In situ 5-sulfosalicylate decarboxylation or dimethylformamide hydrolysis generating supramolecular assembly architectures

Six transition-metal complexes, {[Co(4,4′-bipy)(H2O)4](Hbs)2 · 3H2O}n (1), [Mn(4,4′-bipy)2(H2O)4](Hbs)2 · 2H2O (2), {[Mn(HCOO)(H2O)2(4,4′-bipy)]2[Mn(4,4′-bipy)(Hssal)2(H2O)2]}n (3), [Cd(4,4′-bipy)2(H2O)4](Hbs)2 · 2H2O (4), {[Cd3(CH3COO)4(4,4′-bipy)4](Hbs)2 · 10H2O}n (5), and {[Cd(HCOO)(H2O)2(4,4′-bipy)]2[Cd(4,4′-bipy)(Hssal)2(H2O)2]}n (6), have been synthesized by hydrothermal or reflux synthetic method and characterized by single-crystal X-ray diffraction, IR, elemental analysis, thermogravimetric analysis and fluorescence analysis, where Hssal2− is doubly deprotonated 5-sulfosalicylate, Hbs− is 4-hydroxybenzenesulfonate and 4,4′-bipy is 4,4′-bipyridine. The structural analyses showed that all of the six complexes are cation–anion species containing in situ synthesized ligands, Hbs− or HCOO−, and the former arises from the decarboxylation of 5-sulfosalicylic acid under the hydrothermal conditions. The formate anions derived from the hydrolysis of DMF. A series of supramolecular compounds show that the structural diversity is strongly associated with their properties.