Building a computational ready database for macrocycles and organic cages

The development and sharing of computational databases for metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) has greatly accelerated the discovery of these materials for various applications. Besides porous frameworks, molecular materials have recently grown as an emerging subclass of porous materials benefit from its crystallinity, modularity and processibility. Among them, macrocycles and cages are the most representative molecules. In this study, we present what we believe to be the most comprehensive macrocycles and cages database to date, comprising 7,939 structures. Our Macrocycles and Cages Database (MCD) was constructed by a series of steps: (1) automated identification of Cambridge Structural Database (CSD) entries likely to contain macrocycles or cages, (2) manual filtering to eliminate inaccuracies, (3) thorough verification and cleaning of the structures containing macrocycles or cages, (4) geometric optimisation of the validated experimental structures, and (5) calculation of Density-Derived Electrostatic and Chemical (DDEC6) charges for the optimised structures. Using the MCD, we performed simulations of binary CO2/CH4 competitive adsorption under industrially relevant conditions, resulting in a structure-property-function relationship that facilitates the identification of promising materials for this separation. In addition, this map supports the formulation and exploration of potential material design principles.