Supramolecular networks through second-sphere coordination based on 1D metal-4,4′-dipyridyldisulfide coordination polymers and hydrogenfumarate or sulfonate anions

Four hydrogen-bonded assemblies of formula [M(dpds)2(OH2)2]A2·nH2O (A = anion) are described. These assemblies result from the second-sphere coordination interactions between the 1D coordination polymers [M(dpds)2(OH2)2]2+, M = Zn(II) and Cu(II), dpds = 4,4′-dipyridyldisulfide, and the pyridine-3-sulfonate (3pySO3−) or hydrogenfumarate (Hfum−) anions. Significantly, supramolecular structural variations are observed depending on the presence of water lattice molecules, which formed discrete aggregates when the Hfum− anion was used. The effects of geometrical variations in the building blocks are also evident on using Jahn–Teller-distorted divalent Cu(II) ions or regular octahedral species based on Zn(II) ions. The second-sphere effects on the stabilization of the compounds are illustrated by TGA experiments.

Four metallosupramolecular assemblies have been prepared by combination of the 1D cationic coordination polymers [M(dpds)2(OH2)2]2+, M = Cu(II), Zn(II), dpds = 4,4′-dipyridyldisulfide, and a second-sphere coordination based on hydrogenfumarate or pyridine-3-sulfonate anions. The metallosupramolecular organization was analyzed and the stabilization of the compounds was investigated by TGA analysis.Figure optionsDownload as PowerPoint slideHighlights
► Geometrical variations in the building blocks imposed by the different metal centers.
► Transformation of malate to hydrogenfumarate.
► Formation of hydrogen bonded water–hydrogenfumarate layers.
► Formation of discrete water aggregates, R4 and D5.