Benzannulation of aromatic molecules is often used to red-shift absorption and emission bands of organic and inorganic, molecular, and polymeric materials; however, in some cases, either red or blue shifts are observed, depending on the site of benzannulation. A series of five platinum(II) complexes of the form (N∧N∧N)PtCl are reported here that illustrate this phenomenon, where N∧N∧N represents the tridentate monoanionic ligands 2,5-bis(2-pyridylimino)3,4-diethylpyrrolate (1), 1,3-bis(2-pyridylimino)isoindolate (2), 1,3-bis(2-pyridylimino)benz(f)isoindolate (3), 1,3-bis(2-pyridylimino)benz(e)isoindolate (4), and 1,3-bis(1-isoquinolylimino) isoindolate (5). For this series of molecules, either a blue shift (2 and3) or a red shift (4 and 5) in absorption and emission maxima, relative to their respective nonbenzannulated compounds, was observed that depends on the site of benzannulation. Experimental data and first principles calculations suggest that a similar HOMO energy level and a destabilized or stabilized LUMO with benzannulation is responsible for the observed trends. A rationale for LUMO stabilization/destabilization is presented using simple molecular orbital theory. This explanation is expanded to describe other molecules with this unusual behavior.