All about that base: investigating the role of ligand basicity in pyridyl complexes derived from a copper-Schiff base coordination polymer.

The role of ligand basicity in complex formation has been investigated using monodentate pyridyls or benzimidazole (mP) in combination with a solution-stable species derived form a coordination polymer, [Cu(L)] (where L = 2-(2-hydroxybenzylidene-amino)phenol). The 12 [Cu(L)(mP)n] complexes generated, combined with the {[Cu(L)]2(pP)} complexes from our previous work (where pP is a polypyridyl ligand), allow us to gauge the likelihood of complex formation based on the pKa of the conjugate acid of the pyridyl ligands and Hammett parameter, σ. Above pKa ≈ 4.5, complexes are formed where the only ligands are L2- and mP or pP and the packing interactions are predominantly van der Waals. Below this value, complex formation is unlikely unless there are additional oxygen ligands in the Jahn-Teller axis of the Cu(ii) ion. The structures of two literature [Cu(L)(bP)] complexes, where bP is a chelating bidentate pyridyl ligand are also re-examined to resolve the positional disorder in the [Cu(L)] moiety.