Open AccessBreathing-Dependent Redox Activity in a Tetrathiafulvalene-Based Metal–Organic Framework
Author(s) -
Manuel Souto,
Jorge Romero,
Joaquín Calbo,
Íñigo J. VitóricaYrezábal,
José L. Zafra,
Juan Casado,
Enrique Ortı́,
Aron Walsh,
Guillermo Mı́nguez Espallargas
Publication year - 2018
Publication title -
journal of the american chemical society
Language(s) - Uncategorized
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.8b05890
Subject(s) - tetrathiafulvalene , chemistry , redox , raman spectroscopy , electrochemistry , planarity testing , metal organic framework , nanotechnology , adsorption , molecule , inorganic chemistry , organic chemistry , electrode , materials science , crystallography , physics , optics
"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.
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