Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange

doi:10.1021/acs.inorgchem.7b00149

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 »« less

Authors:

Miera, Greco Gonzalez ^[1];

^[1]; Chupas, Peter J. ^[2];

^[1]; Chapman, Karena W. ^[2];

^[2]

Stockholm Univ., Stockholm (Sweden)
Argonne National Lab. (ANL), Argonne, IL (United States)

Publication Date:: 2017-04-06

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

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.

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                    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.  doi:10.1021/acs.inorgchem.7b00149.

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                    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.  doi:10.1021/acs.inorgchem.7b00149.  https://www.osti.gov/servlets/purl/1373900.

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@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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Journal Article:

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DOI: 10.1021/acs.inorgchem.7b00149

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Cited by: 8 works

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Figures / Tables:

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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Works referencing / citing this record:

CCDC 1502535: Experimental Crystal Structure Determination: HAQSIE : catena-[tetrakis(μ-biphenyl-4,4'-dicarboxylato)-tetrakis(μ-6-aminopurinyl)-bis(μ-oxo)-octa-zinc tetrahydrate]
dataset, December 2016

Miera, Greco González; Gómez, Antonio Bermejo; Chupas, Peter J.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1mfhwf

A novel 3D POMOF based on Wells–Dawson arsenomolybdates with excellent photocatalytic and lithium-ion battery performance
journal, January 2017

Cong, Bo-Wen; Su, Zhan-Hua; Zhao, Zhi-Feng
CrystEngComm, Vol. 19, Issue 47
DOI: 10.1039/c7ce01734k

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

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Title: Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange

Abstract

Citation Formats

Figures / Tables:

CCDC 1502535: Experimental Crystal Structure Determination: HAQSIE : catena-[tetrakis(μ-biphenyl-4,4'-dicarboxylato)-tetrakis(μ-6-aminopurinyl)-bis(μ-oxo)-octa-zinc tetrahydrate] dataset, December 2016

A novel 3D POMOF based on Wells–Dawson arsenomolybdates with excellent photocatalytic and lithium-ion battery performance journal, January 2017

CCDC 1502535: Experimental Crystal Structure Determination: HAQSIE : catena-[tetrakis(μ-biphenyl-4,4'-dicarboxylato)-tetrakis(μ-6-aminopurinyl)-bis(μ-oxo)-octa-zinc tetrahydrate]
dataset, December 2016

A novel 3D POMOF based on Wells–Dawson arsenomolybdates with excellent photocatalytic and lithium-ion battery performance
journal, January 2017