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

摘要

The reaction of either 4,4′,6,6′-tetramethyl-2,2′- bipyridine, L, or 4,4′,6,6′-tetracarboxy-2,2′-bipyridine, H_4L, with Cu(OAc)_2·H_2O under acidic hydrothermal conditions (50:1 H_2O/HNO_3; 160 °C) led to the formation of crystalline {[Cu(HL′)(H_2O)]·H _2O}, 1, which was structurally characterised to identify H _3L′ as 4,4′,6-tricarboxy-2,2′-bipyridine. Clearly, in situ mono-decarboxylation of a tetracarboxylic acid ligand gave the tricarboxy-analogue, H_3L′. 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 H_4L at the 6′-carboxylic acid position may also be affected by heating L or H _4L in acidic solution under hydrothermal conditions (2:1 H _2O/HNO_3; 160°C) to yield crystalline 4,4′,6-tricarboxy-2,2′-bipyridinium nitrate hydrate {[H _4L′][NO_3]·H_2O}, 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