"Breathing" metal-organic frameworks (MOFs) that involve changes in their structural and physical properties upon an external stimulus are an interesting class of crystalline materials due to their range of potential applications including chemical sensors. The addition of redox activity opens up a new pathway for multifunctional "breathing" frameworks. Herein, we report the continuous breathing behavior of a tetrathiafulvalene (TTF)-based MOF, namely MUV-2, 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 of the MOF, directly impacting on its electrochemical properties and 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.
Bibliographical noteFunding Information:
The work has been supported by the European Union (ERC-2016-CoG 724681-S-CAGE) and the Spanish MINECO (CTQ2014-59209-P, CTQ2017-89528-P and CTQ2015-69391-P). We also thank the Spanish government for the provision of a Maria de Maeztu project (MDM-2015-0538). G.M.E. and M.S. thank MINECO for a Ramon y Cajal and a Juan de la Cierva-Formacion fellowship, respectively.
© 2018 American Chemical Society.