Modeling the Self-Assembly of Cage Molecules

Porous molecular materials constituted by cage molecules are gathering the interest of the scientific community due to their promising applications, like chemical separations, gas adsorption or as agents to increase the porosity in composite materials. In the recent years, the development of organic cage molecules has vastly improved. The synthesis of these compounds in one-pot reactions relying on the self-assembly of the constituting monomers is now a common practice. Some steps have been taken to understand the underlying mechanism of the molecule’s self-assembly, mostly for metallocages, and to see which parameters control the reaction outcome, but there is still much to uncover.

In this work we attempt to further the understanding on the self-assembly of cage molecules through computational modeling, focusing on imine cages which are part of the family of organic cage molecules.

In this work we provide a detailed study on the imine condensation reaction which governs the self-assembly of imine cages, in which reproduction of the raw experimental kinetic data is achieved. Then, through a combined approach of computational quantum chemistry and kinetic modeling we present a model compatible with the different reactor setups used for the synthesis of the CC1 imine cage. From this combined study, we derive which intermediates play a major role in the outcome product, as well as how other variables, initial concentrations and temperature, influence the outcome.