Supramolecular Free Radicals: Fabrication, Modulation and Functions
Jiao,Yang;Zhang,Xi;Department of Chemistry,Key Laboratory of Organic Optoelectronics and Molecular Engineering,Tsinghua University;
Modulating the activity of radicals is of great importance for the applications in radical-based materials and radical-mediated reactions. To this end, we have proposed a new concept of "supramolecular free radicals", which refers to the free radicals stabilized or activated through supramolecular approaches. Based on the host-guest chemistry of cucurbiturils(CB), we have fabricated three kinds of supramolecular free radicals to modulate the activity and realize diverse functions. Firstly, radical anions can be stabilized by the steric effect and electrostatic effect of CB. As a result, we have constructed a highly efficient near-infrared photothermal conversion system, which displays selective antibacterial performance. Secondly, owing to the electrostatic effect of CB, radical cations can be activated to induce a significant acceleration of Fenton oxidation reaction. Thirdly, by taking advantage of the dynamic nature of host-guest interactions, we can endow the reaction intermediate with adaptive reactivity, which greatly improves the catalytic efficiency of alcohol oxidation. It is highly anticipated that this series of research opens a new horizon in supramolecular materials and supramolecular catalysis.