Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66

Jessica Bristow; Katrine Svane; Davide Tiana; Jonathan Skelton; Julian D.  Gale; Aron Walsh

doi:10.1021/acs.jpcc.6b01659

Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66

Jessica Bristow, Katrine Svane, Davide Tiana, Jonathan Skelton, Julian D. Gale, Aron Walsh

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Abstract

We report an investigation of the `missing-linker phenomenon' in the Zr-based metal-organic framework UiO-66 using atomistic forcefield and quantum chemical methods. For a vacant benzene dicarboxylate ligand, the lowest energy charge capping mechanism involves acetic acid or Cl-/H2O. The calculated defect free energy of formation is remarkably low, consistent with the high defect concentrations reported experimentally. A dynamic structural instability is identified for certain higher defect concentrations. In addition to the changes in material properties upon defect formation, we assess the formation of molecular aggregates, which provide an additional driving force for ligand loss. These results are expected to be of relevance to a wide range of metal-organic frameworks.

Original language	English
Pages (from-to)	9276-9281
Journal	Journal of Physical Chemistry C
Volume	120
Issue number	17
Early online date	12 Apr 2016
DOIs	https://doi.org/10.1021/acs.jpcc.6b01659
Publication status	Published - 5 May 2016

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This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C, copyright (C) American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see of a paper published in: http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.6b01659
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http://dx.doi.org/10.1021/acs.jpcc.6b01659

Cite this

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title = "Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66",

abstract = "We report an investigation of the `missing-linker phenomenon' in the Zr-based metal-organic framework UiO-66 using atomistic forcefield and quantum chemical methods. For a vacant benzene dicarboxylate ligand, the lowest energy charge capping mechanism involves acetic acid or Cl-/H2O. The calculated defect free energy of formation is remarkably low, consistent with the high defect concentrations reported experimentally. A dynamic structural instability is identified for certain higher defect concentrations. In addition to the changes in material properties upon defect formation, we assess the formation of molecular aggregates, which provide an additional driving force for ligand loss. These results are expected to be of relevance to a wide range of metal-organic frameworks.",

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T1 - Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66

AU - Bristow, Jessica

AU - Svane, Katrine

AU - Tiana, Davide

AU - Skelton, Jonathan

AU - Gale, Julian D.

AU - Walsh, Aron

PY - 2016/5/5

Y1 - 2016/5/5

N2 - We report an investigation of the `missing-linker phenomenon' in the Zr-based metal-organic framework UiO-66 using atomistic forcefield and quantum chemical methods. For a vacant benzene dicarboxylate ligand, the lowest energy charge capping mechanism involves acetic acid or Cl-/H2O. The calculated defect free energy of formation is remarkably low, consistent with the high defect concentrations reported experimentally. A dynamic structural instability is identified for certain higher defect concentrations. In addition to the changes in material properties upon defect formation, we assess the formation of molecular aggregates, which provide an additional driving force for ligand loss. These results are expected to be of relevance to a wide range of metal-organic frameworks.

AB - We report an investigation of the `missing-linker phenomenon' in the Zr-based metal-organic framework UiO-66 using atomistic forcefield and quantum chemical methods. For a vacant benzene dicarboxylate ligand, the lowest energy charge capping mechanism involves acetic acid or Cl-/H2O. The calculated defect free energy of formation is remarkably low, consistent with the high defect concentrations reported experimentally. A dynamic structural instability is identified for certain higher defect concentrations. In addition to the changes in material properties upon defect formation, we assess the formation of molecular aggregates, which provide an additional driving force for ligand loss. These results are expected to be of relevance to a wide range of metal-organic frameworks.

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DO - 10.1021/acs.jpcc.6b01659

M3 - Article

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EP - 9281

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 17

ER -

Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66

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Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

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Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66

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Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

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High Performance Computing (HPC) Facility

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