Coordination polymers based on rhenium octahedral chalcocyanide cluster [Re6Se8(CN)6]4– and lanthanide ions solvated with dimethylformamide

It was found that formation of coordination polymers composed of octahedral rhenium cluster [Re 6 Se 8 (CN) 6 ] 4– and Ln 3+ complexes with dimethylformamide (DMF) strongly depends on the rate of DMF release in the reaction mixture. • Cluster [Re 6 Se 8 (CN) 6 ] 4– and {Ln(DMF) n (H2O) m } 3+ ions form coordination polymers. • Direct addition of DMF led to formation of polymers with framework structure. • Slow release of DMF led to formation of polymers with layered structure. In this work, we demonstrate influence of the source of organic ligand on the formation of supramolecular structures based on the octahedral metal clusters. Two series of coordination polymers based on the rhenium clusters [Re 6 Se 8 (CN) 6 ] 4– and Ln 3+ complexes (Ln = Sm, Eu, Tb, Dy) with dimethylformamide (DMF) were obtained. The first series was obtained by direct addition of DMF in the reaction mixture. The series consist of the compounds crystallizing in trigonal crystal system, R 3 ̅c space group, and possessing a framework porous structures composed of cluster anions and [Ln(dmf) 3 (H 2 O) 2 ] 3+ complexes. Compounds of the second series were obtained as a result of in situ generation of DMF by hydrolysis of N, N -dimethylformamide dimethyl acetal (DMF DMA). These compounds were crystallized in orthorhombic crystal system, Pnma space group, and possessed a layered structure consisting of cluster anions and [Ln(dmf) 2 (H 2 O) 2 ] 3+ complexes. It was found that the difference in the structures formed depends on the source of DMF rather than other reaction conditions.