Controlling the Flexibility of Carbazole‐Based Metal–Organic Frameworks by Substituent Effects

We have developed highly porous Cu-based metal-organic frameworks (MOFs) using carbazole-type linkers. The novel topological structure of these MOFs was revealed by single-crystal X-ray diffraction analysis. Molecular adsorption/desorption experiments indicated that these MOFs are flexible and change their structure upon adsorption/desorption of organic solvents and gas molecules. These MOFs exhibit unprecedented properties that allow controlling their flexibility by adding a functional group onto the central benzene ring of the organic ligand. For example, the introduction of electron-donating substituents increases the robustness of the resulting MOFs. These MOFs also exhibit flexibility-dependent differences in gas-adsorption and -separation performance. Thus, this study represents the first example of controlling the flexibility of MOFs with the same topological structure via the substituent effect of functional groups introduced into the organic ligand.