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 [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.

Raman Spectroscopy of a Series of the Rare Earth Thiophosphate(LnPS4,Ln=Y,La～Lu)

The Raman spectroscopy study of LnPS 4 series compounds with tetragonal xenotime structure shows that the symmetrical stretching vibration frequency ν 1 increases linearly with the lanthanide contraction, i.e., the decrease of the effective ionic radius r Ln 3+ ; moreover, the ν 1 frequency for the non tetragonal LuPS 4 falls off the line running through the corresponding values for the tetragonal phases. This observation is consistent with their structural chemistry modifications.