Thermodynamics and kinetics of protonated merocyanine photoacids in water.

Chemical Science
Cesare BertonCristian Pezzato

Abstract

Metastable-state photoacids (mPAHs) are chemical species whose photo-activated state is long-lived enough to allow for proton diffusion. Liao's photoacid (1) represents the archetype of mPAHs, and is being widely used on account of its unique capability to change the acidity of aqueous solutions reversibly. The behavior of 1 in water, however, still remains poorly understood. Herein, we provide in-depth insights on the thermodynamics and kinetics of 1 in water through a series of comparative 1H NMR and UV-Vis studies and relative modelling. Under dark conditions, we quantified a three-component equilibrium system where the dissociation (Ka) of the open protonated form (MCH) is followed by isomerization (Kc) of the open deprotonated form (MC) to the closed spiropyran form (SP) - i.e., in the absence of light, the ground state acidity can be expressed as KGSa = Ka(1 + Kc). On the other hand, under powerful and continuous light irradiation we were able to assess, for the first time experimentally, the dissociation constant (KMSa) of the protonated metastable state (cis-MCH). In addition, we found that thermal ring-opening of SP is always rate-determining regardless of pH, whereas hydrolysis is reminiscent of what is found for Schi...Continue Reading

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Citations

Apr 20, 2021·The Journal of Physical Chemistry. B·Cody R AldazRoseanne J Sension
Aug 17, 2021·Frontiers in Chemistry·Andrew FaganSilvia Giordani
Aug 13, 2021·Angewandte Chemie·Cesare BertonCristian Pezzato
Oct 1, 2021·Chemical Society Reviews·Jana VolarićBen L Feringa
Oct 5, 2021·Acta Crystallographica. Section D, Structural Biology·Diana C F MonteiroArwen R Pearson
Nov 25, 2021·Organic & Biomolecular Chemistry·Emanuele SpatolaStefano Di Stefano
Dec 1, 2021·Journal of the American Chemical Society·Laura WimbergerJonathon E Beves

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Methods Mentioned

BETA
X-ray
NMR

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