Ultrafast Excimer Formation and Solvent Controlled Symmetry Breaking Charge Separation in the Excitonically Coupled Subphthalocyanine Dimer

Knowledge of the factors controlling excited state dynamics in excitonically coupled dimers and higher aggregates is critical for understanding natural and artificial solar energy conversion. In this work, we report ultrafast solvent polarity dependent excited state dynamics of the structurally well‐defined subphthalocyanine dimer, μ‐OSubPc2. Stationary electronic spectra demonstrate strong exciton coupling in μ‐OSubPc2. Femtosecond transient absorption measurements reveal ultrafast excimer formation from the initially excited exciton, mediated by intramolecular structural evolution. In polar solvents the excimer state decays directly through symmetry breaking charge transfer to form a charge separated state. Charge separation occurs under control of solvent orientational relaxation. Solvent polarity tunes the interplay of excimer formation and symmetry breaking charge separation (SB–CS) in the photoexcited subphthalocyanine dimer.