Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 123, Issue 26, Pages 5524-5535Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.9b01916
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Funding
- UAREN program
- National Science Foundation (CAREER Grant) [1454047]
- NSF Major Research Instrumentation Grant [0958790]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1454047] Funding Source: National Science Foundation
- Directorate For Engineering
- Div Of Chem, Bioeng, Env, & Transp Sys [0958790] Funding Source: National Science Foundation
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The optical properties and ultrafast dynamics of hexaethyl tripyrrin-1,14-dione (H(3)TD1) are tuned by hydrogen-bonding interactions between the solute and the solvent. In solvents with low hydrogen-bonding affinity, H(3)TD1 preferentially forms hydrogen-bonded dimers, whereas in solvents that can either donate or accept hydrogen bonds H(3)TD1 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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