RESUMO
Photoisomerization of retinal is pivotal to ion translocation across the bacterial membrane and has served as an inspiration for the development of artificial molecular switches and machines. Light-driven synthetic systems in which a macrocyclic component transits along a nonsymmetric axle in a specific direction have been reported; however, unidirectional and repetitive translocation of protons has not been achieved. Herein, we describe a unique protonation-controlled isomerization behavior for hemi-indigo dyes bearing N-heterocycles, featuring intramolecular hydrogen bonds. Light-induced isomerization from the Z to E isomer is unlocked when protonated, while reverse E â Z photoisomerization occurs in the neutral state. As a consequence, associated protons are displaced in a preferred direction with respect to the photoswitchable scaffold. These results will prove to be critical in developing artificial systems in which concentration gradients can be effectively generated using (solar) light energy.
RESUMO
The catalytic effect of various weakly interacting Lewis acids (LAs) across the periodic table, based on hydrogen (Groupâ
1), pnictogen (Groupâ
15), chalcogen (Groupâ
16), and halogen (Groupâ
17) bonds, on the Diels-Alder cycloaddition reaction between 1,3-butadiene and methyl acrylate was studied quantum chemically by using relativistic density functional theory. Weakly interacting LAs accelerate the Diels-Alder reaction by lowering the reaction barrier up to 3â
kcal mol-1 compared to the uncatalyzed reaction. The reaction barriers systematically increase from halogen