Theoretical Investigation of the Topology of Spiroborate‐Linked Ionic Covalent Organic Frameworks (ICOFs)

A novel type of ionic covalent organic framework (ICOF) with a spiroborate linkage has been recently designed and synthesized by Zhang and co-workers (Ionic Covalent Organic Frameworks with Spiroborate Linkage, Angew. Chem. Int. Ed. 2016, 55, 1737-1741). The spiroborate-linked ICOFs exhibit high Brunauer-Emmett-Teller (BET) surface areas and significant amounts of H2 and CH4 uptakes, combined with excellent thermal and chemical stabilities. Inspired by the novel properties of ICOFs, with the aim of gaining better understanding of the structure of such spiroborate-linked ICOFs, a series of potential 3D network configurations of ICOFs connected with tetrahedral [BO4 ]- nodes were proposed, assuming the [BO4 ]- node in spiroborate segments takes a tetrahedral configuration. These ICOFs, in terms of 2D and 3D topology through torsional energy of the [BO4 ]- fragment, pore-size distribution, total energy of the framework, and gas adsorption properties were compared and systematically investigated by density functional theory calculations, molecular mechanics, and well-established Grand canonical Monte Carlo simulations. The results indicate that spiroborate-linked ICOFs are likely a mixture of various topologies. Among these architectures, the five-fold interpenetrating model shows the lowest energy and reasonable gas uptakes, therefore, it is considered to be the most possible structure. More importantly, the five-fold interpenetrating model, showing high CH4 uptakes compared with several classic porous materials, represents a promising CH4 storage material.