Rational Design of 7-Azaindole-Based Robust Microporous Hydrogen-Bonded Organic Framework for Gas Sorption

7-Azaindole has been integrated as building block with complementary N-H⋅⋅⋅N hydrogen bonding sites for the synthesis of a tetrahedral molecular tecton, namely tetra(α-carbolin-6-yl)methane, TACM. The self-assembly of this molecule results in a 3D hydrogen-bonded organic framework (HOF). This supramolecular structure constitutes a crystalline microporous material with an extraordinary thermal and chemical robustness. Single crystal X-ray diffraction reveals how the five-fold catenation of diamonoid systems, stabilized by hydrogen bonds and π-π interactions, form an interpenetrated network with monodimensional channels. The structural features of the crystalline material are also observed by transmission electron microscopy (TEM). Additionally, the microporosity of the activated TACM-HOF is characterized by gas sorption (N₂, CO₂, CH₄ and H₂) experiments performed at different pressures. A selective adsorption is observed for CO₂ uptake and TACM-HOF also presents a good adsorption capacity for H₂ among supramolecular organic frameworks.