Theoretical Study on the Photoacidity of Hydroxypyrene Derivatives in DMSO Using ADC(2) and CC2.

Abstract

This work applies the thermodynamic Förster cycle to theoretically investigate the pKa*, i.e., excited-state pKa values of pyranine-derived superphotoacids developed by Jung and co-workers. The latter photoacids are strong enough to transfer a proton to the aprotic solvent dimethyl sulfoxide (DMSO). The Förster cycle provides access to pKa* via the ground-state pKa and the electronic excitation energies. We use the conductor-like screening model for real solvents (COSMO-RS) to compute the ground-state pKa and the correlated wavefunction-based methods ADC(2) and CC2 with the continuum solvation model COSMO to calculate the pKa change upon excitation. A comparison of the calculated UV/Vis absorption and fluorescence emission energies to the experimental results leads us to infer that this approach allows for a proper description of the electronic excitations. In particular, implicit solvation by means of the COSMO model appears to be sufficient for the treatment of these photoacids in DMSO. The calculations confirm the presumption that a charge redistribution from the hydroxy group to the aromatic ring and the electron-withdrawing substituents is the origin of photoacidity for these photoacids. Moreover, the calculations with the continuum solvation model predict that the pKa jump upon excitation decreases with increasing solvent polarity, as rationalized based on the Förster cycle.