Interaction of Co(II), Ni(II) and Cu(II) with dibenzo-substituted macrocyclic ligands incorporating both symmetrically and unsymmetrically arranged N, O and S donors

The synthesis and characterisation of four 17-membered, dibenzo-substituted macrocyclic ligands incorporating unsymmetrical arrangements of their N3S2, N3O2 and N3OS (two ligands) donor atoms are described; these rings complete the matrix of related macrocyclic systems incorporating both symmetric and unsymmetric donor sets reported previously. The X-ray structures of three of the new macrocycles are reported. In two of the Cu(II) structures only three of the possible five donor atoms present in the corresponding macrocyclic ligand bind to the Cu(II) site, whereas all five donors are coordinated in each of the remaining complexes. The interaction of Co(II), Ni(II) and Cu(II) with the unsymmetric macrocycle series has been investigated by potentiometric (pH) titration in 95% methanol; X-ray structures of two nickel and three copper complexes of these ligands, each exhibiting 1 : 1 (M :L) ratios, have been obtained. The results are discussed in the context of previous results for these metals with the analogous 17-membered ring systems incorporating symmetrical arrangements of their donor atoms, with emphasis being given to both the influence of the donor atom set, as well as the donor atom sequence, on the nature of the resulting complexes

Metallo-supramolecular assemblies incorporating 1,3-and 1,4-aryl linked bis-beta-diketones - Some recent studies

A review of recent work in the authors' laboratories involving the interaction of 1,3- and 1,4-aryl linked bis-β-diketone derivatives with divalent and trivalent metal ions is presented. In some instances, bifunctional bridging ligands have been employed to extend the resulting structures from two to three dimensions. Examples of metallo-supramolecular dinuclear 'platforms', tetranuclear cofacial dimers, dinuclear helicates, trinuclear triangles, stepped metallo-polymers, a prismatic columnar polymer and large cavity-containing, tetranuclear tetrahedra are all discussed

Manganese(II), iron(II), cobalt(II), and copper(II) complexes of an extended inherently chiral tris-bipyridyl cage

Manganese(II), iron(II), cobalt(II), and copper(II) derivatives of two inherently chiral, Tris(bipyridyl) cages (L and L′) of type [ML]-(PF(6))(2)(solvent)(n) and [FeL′](ClO(4))(2) are reported, where L is the hexa-tertiary butyl-substituted derivative of L′. These products were obtained by using the free cage and metal template procedures; the latter involved the reductive amination of the respective Tris-dialdehyde precursor complexes of iron(II), cobalt(II), or nickel(II). Electrochemical, EPR, and NMR studies have been used to probe the nature of the individual complexes. X-ray structures of the manganese(II), iron(II), and copper(II) complexes of L and the iron(II) complex of L′ are presented; these are compared with the previously reported structures of the corresponding nickel(II) complex and metal-free cage (L). In each complex the metal cation occupies the cage's central cavity and is coordinated to six nitrogens from the three bipyridyl groups. The cations [MnL](2+) and [FeL](2+) are isostructural but both exhibit a different arrangement of the bound cage to that observed in the corresponding nickel(II) and copper(II) complexes. The latter have an exo-exo arrangement of the bridgehead nitrogen lone pairs, with the metal inducing a triple helical twist that extends ≈22 Å along the axial length of each complex. In contrast, [MnL](2+) and [FeL](2+) have their terminal nitrogen lone pairs directed endo, causing a significant change in the configuration of the bound ligand. In [FeL′](2+), the cage has both bridgehead nitrogen lone pairs orientated exo. Semiempirical calculations indicate that the observed endo-endo and exo-exo arrangements are of comparable energy