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

被引:72
作者
Souto, Manuel [1 ]
Romero, Jorge [1 ]
Calbo, Joaquin [2 ]
Vitorica-Yrezabal, Inigo J. [4 ]
Zafra, Jose L. [5 ]
Casado, Juan [5 ]
Orti, Enrique [1 ]
Walsh, Aron [2 ,3 ]
Minguez Espallargas, Guillermo [1 ]
机构
[1] Univ Valencia, Inst Ciencia Mol ICMo1, C Catedratico Jose Beltran 2, Paterna 46980, Spain
[2] Imperial Coll London, Dept Mat, London SW7 2AZ, England
[3] Yonsei Univ, Dept Mat Sci & Engn, Seoul 03722, South Korea
[4] Univ Manchester, Sch Chem, Oxford Rd, Manchester M13 9PL, Lancs, England
[5] Univ Malaga, Dept Quim Fis, E-29071 Malaga, Spain
基金
英国工程与自然科学研究理事会;
关键词
CONDUCTIVITY; UNITS; MOFS; NI;
D O I
10.1021/jacs.8b05890
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
"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.
引用
收藏
页码:10562 / 10569
页数:8
相关论文
共 38 条
[1]   Theoretical study of a new building block for organic conductors:: Tetrathiapentalene and its radical cation [J].
Adamo, C ;
Arnaud, R ;
Scalmani, G ;
Müller, H ;
Sahli, F ;
Barone, V .
JOURNAL OF PHYSICAL CHEMISTRY B, 1999, 103 (33) :6863-6869
[2]   Solvothermal Preparation of an Electrocatalytic Metalloporphyrin MOF Thin Film and its Redox Hopping Charge-Transfer Mechanism [J].
Ahrenholtz, Spencer R. ;
Epley, Charity C. ;
Morris, Amanda J. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (06) :2464-2472
[3]   A new series of π-extended tetrathiafulvalene derivatives incorporating fused furanodithiino and thienodithiino units:: a joint experimental and theoretical study [J].
Berridge, R ;
Serebryakov, IM ;
Skabara, PJ ;
Ortí, E ;
Viruela, R ;
Pou-Amérigo, R ;
Coles, SJ ;
Hursthouse, MB .
JOURNAL OF MATERIALS CHEMISTRY, 2004, 14 (18) :2822-2830
[4]   Ab initio molecular simulations with numeric atom-centered orbitals [J].
Blum, Volker ;
Gehrke, Ralf ;
Hanke, Felix ;
Havu, Paula ;
Havu, Ville ;
Ren, Xinguo ;
Reuter, Karsten ;
Scheffler, Matthias .
COMPUTER PHYSICS COMMUNICATIONS, 2009, 180 (11) :2175-2196
[5]  
Carrington EJ, 2017, NAT CHEM, V9, P882, DOI [10.1038/nchem.2747, 10.1038/NCHEM.2747]
[6]   Exploiting redox activity in metal-organic frameworks: concepts, trends and perspectives [J].
D'Alessandro, D. M. .
CHEMICAL COMMUNICATIONS, 2016, 52 (58) :8957-8971
[7]   Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal-Organic Framework [J].
Darago, Lucy E. ;
Aubrey, Michael L. ;
Yu, Chung Jui ;
Gonzalez, Miguel I. ;
Long, Jeffrey R. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (50) :15703-15711
[8]   Ultraporous, Water Stable, and Breathing Zirconium-Based Metal-Organic Frameworks with ftw Topology [J].
Deria, Pravas ;
Gomez-Gualdron, Diego A. ;
Bury, Wojciech ;
Schaef, Herbert T. ;
Wang, Timothy C. ;
Thallapally, Praveen K. ;
Sarjeant, Amy A. ;
Snurr, Randall Q. ;
Hupp, Joseph T. ;
Farha, Omar K. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (40) :13183-13190
[9]   Large breathing effects in three-dimensional porous hybrid matter: facts, analyses, rules and consequences [J].
Ferey, Gerard ;
Serre, Christian .
CHEMICAL SOCIETY REVIEWS, 2009, 38 (05) :1380-1399
[10]   Reversible Tuning Hydroquinone/Quinone Reaction in Metal-Organic Framework: Immobilized Molecular Switches in Solid State [J].
Gui, Bo ;
Meng, Xiangshi ;
Chen, Yi ;
Tian, Jianwu ;
Liu, Guoliang ;
Shen, Chencheng ;
Zeller, Matthias ;
Yuan, Daqiang ;
Wang, Cheng .
CHEMISTRY OF MATERIALS, 2015, 27 (18) :6426-6431