Two isoelectronic and isostructural W(0) and Re(I) complexes mer-W(CO)3(PNP) (1) and [mer-Re(CO)3(PNP)]Cl (2) (PNP = 4,5-bis(diphenylphosphino)acridine) were synthesized and characterized by X-ray diffraction, infrared, electronic absorption and emission spectroscopy, and cyclic voltammetry. Structures of these complexes show a metal center bonded to the pincer ligand and two axial CO and one equatorial CO ligands. DFT calculations showed that the LUMOs of both complexes are the lowest energy π* orbitals localized in the acridine part of the ligand. The HOMO of 1 is dominated by the dπ orbital of W(0) while the HOMO of 2 has a substantial contribution from the highest energy π orbital of the acridine ring. TD-DFT calculations were performed to assist assignment of the UV-vis absorption spectra. The UV-vis absorption spectrum of 1 shows a very low energy W → π* (acridine) metal-to-ligand-charge-transfer (MLCT) absorption band that ranges from visible (500 nm) to near-infrared (>900 nm) regions and an intense acridine π → π* absorption band at 410 nm. There is a blue-green window in the ∼450-500 nm range between the π → π* and W → π*(acridine) MLCT absorptions. The absorption spectrum of 2, dominated by intense π → π* absorptions, shows no distinct low energy MLCT band. Complex 1 is luminescent, displaying acridine-based ππ* fluorescence at 501 nm which is anti-Kasha as it is higher in energy than the lowest energy excited state.