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 H and CH 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 [BO ] nodes were proposed, assuming the [BO ] node in spiroborate segments takes a tetrahedral configuration. These ICOFs, in terms of 2D and 3D topology through torsional energy of the [BO ] 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 CH uptakes compared with several classic porous materials, represents a promising CH storage material.