We discuss the recent advances and main approaches towards the design of electrically conductive COFs, highlight some of the challenges in such design and give our views on the future directions of this field.

“Breathing” metal-organic frameworks (MOFs) exhibiting changes in their structural and physical properties upon an external stimulus are an interesting class of crystalline materials due to their potential applications including chemical sensors. The addition of redox activity opens up a new pathway for multi-functional “breathing” frameworks. Herein we report the continuous breathing behavior of a tetrathiafulvalene (TTF)-based MOF showing a reversible swelling (up to ca. 40% of the volume cell) upon solvent adsorption. Importantly, the planarity of the TTF linkers is influenced by the breathing behavior, directly impacting on their electrochemical properties, thus opening the way for the development of new electrochemical sensors. Quantum chemical calculations and Raman spectroscopy have been used to provide insights into the tunability of the oxidation potential.

A highly stable Metal–Organic Framework with a hierarchical structure based on the Fe₃O cluster and a TTF-based ligand is presented.

We review some recent strategies to improve the energy density, power density and cycling stability of redox-active COF-based electrodes for rechargeable batteries from the perspective of molecular design and electrode optimisation.