Solvent dependence of excited-state proton transfer from pyranine-derived photoacids

Literature Information

Publication Date 2014-03-26
DOI 10.1039/C3CP55292F
Impact Factor 3.676
Authors

Christian Spies, Shay Shomer, Björn Finkler, Dina Pines, Ehud Pines, Gregor Jung, Dan Huppert


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Abstract

Steady-state and time-resolved techniques were employed to study the excited-state proton-transfer (ESPT) rate of two newly synthesized 8-hydroxy-1,3,6-pyrenetrisulfonate (pyranine, HPTS) derived photoacids in three protic solvents, water, methanol and ethanol. The ESPT rate constant kPT of tris(1,1,1,3,3,3-hexafluoropropan-2-yl)-8-hydroxypyrene-1,3,6-trisulfonate, 1a, whose pKa* ∼ −4, in water, methanol and ethanol is 3 × 1011 s−1, 8 × 109 s−1 and 5 × 109 s−1 respectively. (8-Hydroxy-N1,N3,N6-tris(2-hydroxyethyl)-N1,N3,N6-trimethylpyrene-1,3,6 trisulfonamide, 1b) is a weaker acid than 1a but still a strong photoacid with pKa* ∼ −1 and the ESPT rate in water, methanol and ethanol is 7 × 1010 s−1, 4 × 108 s−1 and 2 × 108 s−1. We qualitatively explain our kinetic results by a Marcus-like free-energy correlation which was found to have a general form suitable for describing proton transfer reactions in both the proton-adiabatic and the proton-non-adiabatic limits.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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