Understanding disorder and linker deficiency in porphyrinic zirconium-based metal–organic frameworks by resolving the Zr8O6 cluster conundrum in PCN-221

Charlotte Koschnick, Robert Stäglich, Tanja Scholz, Maxwell W. Terban, Alberto Mankowski, Gökcen Savasci, Florian Binder, Alexander Schökel, Martin Etter, Jürgen Nuss, Renée Siegel, Luzia S. Germann, Christian Ochsenfeld, Robert E. Dinnebier, Jürgen Senker () and Bettina V. Lotsch ()
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Charlotte Koschnick: Max Planck Institute for Solid State Research
Robert Stäglich: University of Bayreuth
Tanja Scholz: Max Planck Institute for Solid State Research
Maxwell W. Terban: Max Planck Institute for Solid State Research
Alberto Mankowski: Max Planck Institute for Solid State Research
Gökcen Savasci: Max Planck Institute for Solid State Research
Florian Binder: Max Planck Institute for Solid State Research
Alexander Schökel: Deutsches Elektronen-Synchrotron (DESY)
Martin Etter: Deutsches Elektronen-Synchrotron (DESY)
Jürgen Nuss: Max Planck Institute for Solid State Research
Renée Siegel: University of Bayreuth
Luzia S. Germann: Max Planck Institute for Solid State Research
Christian Ochsenfeld: Max Planck Institute for Solid State Research
Robert E. Dinnebier: Max Planck Institute for Solid State Research
Jürgen Senker: University of Bayreuth
Bettina V. Lotsch: Max Planck Institute for Solid State Research

Nature Communications, 2021, vol. 12, issue 1, 1-9

Abstract: Abstract Porphyrin-based metal–organic frameworks (MOFs), exemplified by MOF-525, PCN-221, and PCN-224, are promising systems for catalysis, optoelectronics, and solar energy conversion. However, subtle differences between synthetic protocols for these three MOFs give rise to vast discrepancies in purported product outcomes and description of framework topologies. Here, based on a comprehensive synthetic and structural analysis spanning local and long-range length scales, we show that PCN-221 consists of Zr6O4(OH)4 clusters in four distinct orientations within the unit cell, rather than Zr8O6 clusters as originally published, and linker vacancies at levels of around 50%, which may form in a locally correlated manner. We propose disordered PCN-224 (dPCN-224) as a unified model to understand PCN-221, MOF-525, and PCN-224 by varying the degree of orientational cluster disorder, linker conformation and vacancies, and cluster–linker binding. Our work thus introduces a new perspective on network topology and disorder in Zr-MOFs and pinpoints the structural variables that direct their functional properties.

Date: 2021
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DOI: 10.1038/s41467-021-23348-w

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