Covalently linking two square planar platinum(II) centers using two pyrazolate bridging ligands allows the filled dz(2) orbitals on each Pt center to overlap, producing a Pt-Pt σ interaction and new low energy dσ* → π* metal-metal-to-ligand charge transfer (MMLCT) transitions terminating on an appropriate π-acceptor ligand such as 2-phenylpyridine (ppy). In an effort to extend the lifetime of the associated MMLCT excited state, we decided to append piperidinyl naphthalimide (PNI) chromophores to the 2-phenylpyridine charge transfer ligands. This structural modification introduces low-lying PNI-based triplet states serving as long-lived triplet population reservoirs, thermally capable of repopulating the charge transfer state at room temperature (RT), thereby extending its excited state lifetime. Specifically, [Pt(PNI-ppy)(μ-Ph2pz)]2 (1), where PNI-ppy is N-(2-phenylpyridine)-4-(1-piperidinyl)naphthalene-1,8-dicarboximide and Ph2pz is 3,5-diphenylpyrazolate, was synthesized and structurally characterized. The static and dynamic photophysical behavior of 1 was directly compared to the MMLCT complex [Pt(ppy)(μ-Ph2pz)]2 (2), lacking the PNI substituents, as well as the naked PNI-ppy ligand 3, intended to independently model the MMLCT and NI excited state properties, respectively. Ultimately, experimental evidence for the presence of both the (3)PNI and (3)MMLCT excited states in 1 were revealed at RT in nanosecond transient absorbance and time-resolved photoluminescence spectroscopy, respectively. Temperature-dependent transient absorption spectroscopy permitted the extraction of an energy gap of 1740 cm(-1) between the MMLCT and PNI triplet states in 1 along with the time constants associated with the interconversions between the various excited states resident on this complex chromophore, ultimately decaying back to the ground state with a time constant of 65 μs at RT.