Acid directed in situ oxidation and decarboxylation of 4,4′,6,6′-tetra-methyl-2,2′-bipyridine: Synthesis and structural characterisation of 4,4′,6-tri-carboxy-2,2′-bipyridine and its copper(II) coordination polymer

The reaction of either 4,4′,6,6′-tetramethyl-2,2′-bipyridine, L, or 4,4′,6,6′-tetracarboxy-2,2′-bipyridine, H4L, with Cu(OAc)2·H2O under acidic hydrothermal conditions (50:1 H2O/HNO3; 160 °C) led to the formation of crystalline {[Cu(HL′)(H2O)]·H2O}, 1, which was structurally characterised to identify H3L′ as 4,4′,6-tricarboxy-2,2′-bipyridine. Clearly, in situ mono-decarboxylation of a tetracarboxylic acid ligand gave the tricarboxy-analogue, H3L′. The structure of 1 consists of a 1D coordination polymer that cross-links through hydrogen-bonding between adjacent carboxylic acid and carboxylate groups, as well as through an aqua ligand and lattice water molecule, to form a densely interconnected 3D network. Regioselective mono-decarboxylation of L or H4L at the 6′-carboxylic acid position may also be affected by heating L or H4L in acidic solution under hydrothermal conditions (2:1 H2O/HNO3; 160 °C) to yield crystalline 4,4′,6-tricarboxy-2,2′-bipyridinium nitrate hydrate {[H4L′][NO3]·H2O}, 2, which was also structural characterised. The structure of 2 features an array of hydrogen-bonding interactions that generate a 3D network. More forceful heating of the acidic solution at 180 °C led to double decarboxylation and the formation of 4,4′-dicarboxy-2,2′-bipyridine, whereas heating at 200 °C led to total decarboxylation and the formation of 2,2′-bipyridine. Details of the structures of 1 and 2 along with their synthesis are discussed.

Graphical abstractThe reaction of either 4,4′,6,6′-tetramethyl-2,2′-bipyridine or 4,4′,6,6′-tetracarboxy-2,2′-bipyridine with Cu(II) under acidic hydrothermal conditions led to the formation of {[Cu(HL′)(H2O)]·H2O}, 1, which was structurally characterised to identify H3L′ as 4,4′,6-tricarboxy-2,2′-bipyridine. The structure of 1 consists of a 1D coordination polymer that cross-links through hydrogen-bonding to form an intricately bonded 3D network.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► In situ ligand oxidation and regio-selective decarboxylation in ligand synthesis. ► Solvothermal techniques in coordination polymer and ligand synthesis. ► First example of 4,4′,6-tricarboxy-2,2′-bipyridine in coordination chemistry. ► Structural determination of 3D hydrogen bonded networks.