A novel kind of supramolecular free radical with significantly improved free radical yield and enhanced near-infrared photothermal conversion has been fabricated.
Dissipative self-assembly is a challenging but attractive field of supramolecular science, because it generally concerns complex system but is more close to the self-assembly of living bodies. We successfully realized dissipative self-assembly by coupling a supra-amphiphile with a chemical oscillator.
Fuel-driven self-assembly widely exists in the biological world since functional micro-or nanostructures in living bodies are usually transiently formed by biomolecular self-assembly far from thermodynamic equilibrium driven by active molecules (chemical fuel), for example, adenosine triphosphate (ATP). Therefore, research focusing on artificial fuel-driven self-assembly has drawn extensive attention in recent years. Compared with spontaneous molecular self-assembly at thermodynamic equilibrium, constructing a fuel-driven self-assembly remains complicated because it requires a delicately designed chemical reaction network mainly involving an "activation" and a "deactivation". In this Minireview, we will review recent developments in fuel-driven self-assembly and generalize several strategies for constructing such a self-assembly. Besides that, the functional micro-or nanostructures and materials achieved by these fuel-driven self-assemblies will also be discussed.
Tuning the activity of radicals is crucial for radical reactions and radical-based materials. Herein, we report a supramolecular strategy to accelerate the Fenton reaction through the construction of supramolecularly activated radical cations. As a proof of the concept, cucurbit[7]uril (CB[7]) was introduced, through host-guest interactions, onto each side of a derivative of 1,4-diketopyrrolo[3,4-c]pyrrole (DPP), a model dye for Fenton oxidation. The DPP radical cation, the key intermediate in the oxidation process, was activated by the electrostatically negative carbonyl groups of CB[7]. The activation induced a drastic decrease in the apparent activation energy and greatly increased the reaction rate. This facile supramolecular strategy is a promising method for promoting radical reactions. It may also open up a new route for the catalytic oxidation of organic pollutants for water purification and widen the realm of supramolecular catalysis.
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