Modifying electron injection kinetics for selective photoreduction of nitroarenes into cyclic and asymmetric azo compounds.

Modifying the reactivity of substrates by encapsulation is essential for microenvironment catalysts. Herein, we report an alternative strategy that modifies the entry behaviour of reactants into the microenvironment and substrate inclusion thermodynamics related to the capsule to control the electron injection kinetics and the selectivity of products from the nitroarenes photoreduction. The strategy includes the orchestration of capsule openings to control the electron injection kinetics of electron donors, and the capsule's pocket to encapsulate more than one nitroarene molecules, facilitating a condensation reaction between the in situ formed azanol and nitroso species to produce azo product. The conceptual microenvironment catalyst endows selective conversion of asymmetric azo products from different nitroarenes, wherein, the estimated diameter and inclusion Gibbs free energy of substrates are used to control and predict the selectivity of products. Inhibition experiments confirm a typical enzymatic conversion, paving a new avenue for rational design of photocatalysts toward green chemistry.