화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.142, No.5, 2134-2139, 2020
Host-Guest-Induced Electron Transfer Triggers Radical-Cation Catalysis
Modifying the reactivity of substrates by encapsulation is a fundamental principle of capsule catalysis. Here we show an alternative strategy, wherein catalytic activation of otherwise inactive quinone "co-factors" by a simple Pd2L4 capsule promotes a range of bulk-phase, radical-cation cycloadditions. Solution electron-transfer experiments and cyclic voltammetry show that the cage anodically shifts the redox potential of the encapsulated quinone by a significant 1 V. Moreover, the capsule also protects the reduced semiquinone from protonation, thus transforming the role of quinones from stoichiometric oxidants into catalytic single-electron acceptors. We envisage that the host-guest-induced release of an "electron hole" will translate to various forms of non-encapsulated catalysis that involve other difficult-to-handle, highly reactive species.