Insights Into the Mechanism of Energy Transfer with Poly(Heptazine Imide)s in a Deoximation Reaction
Alexey Galushchinskiy, Katharina ten Brummelhuis, Markus Antonietti, Aleksandr Savateev
Abstract
Abstract Following our previous studies on potassium poly(heptazine imide) (K‐PHI), that is, catalyzed photooxidative [3+2] aldoxime‐to‐nitrile addition to form 1,2,4‐oxadiazoles, we discovered that electron‐rich oximes yield the parent aldehydes instead of target products. In this work, the mechanism of this singlet oxygen‐mediated deoximation process was established using a series of control reactions and spectroscopic measurements such as steady‐state and time‐resolved fluorescence quenching experiments. Additionally, the singlet‐triplet energy gap value was obtained for K‐PHI in suspension, and the reaction scope was broadened to include ketoximes.
Topics & Concepts
ImideNitrileChemistryPhotochemistryQuenching (fluorescence)Singlet stateYield (engineering)Electron transferEnergy transferSinglet oxygenExcited stateFluorescenceOxygenPolymer chemistryOrganic chemistryMaterials sciencePhysicsMetallurgyMolecular physicsQuantum mechanicsNuclear physicsRadical Photochemical ReactionsCO2 Reduction Techniques and CatalystsOrganic Light-Emitting Diodes Research