Kinetic Trapping of Rylene Diimide Covalent Organic Cages

Formation of imine organic cages relies on error-correction of dynamic covalent chemistry. Here, we demonstrate kinetically-trapped rylene diimide cages formed in high yields and we investigate the effect of substituents on their formation kinetics and stability. Thereby, we identified that alkoxy groups in triformylbenzene, used to stabilize covalent organic cages or COFs, act as stereoelectronic chameleons. We underscore critical factors governing the chemistry of kinetically-trapped imine assemblies like sterics, electronics, catalysis, and water concentration.