Graphical Abstract: New supramolecular systems of Ni(II) and Cd(II) with 1,10-phenanthroline constructed by non-covalent interactions have been synthesized and characterized by single-crystal X-ray diffractometry. The smaller nickel(II) ion forms a cis complex with outer-sphere perchlorates, while the cadmium(II) ion forms a trans complex involving inner-sphere perchlorates. Both compoundsrevealintraligand-basedluminescentproperties.