 12CH(3)OH center dot 5H(2)O (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 2e5 are isostructural and feature a hexagonal structure, shaped like a "Star of David". Isostructural 6e10 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 insitu 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. (c) 2023 The Authors. Published by Elsevier B.V. on behalf of Chinese Society of Rare Earths.