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Breathing-dependent redox activity in a tetrathiafulvalene-based metal-organic framework

DOI: 10.1021/jacs.8b05890 DOI Help

Authors: Manuel Souto (Universidad de Valencia) , Jorge Romero (Universidad de Valencia) , Joaquín Calbo (Imperial College London) , Iñigo J. Vitorica-yrezabal (University of Manchester) , Jose L. Zafra (Universidad de Málaga) , Juan Casado Cordón (Universidad de Málaga) , Enrique Ortí (Universidad de Valencia) , Aron Walsh (Imperial College London; Yonsei University) , Guillermo Minguez Espallargas (Universidad de Valencia)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: July 2018
Diamond Proposal Number(s): 17379

Abstract: “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.

Journal Keywords: Metal-Organic Framework; breathing behavior; tetrathiafulvalene; redox activity

Subject Areas: Materials, Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction