Kinetic Trapping of Rylene Diimide Covalent Organic Cages

Formation of imine organic cages relies on the error correction of dynamic covalent chemistry. Here, we demonstrate kinetically trapped rylene diimide [2 + 3] 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 2,4,6-trialkoxy-1,3,5-triformylbenzene, which are used to stabilize covalent organic cages or COFs, act as stereoelectronic chameleons. They increase the electrophilicity of the tritopic aldehyde and the rate of the imine bond formation but simultaneously diminish its kinetic stability in solution. We also show that aldehydes present in the solution may have a detrimental effect on the cage's kinetic stability. In addition, we observed [2 + 2] macrocycles as intermediates in the cage formation and decomposition. We propose that these intermediates represent interesting targets to explore the threshold at which an imine assembly with a rung structure may turn from thermodynamic to kinetic control. Generally, this work underscores critical factors governing the chemistry of kinetically trapped imine assemblies, such as steric bulk, (stereo)electronics, presence of catalysts, and water concentration.