A range of 1,3-aryl linked, bis-β-diketone derivatives (LH 2) has been employed to synthesise neutral bis(ligand), dinuclear complexes incorporating square-planar copper(II) and tris(ligand) dinuclear helical derivatives containing octahedral iron(III). The 1H NMR spectra of the free ligands contain singlet peaks at ca. 16.2 ppm, indicative of enolic protons, confirming that the (bis) enol tautomer is present in solution. An X-ray structure of a ligand from the series incorporating tert-butyl terminal substituents confirms that the same tautomer persists in the solid and that the relative orientation of the bis-β-diketone fragments is such that the coordination vectors lie at approximately 120° to each other. The planar, dinuclear copper complexes form 1 : 2 adducts with pyridine and 4-(dimethylamino)pyridine, confirmed by X-ray structures, that incorporate five-coordinate metal centres. Based on this behaviour, the prospect of linking copper centres in the dinuclear complexes using the difunctional heterocyclic bases, 4,4′-bipyridine, 4,4′-trans-azopyridine and pyrazine as co-ligands has been probed. However, 4,4′-bipyridine was observed to coordinate through only one of its heterocyclic nitrogen atoms in the solid state to form a 1 : 2 ([Cu2(L)2]: 4,4′-bipyridine) adduct, analogous to the structures obtained with the above mono-functional nitrogen bases. Nevertheless, an X-ray structure determination shows that the related difunctional base, 4,4′-trans-azopyridine, coordinates in a bridging fashion via both its heterocyclic nitrogen atoms on alternate sides of each planar [Cu2(L)2] unit to produce an infinite one dimensional metallo chain. In contrast, with pyrazine, a new neutral, discrete assembly of type [Cu4(L)4(pyrazine)2] is formed. The X-ray structure shows that two planar dinuclear complexes are linked by two pyrazine molecules in a sandwich arrangement such that the coordination environment of each copper ion is approximately square pyramidal with the overall tetranuclear structure thus taking the form of a 'dimer of dimers'.