Abstract
The optical properties and ultrafast dynamics of hexaethyl tripyrrin-1,14-dione (H3TD1) are tuned by hydrogen-bonding interactions between the solute and the solvent. In solvents with low hydrogen-bonding affinity, H3TD1 preferentially forms hydrogen-bonded dimers, whereas in solvents that can either donate or accept hydrogen bonds H3TD1 is present as a monomer. The distinction between dimer and monomer determines the dynamics of the system, with faster internal conversion observed in the dimer form. The ultrafast dynamics were characterized using time-correlated single photon counting, fluorescence upconversion, and transient absorption measurements. The time-resolved dynamics of both the monomer and dimer in solution were modeled using a Pauli master equation treatment for a three level system. The solvent-dependent optical properties were measured using steady-state absorption and fluorescence. This data was then used to calculate the quantum yield and extinction coefficients.
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