Abstract
AbstractKnowledge 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.
Highlights
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 nonpolar toluene the first two components are required to describe the formation of the excimer stimulated emission, which initially appears in 2.2 ps
The second slower component in excimer formation is essential for a good fit and appears in evolution of both the stimulated emission and the 16 500 cmÀ1 transient absorption
Summary
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 the weakly polar MTHF solvent intermediate behaviour is observed, with both stimulated emission due to excimer formation along with a slower rise and broadening in the transients in both visible and NIR (See the Supporting Information, Figure S4b).
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