Expanding the horizons of porphyrin metal-organic frameworks via catecholate coordination: exploring structural diversity, material stability and redox properties


Porphyrin based Metal-Organic Frameworks (MOFs) have generated high interest because of their unique combination of light absorption, electron transfer and guest adsorption/desorption properties. In this study, we expand the range of available MOF materials by focusing on the seldom studied porphyrin ligand H(10)TcatPP, functionalized with tetracatecholate coordinating groups. A systematic evaluation of its reactivity with M(III) cations (Al, Fe, and In) led to the synthesis and isolation of three novel MOF phases. Through a comprehensive characterization approach involving single crystal and powder synchrotron X-ray diffraction (XRD) in combination with the local information gained from spectroscopic techniques, we elucidated the structural features of the solids, which are all based on different inorganic secondary building units (SBUs). All the synthesized MOFs demonstrate an accessible porosity, with one of them presenting mesopores and the highest reported surface area to date for a porphyrin catecholate MOF (>2000 m(2) g(-1)). Eventually, the redox activity of these solids was investigated in a half-cell vs. Li with the aim of evaluating their potential as electrode positive materials for electrochemical energy storage. One of the solids displayed reversibility during cycling at a rather high potential (similar to 3.4 V vs. Li+/Li), confirming the interest of redox active phenolate ligands for applications involving electron transfer. Our findings expand the library of porphyrin-based MOFs and highlight the potential of phenolate ligands for advancing the field of MOFs for energy storage materials.



subject category

Chemistry; Energy & Fuels; Materials Science


De, SDR; Mouchaham, G; Liu, FB; Affram, M; Abeykoon, B; Guillou, N; Jeanneau, E; Grenèche, JM; Khrouz, L; Martineau-Corcos, C; Boudjema, L; Salles, F; Salcedo-Abraira, P; Valente, G; Souto, M; Fateeva, A; Devic, T

our authors


Funding from the region Pays de la Loire (project MatHySE2), from the region Auvergne Rhone Alpes (project SCUSI), the ANR (projects STREAM ANR-17-CE09-0029-01, CONDMOF ANR-06-BLAN-0202-02, ThioMOFs ANR-19-CE08-0029-01 and LABEX CHARMMMAT ANR-11-LABEX-0039) is acknowledged. This work was supported by the LABEX iMUST of the University of Lyon (ANR-10-LABX-0064), created within the program << Investissements d'Avenir >> set up by the French government and managed by the French National Research Agency (ANR). The French Ministry of higher education and research is acknowledged for the studentship of B. A. F. L. acknowledges the support of the CSC (China Scholarship Council) scholarship. This work has also received funding from the European Research Council (ERC) under the Horizon Europe Framework Programme (101039748-ELECTROCOFS), FCT (PTDC/QUI-ELT/2593/2021) and CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020 & LA/P/0006/2020, financed by national funds through the FCT/MEC (PIDDAC). The authors also thank the synchrotron Soleil for providing access to the beamline Cristal Soleil, and scientific and technical help from Erik Elkaim and Pierre Fertey. The network RECIPROCS, Lise Marie Chamoreau, and Benoit Baptiste are warmly acknowledged for the data collection. The Centre Technologique des Microstructures of Lyon University is acknowledged for providing electronic microscopy facilities. The authors thank Francois Guillonneau from the University Paris Descatrtes for the MALDI analysis of the ligands. Philippe Poizot is also thanked for fruitful discussion of the electrochemical experiments. A. F. warmly thanks Pr Jo & atilde;o Rocha for welcoming her at CICECO-Aveiro. We thank Justin Andrews and Mircea Dinc & abreve; (MIT) for assistance with the electrical measurements.

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