Breathing-Dependent Redox Activity in a Tetrathiafulvalene-Based Metal-Organic Framework

Manuel Souto; Jorge Romero; Joaquín Calbo; Iñigo J. Vitórica-Yrezábal; José L. Zafra; Juan Casado; Enrique Ortí; Aron Walsh; Guillermo Mínguez Espallargas

doi:10.1021/jacs.8b05890

Breathing-Dependent Redox Activity in a Tetrathiafulvalene-Based Metal-Organic Framework

Manuel Souto, Jorge Romero, Joaquín Calbo, Iñigo J. Vitórica-Yrezábal, José L. Zafra, Juan Casado, Enrique Ortí, Aron Walsh, Guillermo Mínguez Espallargas

Department of Physics

Research output: Contribution to journal › Article › peer-review

56 Scopus citations

Abstract

"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.

Original language	English
Pages (from-to)	10562-10569
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	140
Issue number	33
DOIs	https://doi.org/10.1021/jacs.8b05890
State	Published - 22 Aug 2018

Bibliographical note

Funding 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.

Publisher Copyright:
© 2018 American Chemical Society.

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title = "Breathing-Dependent Redox Activity in a Tetrathiafulvalene-Based Metal-Organic Framework",

abstract = "{"}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.",

author = "Manuel Souto and Jorge Romero and Joaqu{\'i}n Calbo and Vit{\'o}rica-Yrez{\'a}bal, {I{\~n}igo J.} and Zafra, {Jos{\'e} L.} and Juan Casado and Enrique Ort{\'i} and Aron Walsh and {M{\'i}nguez Espallargas}, Guillermo",

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AU - Romero, Jorge

AU - Calbo, Joaquín

AU - Vitórica-Yrezábal, Iñigo J.

AU - Zafra, José L.

AU - Casado, Juan

AU - Ortí, Enrique

AU - Walsh, Aron

AU - Mínguez Espallargas, Guillermo

N1 - Funding 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. Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/8/22

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Breathing-Dependent Redox Activity in a Tetrathiafulvalene-Based Metal-Organic Framework

Abstract

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