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 bridging ligands, they interact through their dz² orbitals and the S₁ and T₁ states are best characterized as metal-metal-to-ligand charge transfer (MMLCT) in character. The results of the femtoseconds TA experiments reveal that intersystem crossing (ISC) occurs on ultrafast time scales (τ_S1 < 200 fs), while there are two relaxation processes occurring within the triplet manifold, τ₁ = 0.5-3.2 ps and τ₂ = 20-70 ps; the longer time constants correspond to the presence of bulkier bridging ligands. DFT calculations illustrate that the Pt-Pt distances further contract in the T₁ ³MMLCT states; therefore, slower relaxation may be related to a larger structural reorganization. Subsequent investigations using faster time resolution are planned to measure the ISC process as well as to identify any potential coherent interaction(s) between the platinum centers that may occur.