When a Twist Makes a Difference.

In Photosystem II of plants, the proton motive force that is essential for life is generated partly by the water oxidation process where the tyrosine and histidine 190 (hydrogen bonded) amino acids play an important role. The proton-coupled electron transfer (PCET) process involving these two molecules has been replicated using a benzimidazole-phenol (BIP) construct as an artificial model of both the intramolecular hydrogen bond interaction and the associated PCET process. BIP is a nearly planar molecule and features a strong intramolecular hydrogen bond between the phenol and the nitrogen of the benzimidazole. When the molecule is oxidized electrochemically, the phenolic proton is transferred to the nitrogen of the benzimidazole moiety in a PCET mechanism. Herein the design, synthesis, and physicochemical characterization of a new BIP derivative is described. By introducing a methyl group in the new design, we intentionally increase the dihedral angle between the benzimidazole and phenol rings. The presence of the methyl group affects the ground-state PCET and the excited-state intramolecular proton transfer processes as well. The break in the coplanarity weakens the strength of the intramolecular hydrogen bond, decreases the chemical reversibility, and quenches the emission from the excited-state intramolecular proton transfer state. The findings contribute to understanding the importance of having a nearly planar structure in bioinspired artificial photosynthetic systems.