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Title: On the Role of Enthalpic and Entropic Contributions to the Conformational Free Energy Landscape of MIL‐101(Cr) Secondary Building Units

Abstract

The thermo-structural behavior of metal-organic framework (MOF) precursors is responsible for regulating the introduction of defects in MOF structures during synthesis. In this paper, factors affecting the flexibility of MIL-101(Cr) half-secondary building units (half-SBUs) are evaluated in solution using enhanced sampling methods. In particular, entropic and enthalpic contributions to the conformational free energy landscape of isolated MIL-101(Cr) half-SBUs are calculated in water, in the presence and absence of ionic species (Na+ and F-), and in N, N-dimethylformamide (DMF). This analysis leads to the observation that the interplay between enthalpy and entropy determines the most probable conformational state for half-SBUs. This observation extends to the most relevant SBU intermediate, in which conformational entropy plays a key role in stabilizing configurations that differ from those found in the MIL-101(Cr) crystal structure. The findings highlight the importance of explicitly considering entropic effects, associated with finite-temperature sampling when estimating the relative stability of different conformers of SBUs.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]
  1. Thomas Young Centre and Department of Chemical Engineering University College London London WC1E 7JE UK
  2. Chemical and Materials Engineering Department University of Nevada Reno Reno NV 89557 USA
  3. Basic and Applied Molecular Foundations Pacific Northwest National Laboratory Richland WA 99352 USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1664462
Alternate Identifier(s):
OSTI ID: 1664463; OSTI ID: 1755007
Report Number(s):
PNNL-SA-147621
Journal ID: ISSN 2513-0390
Grant/Contract Number:  
AC05-76RL01830; AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Advanced Theory and Simulations
Additional Journal Information:
Journal Name: Advanced Theory and Simulations Journal Volume: 3 Journal Issue: 12; Journal ID: ISSN 2513-0390
Publisher:
Wiley
Country of Publication:
Germany
Language:
English
Subject:
42 ENGINEERING; entropy; metal-organic frameworks; molecular dynamics

Citation Formats

Kollias, Loukas, Cantu, David C., Glezakou, Vassiliki‐Alexandra, Rousseau, Roger, and Salvalaglio, Matteo. On the Role of Enthalpic and Entropic Contributions to the Conformational Free Energy Landscape of MIL‐101(Cr) Secondary Building Units. Germany: N. p., 2020. Web. https://doi.org/10.1002/adts.202000092.
Kollias, Loukas, Cantu, David C., Glezakou, Vassiliki‐Alexandra, Rousseau, Roger, & Salvalaglio, Matteo. On the Role of Enthalpic and Entropic Contributions to the Conformational Free Energy Landscape of MIL‐101(Cr) Secondary Building Units. Germany. https://doi.org/10.1002/adts.202000092
Kollias, Loukas, Cantu, David C., Glezakou, Vassiliki‐Alexandra, Rousseau, Roger, and Salvalaglio, Matteo. Tue . "On the Role of Enthalpic and Entropic Contributions to the Conformational Free Energy Landscape of MIL‐101(Cr) Secondary Building Units". Germany. https://doi.org/10.1002/adts.202000092.
@article{osti_1664462,
title = {On the Role of Enthalpic and Entropic Contributions to the Conformational Free Energy Landscape of MIL‐101(Cr) Secondary Building Units},
author = {Kollias, Loukas and Cantu, David C. and Glezakou, Vassiliki‐Alexandra and Rousseau, Roger and Salvalaglio, Matteo},
abstractNote = {The thermo-structural behavior of metal-organic framework (MOF) precursors is responsible for regulating the introduction of defects in MOF structures during synthesis. In this paper, factors affecting the flexibility of MIL-101(Cr) half-secondary building units (half-SBUs) are evaluated in solution using enhanced sampling methods. In particular, entropic and enthalpic contributions to the conformational free energy landscape of isolated MIL-101(Cr) half-SBUs are calculated in water, in the presence and absence of ionic species (Na+ and F-), and in N, N-dimethylformamide (DMF). This analysis leads to the observation that the interplay between enthalpy and entropy determines the most probable conformational state for half-SBUs. This observation extends to the most relevant SBU intermediate, in which conformational entropy plays a key role in stabilizing configurations that differ from those found in the MIL-101(Cr) crystal structure. The findings highlight the importance of explicitly considering entropic effects, associated with finite-temperature sampling when estimating the relative stability of different conformers of SBUs.},
doi = {10.1002/adts.202000092},
journal = {Advanced Theory and Simulations},
number = 12,
volume = 3,
place = {Germany},
year = {2020},
month = {9}
}

Journal Article:
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https://doi.org/10.1002/adts.202000092

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