Carborane-Based Three-Dimensional Covalent Organic Frameworks

The predesignable porous structure and high structural flexibility of covalent organic frameworks (COFs) render this material desirable as a platform for addressing various cutting-edge issues. Precise control over their composition, topological structure, porosity, and stability to realize tailor-made functionality still remains a great challenge. In this work, we developed a new kind of three-dimensional (3D) carborane-based COF with a 7-fold interpenetrating dia topological diagram. The resulting COFs exhibited high crystallinity, exceptional porosity, and strong robustness. The slightly lower electronegativity of boron (2.04) than that of hydrogen (2.20) can lead to the polarization of the B–H bond into a B^δ+–H^δ− mode, which renders these COFs as high-performance materials for the adsorption and separation of hexane isomers through the B–H^δ−···H^δ+–C interaction. Significantly, the carborane content of obtained COFs reached up to 54.2 wt %, which gets the highest rank among all the reported porous materials. Combining high surface area, strong robustness, and high content of carborane, the obtained COFs can work as efficient adsorbents for the separation of the five hexane isomers with high separation factors. This work not only enhances the diversity of 3D functional COFs but also constitutes a further step toward the efficient separation of alkane isomers.