Ab-initio calculations with static and dynamic correlation are required to obtain reliable energy gaps. These calculations are prohibitive for these molecules due to their size. However, the small HS-LS gap obtained for [Co(1)](ClO4)2 is in line with the significant multiconfigurational character obtained at CASSCF and CASPT2 calculations for the reduced model systems. Consistent with this, the EPR spectra of polycrystalline [Co(1)](ClO4)2 show that the complex exhibits both HS and LS configurations in the solid state (vide infra), in line with the EPR spectroscopic data previously obtained on frozen solutions. Having validated our de novo computational approach in the case of [Co(1)](ClO4)2, we modelled complexes based on interlocked ligands containing other readily available macrocycle components, 41 one of which ( ) is more rigid and the other (3) contains a potentially weakly coordinating ether unit near to the bipyridine ligand (Figure ). [Co(2)] 2+ was predicted to display an all-neutral N, 5-coordinate environment similar to that of [Co(1)](ClO4)2 but in this case, π-Co and π-π interactions appear to result in distortion of the sbpy geometry and a twisting of the macrocycle relative to the axle (Figure ). In the case of [Co(3)] 2+ , the weakly coordinating ether O was predicted to bind to the metal ion in lowest energy model obtained, resulting in a pseudo-octahedral geometry, although once again the N donors are arranged in a sbpy geometry (Figure ).