Issue 46, 2023

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

Abstract

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 H10TcatPP, 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 m2 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 (∼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.

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

Supplementary files

Article information

Article type
Paper
Submitted
28 7 2023
Accepted
31 10 2023
First published
03 11 2023
This article is Open Access
Creative Commons BY-NC license

J. Mater. Chem. A, 2023,11, 25465-25483

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

S. De, G. Mouchaham, F. Liu, M. Affram, B. Abeykoon, N. Guillou, E. Jeanneau, J. Grenèche, L. Khrouz, C. Martineau-Corcos, L. Boudjema, F. Salles, P. Salcedo-Abraira, G. Valente, M. Souto, A. Fateeva and T. Devic, J. Mater. Chem. A, 2023, 11, 25465 DOI: 10.1039/D3TA04490D

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