SYNTHESIS OF COMPOUNDS BASED ON RHENIUM CHALCOCYANIDE CLUSTER ANIONS [Re4Q4(CN)12]4– (Q = S, Se, Te) AND CATIONIC COMPLEXES OF RARE-EARTH METALS

I.M. Litvinova1, Y. M. Gayfulin1, N. V. Kuratieva1,2, Y. V. Mironov1, 2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russian Federation
2Novosibirsk State University, Novosibirsk, Russian Federation
litvjm@gmail.com

The design of self-assembling systems from pre-made building blocks is an area of intense interest as a route to the rational generation of functional materials. Tetrahedral rhenium chalcocyanide cluster anions [Re4Q4(CN)12]4– (Q = S, Se, Te)1, 2 (see figure) were found to be perspective building blocks for synthesis of coordination polymers with different structures and physicochemical properties due to the presence of large number of multidirectional CN-groups. Ambidentate nature of cyanide ligands makes it possible to form coordination polymers with transition and post transition metals. 
Of particular interest is construction of coordination polymers, containing rare-earth cations in their structure due to the fact that lanthanides can possibly open the way to cluster-based materials with magnetic and luminescence properties. Earlier was shown that the presence of organic ligands in the system Ln3+/[Re4Q4(CN)12]4-can influence on the structure and dimensionality of the resultant coordination polymer3.The goal of our work is the synthesis of compounds based on the rhenium cluster anions [Re4Te4(CN)12]4-, lanthanide cations Ln3+ and N-donor ligand. As ligands 4,4'-bipyridine and 1,10-phenanthroline were used. Interaction of cluster anion salts with cationic complexes of lanthanides in aqueous/ethanolic solutions results in compounds with ionic, oligomeric or polymeric structure. Of particular interest are compounds with oligomeric and polymeric structures with bridging rare-earth cations. The first includes salts of dimeric cluster anions (bipyH2)[{Ln(H2O)6}{Re4Te4(CN)12}]2·10H2O (Ln = Gd (1), Dy (2), Tb (3), Ho (4), Er(5)) and salt of unique hexameric anion[{Tm(phen)(H2O)4}{Tm(phen)2(H2O)3}
{Tm(phen)2(H2O)2}{ReTe4(CN)12}3]3-. Polymeric compounds are presented with large amount of chain structures with various conformations of polymeric chains.It can be linear polymers, spirals or ribbons. The most part of obtained compounds readily undergo amorphization on the open-air due to a large quantity of solvent molecules in their structure.Compounds are black-colored and not luminescence in crystal state. Investigation of magnetic susceptibility revealed that magnetic properties of compounds are correlated with properties of lanthanide sole ions. 
This work was supported by the Russian Science Foundation (Grant № 14-23-00013).

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