Complexes of 2,6-bis[N-(2′-pyridylmethyl)carbamyl]pyridine: formation of mononuclear complexes, and self-assembly of double helical dinuclear and tetranuclear copper(ii) and trinuclear nickel(ii) complexes

Abstract

The potentially pentadentate ligand 2,6-bis[N-(2′-pyridylmethyl)carbamyl]pyridine (H₂L¹), readily prepared from reaction of a diester of pyridine-2,6-dicarboxylic acid (H₂dipic) and 2-aminomethylpyridine (ampy), shows limited tendency to form 1 ∶ 1 M ∶ L complexes with labile metal ions, although [CuL¹] and [NiL¹] were observed as minor species, the latter characterized by a crystal structure analysis. A mononuclear complex formed with inert Co(III) was characterized by a crystal structure as the neutral 1 ∶ 2 complex [Co(L¹)(HL¹)] with two ligands acting as tridentate ligands, one coordinated by the central pyridine and its two flanking deprotonated amido groups, and the other by the central pyridine, one amido and one terminal pyridine group, with the remaining poorly coordinating protonated amide remaining unbound along with other terminal pyridine groups. Fe(III) is known to form a symmetrical 1 ∶ 2 complex, but that complex is anionic due to binding of all four deprotonated amido groups; the unsymmetrical neutral Co(III) complex converts into a symmetrical anionic species only on heating for hours in aqueous base in the presence of activated carbon. The most remarkable tendency of H₂L¹, however, is towards the formation of robust double helical complexes: a dinuclear Cu(II) complex [Cu₂L¹₂] forms, as well as a trinuclear Ni(II) complex [Ni₃(L¹)₂(OAc)₂(MeOH)₂]. Moreover, in the presence of added H₂dipic, the tetranuclear complex [Cu₄(L¹)₂(dipic)₂(OH₂)₂] is obtained. All helical complexes have been characterized by X-ray crystal structure analyses, and all crystals feature a racemic mixture of left- and right-handed double helices stabilized by inter-ligand π-stacking (inter-ring distances of 3.2–3.8 Å) of ligands which each span several metal ions. Using the chelating ligand pentane-2,4-dione (acac), each of the two pairs of adjacent monodentate ligands in [Ni₃(L¹)₂(OAc)₂(OH₂)₂] have been shown to be available for substitution without destroying the helical structure, to form [Ni₃(L¹)₂(acac)₂], also characterized by a crystal structure.