Modulating the Photocyclization Reactivity of Diarylethenes through Changes in the Excited-State Aromaticity of the π-Linker
Baswanth Oruganti, Jun Wang, Bo Durbeej
Abstract
Quantum chemical calculations are performed to explore if the reactivity of diarylethene switches toward photocyclization can be controlled by the excited-state aromaticity of their bridging π-linker. Using an archetypal diarylethene with a non-aromatic π-linker as a reference, completely different outcomes are found when the π-linker is allowed to become either aromatic (no reaction) or antiaromatic (fast reaction) upon photoexcitation. The results demonstrate a possibility to use the excited-state aromaticity concept for actual modulation of photochemical reactivity.
Topics & Concepts
AromaticityAntiaromaticityDiarylethenePhotoexcitationExcited stateLinkerReactivity (psychology)PhotochemistryChemistryPhotochromismMoleculeOrganic chemistryAtomic physicsPhysicsComputer scienceOperating systemPathologyAlternative medicineMedicineSynthesis and Properties of Aromatic CompoundsPhotochromic and Fluorescence ChemistrySynthesis of Indole Derivatives