Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange
Abstract
Metal-organic frameworks (MOFs) have shown to be unsuspectedly dynamic. Here we describe the topological interconversion of a new framework in the bio-MOF-100 family (dia-c) into the known isomer (lcs) by doubling the pore volume, which occurs during post-synthesis modifications. During this transformation, re-assembling of the MOF building blocks into a completely different framework occurs, involving breaking/forming of metal-ligand bonds. MOF crystallinity and local structure are retained, as determined by powder X-ray diffraction (PXRD) and pair distribution function (PDF) analyses, respectively. We have exploited the inherent dynamism of bio-MOF-100 by coupling chemical decorations of the framework using solvent-assisted ligand exchange (SALE) to the topological change. Following this method and starting from the pristine dense dia-c phase, open lcs-bio-MOF-100 was prepared and functionalized in-situ with an iridium complex (IrL). Alternatively, the dia-c MOF could be modified with wide-ranging amounts of IrL up to ca. 50 mol%, as determined by solution 1H Nuclear Magnetic Resonance (NMR) spectroscopy, by tuning the concentration of the solutions used and with no evidence for isomer interconversion. The single-site nature of the iridium complexes within the MOFs was assessed by X-ray absorption spectroscopy (XAS) and PDF analyses. As a result, ligand exchanges occurred quantitatively at room temperature, withmore »
- Authors:
-
- Stockholm Univ., Stockholm (Sweden)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1373900
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 56; Journal Issue: 8; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Miera, Greco Gonzalez, Gomez, Antonio Bermejo, Chupas, Peter J., Martin-Matute, Belen, Chapman, Karena W., and Platero-Prats, Ana E. Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange. United States: N. p., 2017.
Web. doi:10.1021/acs.inorgchem.7b00149.
Miera, Greco Gonzalez, Gomez, Antonio Bermejo, Chupas, Peter J., Martin-Matute, Belen, Chapman, Karena W., & Platero-Prats, Ana E. Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange. United States. https://doi.org/10.1021/acs.inorgchem.7b00149
Miera, Greco Gonzalez, Gomez, Antonio Bermejo, Chupas, Peter J., Martin-Matute, Belen, Chapman, Karena W., and Platero-Prats, Ana E. Thu .
"Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange". United States. https://doi.org/10.1021/acs.inorgchem.7b00149. https://www.osti.gov/servlets/purl/1373900.
@article{osti_1373900,
title = {Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange},
author = {Miera, Greco Gonzalez and Gomez, Antonio Bermejo and Chupas, Peter J. and Martin-Matute, Belen and Chapman, Karena W. and Platero-Prats, Ana E.},
abstractNote = {Metal-organic frameworks (MOFs) have shown to be unsuspectedly dynamic. Here we describe the topological interconversion of a new framework in the bio-MOF-100 family (dia-c) into the known isomer (lcs) by doubling the pore volume, which occurs during post-synthesis modifications. During this transformation, re-assembling of the MOF building blocks into a completely different framework occurs, involving breaking/forming of metal-ligand bonds. MOF crystallinity and local structure are retained, as determined by powder X-ray diffraction (PXRD) and pair distribution function (PDF) analyses, respectively. We have exploited the inherent dynamism of bio-MOF-100 by coupling chemical decorations of the framework using solvent-assisted ligand exchange (SALE) to the topological change. Following this method and starting from the pristine dense dia-c phase, open lcs-bio-MOF-100 was prepared and functionalized in-situ with an iridium complex (IrL). Alternatively, the dia-c MOF could be modified with wide-ranging amounts of IrL up to ca. 50 mol%, as determined by solution 1H Nuclear Magnetic Resonance (NMR) spectroscopy, by tuning the concentration of the solutions used and with no evidence for isomer interconversion. The single-site nature of the iridium complexes within the MOFs was assessed by X-ray absorption spectroscopy (XAS) and PDF analyses. As a result, ligand exchanges occurred quantitatively at room temperature, with no need of excess of the iridium metallolinker.},
doi = {10.1021/acs.inorgchem.7b00149},
journal = {Inorganic Chemistry},
number = 8,
volume = 56,
place = {United States},
year = {Thu Apr 06 00:00:00 EDT 2017},
month = {Thu Apr 06 00:00:00 EDT 2017}
}
Web of Science
Figures / Tables:
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