The synthesis, structural characterization, photoluminescence, and excited state absorption properties of a series of platinum(II) terpyridyl complexes bearing a bipyridyl acetylide subunit are presented. The [(t)Bu(3)tPyPtC Cbpy](+) (1) complex displays a broad and structureless emission profile at room temperature (RT), a lifetime of 5.8 mu s, and transient absorption (TA) difference spectra characteristic of a charge transfer (CT) excited state. Upon coordination of Fe2+ to 1, producing tetranuclear 2, the CT emission was quantitatively quenched presumably through the low-lying iron-based ligand field states present. Surprisingly, the addition of Zn2+ to solutions of 1 produces a higher energy emissive state with a substantially longer excited state lifetime of 16 1 mu s. The combined spectroscopic data measured for the zinc titration product (3) suggests that the overall excited state is dominated by a CT manifold, albeit at higher energy relative to 1 The photophysics of a bis-phosphine complex bearing two trans-disposed bpy-acetylide subunits (4) produced a model chromophore possessing an intraligand triplet excited state with a lifetime of 26 mu s at RT. The bipyridyl analogue of 1, (t)Bu(2)bpyPt(C Cbpy)(2) (5), was also prepared and its photophysics are consistent with a lowest CT parentage at RT. The 77 K emission spectra measured for complexes 1, 3, 4, and 5 are all consistent with a triplet bpy-acetylide localized excited state; the E-00 energies vary over a modest 344 cm(-1) across the series However, the shorter 77 K excited state lifetimes observed for 1, 3, and 5 in comparison to 4 suggests that the energetically proximate CT state in the former compounds significantly influences excited state decay at low temperature.