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Title: 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 » no need of excess of the iridium metallolinker.« less

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [1];  [2]; ORCiD logo [2]
  1. Stockholm Univ., Stockholm (Sweden)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (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 = {2017},
month = {4}
}

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Cited by: 8 works
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Figures / Tables:

Figure 1 Figure 1: a) Structure of the ZABU (Zn8(AD)4O16) nodes [C- grey, O- red, N-light blue and Zn blue]. b) Twisting triplex struts (Zn8(AD)4O2)2(BPDC)3 in bio-MOF-100. c) Representation of the iridium complex H2IrL used in this work to be introduced by SALE in bio-MOF-100.

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