Twelve novel transition-rare-earth metal clusters,formulated as [Ni_(18)Pr_(14)(μ_(3)OH)_(14)(dmpa)_(10)(mmt)_(10)(SO_(4))_(4)(CH_(3)COO)_(16)]·9CH_(3)OH·5H_(2)O(1,H_(3)dmpa=dimethylolpropionic acid,and Hmm...Twelve novel transition-rare-earth metal clusters,formulated as [Ni_(18)Pr_(14)(μ_(3)OH)_(14)(dmpa)_(10)(mmt)_(10)(SO_(4))_(4)(CH_(3)COO)_(16)]·9CH_(3)OH·5H_(2)O(1,H_(3)dmpa=dimethylolpropionic acid,and Hmmt=2-me rcapto-5-methyl-1,3,4-thiadiazole) [Ni_(36)RE_(102)(OH)_(138)(mmt)_(18)(Hdmpa)_(30)(H_(2)dmpa)_(12)(CH_(3)COO)_(72)(NO_(3))_(36)(SO_(4))_(18)(H_(2)O)_(30)]·Br_(6)(RE=Nd(2),Sm(3),Eu(4) and Gd(5))[Ni_(12)RE_(10)(μ_(3)-OH)_(10)(dmpa)_(8)(mmt)_(8)(S(_(4))2(CH_(3)COO)_(8)(H_(2)O)_(4)]·8CH_(3)OH·7H_(2)O(RE = Tb(6),Dy(7),Ho(8),Er(9) and Y(10)) [Ni_(8)Pr_(8)(μ_(3)-OH)_(8)(mmt)_(8)(Hdpga)_(16)(CH3COO)_(8)]·8CH_(3)OH(11,H_(2)dpga=diphe nyl-glycolic acid),and [Ni_(16)Tb_(6)(μ_(3)-OH)_(24)(mmt)_(8)(Hdpga)_(4)(dpga)_(4)(CH_(3)COO)_(2)(NO_(3))_(4)(H_(2)O)_(2)]·12CH_(3)OH·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 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 SO_(4)^(2-) 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.展开更多
基金Project supported by the National Natural Science Foundation of China (21971203)Support Plan of Shaanxi Province for Young Topnotch TalentFundamental Research Funds for Central Universities。
文摘Twelve novel transition-rare-earth metal clusters,formulated as [Ni_(18)Pr_(14)(μ_(3)OH)_(14)(dmpa)_(10)(mmt)_(10)(SO_(4))_(4)(CH_(3)COO)_(16)]·9CH_(3)OH·5H_(2)O(1,H_(3)dmpa=dimethylolpropionic acid,and Hmmt=2-me rcapto-5-methyl-1,3,4-thiadiazole) [Ni_(36)RE_(102)(OH)_(138)(mmt)_(18)(Hdmpa)_(30)(H_(2)dmpa)_(12)(CH_(3)COO)_(72)(NO_(3))_(36)(SO_(4))_(18)(H_(2)O)_(30)]·Br_(6)(RE=Nd(2),Sm(3),Eu(4) and Gd(5))[Ni_(12)RE_(10)(μ_(3)-OH)_(10)(dmpa)_(8)(mmt)_(8)(S(_(4))2(CH_(3)COO)_(8)(H_(2)O)_(4)]·8CH_(3)OH·7H_(2)O(RE = Tb(6),Dy(7),Ho(8),Er(9) and Y(10)) [Ni_(8)Pr_(8)(μ_(3)-OH)_(8)(mmt)_(8)(Hdpga)_(16)(CH3COO)_(8)]·8CH_(3)OH(11,H_(2)dpga=diphe nyl-glycolic acid),and [Ni_(16)Tb_(6)(μ_(3)-OH)_(24)(mmt)_(8)(Hdpga)_(4)(dpga)_(4)(CH_(3)COO)_(2)(NO_(3))_(4)(H_(2)O)_(2)]·12CH_(3)OH·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 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 SO_(4)^(2-) 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.
