Site-Specific Solvation of the Photoexcited Protochlorophyllide a in Methanol: Formation of the Hydrogen-Bonded Intermediate State Induced by Hydrogen-Bond Strengthening

The site-specific solvation of the photoexcited protochlorophyllide a (Pchlide a) in methanol solvent was investigated using the time-dependent density functional theory method for the first time to our knowledge. The intermolecular site-specific coordination and hydrogen-bonding interactions between Pchlide a and methanol molecules play a very important role in the steady-state and time-resolved spectra. All the calculated absorption and fluorescence spectra of the isolated Pchlide a and its coordinated and hydrogen-bonded complexes with methanol demonstrate that the novel fluorescence shoulder at ∼690 nm of Pchlide a in methanol should be ascribed to the coordinated and hydrogen-bonded Pchlide a-(MeOH)4 complex. This coordinated and hydrogen-bonded complex can also account for the intermediate state found in the time-resolved spectroscopic studies. Herein, we have theoretically confirmed that the intermolecular coordination and hydrogen bonds between Pchlide a and methanol molecules can be strengthened in the electronically excited state of Pchlide a. Furthermore, the site-specific solvation of the photoexcited Pchlide a can be induced by the intermolecular coordination and hydrogen-bond strengthening upon photoexcitation. Then the hydrogen-bonded intermediate state is formed in 22–27 ps timescales after the site-specific solvation. All the steady-state and time-resolved spectral features of Pchlide a in different solvents can be explained by the formation of this hydrogen-bonded intermediate state after the site-specific solvation, which is induced by the coordination and hydrogen-bond strengthening.