Add time:07/28/2019         Source:sciencedirect.com

Three-nuclear clusters Nd2LnI5(S2)(S2N2)(THF)9 (Ln = Tb, Tm) were prepared by the disproportionation reaction of iodide-nitride [(NdI)3N2](THF)6 with LnI3(THF)3 in the presence of sulfur. Molecule of the cluster contains a flat inorganic core formed by two Nd and Ln atoms connected by dithiadiazine group. One of the Nd atoms is bound to the Ln3+ ion, besides terminal N atom of the bridge S2N2 fragment, by a bridge fragment S2. The second Nd atom is coordinated by two iodine anions and SN group forming unusual NdSN tree-member cycle. Structure of inorganic framework of the complexes is similar to that of earlier obtained monometallic analogues Ln3I5(S2)(S2N2)(THF)10 (Ln = Nd, Dy). In both new clusters the Ln atoms have the same coordination surrounding consisting of one iodine anion, S2 group and N atom of dithiadiazine ligand and occupy in the framework Nd2Ln(S2)(S2N2) the same position which corresponds to the lowest energy of the molecule. The nitride [(NdI)3N2](THF)6 in the presence of sulfur easy reacts as well with triiodides of La and Sm. Products isolated in these reactions do not form crystals suitable for X-ray study but the data of elemental analysis, fragment analysis, the found Nd: Ln ratio, spectroscopic and magnetic measurements allow to conclude that the structure of La, Sm products is similar to that of the above Tb, Tm analogs.

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