Tunable Excited-State Properties and Dynamics as a Function of Pt–Pt Distance in Pyrazolate-Bridged Pt(II) Dimers

The influence of molecular structure on excited-state properties and dynamics of a series of cyclometalated platinum dimers was investigated through a combined experimental and theoretical approach using femtosecond transient absorption (fs TA) spectroscopy and density functional theory (DFT) calculations. The molecules have the general formula [Pt(ppy)(μ-R2pz)]2, where ppy = 2-phenylpyridine, pz = pyrazolate, and R = H, Me, Ph, or tBu, and are strongly photoluminescent at room temperature. The distance between the platinum centers in this A-frame geometry can be varied depending on the steric bulk of the bridging pyrazolate ligands that exert structural constraints and compress the Pt–Pt distance. At large Pt–Pt distances there is little interaction between the subunits, and the chromophore behaves similar to a monomer with excited states described as mixtures of ligand-centered and metal-to-ligand charge transfer (LC/MLCT) transitions. When the Pt(II) centers are brought closer together with bulky bridg...