A series of first-row transition metal complexes incorporating seven classes of planar heterocyclic ligands based on 2,2ʹ-bipyridine (bipy) and 1,10-phenanthroline (phen), which have aromatic π-π interactions, are investigated. All the complexes obtained are determined and fully structurally characterized using single-crystal X-ray diffraction methods and compared with those of the corresponding analogues. The molecular conformations and inter-molecular interactions are studied in order to understand the behaviour of these molecules. In this study, we classify which of the novel metal complexes could be adsorbed on the surface of graphene (or graphite), so that they can move, interact and react, and possibly form catalytic complexes on a 2D surface.