Kollias, L;
Cantu, DC;
Glezakou, V;
Rousseau, R;
Salvalaglio, M;
(2020)
On the Role of Enthalpic and Entropic Contributions to the Conformational Free Energy Landscape of MIL‐101(Cr) Secondary Building Units.
Advanced Theory and Simulations
10.1002/adts.202000092.
(In press).
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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.
| Type: | Article |
|---|---|
| Title: | On the Role of Enthalpic and Entropic Contributions to the Conformational Free Energy Landscape of MIL‐101(Cr) Secondary Building Units |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1002/adts.202000092 |
| Publisher version: | https://doi.org/10.1002/adts.202000092 |
| Language: | English |
| Additional information: | © 2020 The Authors. Published by Wiley‐VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial‐NoDerivs License (http://creativecommons.org/licenses/by-nc-nd/4.0/). |
| Keywords: | entropy, metal‐organic frameworks, molecular dynamics |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Chemical Engineering |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10110820 |
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