The effects of structural modification of the chelating ligand on mesophase stability in a number of oxovanadium(IV) complexes has been studied. Enantiotropic phases are observed when the complexes exhibit small long-range associations together with anti-ferromagnetic dimerisation. If either case is not satisfied, monotropic phases are observed. The calamitic nature of the observed phases in rationalised in the context of results obtained from molecular simulation experiments on the parent ligands.