Kollias, L;
Cantu, DC;
Tubbs, MA;
Rousseau, R;
Glezakou, V-A;
Salvalaglio, M;
(2019)
Molecular level understanding of the free energy landscape in early stages of MOF nucleation.
Journal of the American Chemical Society
, 141
(14)
pp. 6073-6081.
10.1021/jacs.9b01829.
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Abstract
The assembly mechanism of hierarchical materials controlled by the choice of solvent and presence of spectator ions. In this paper, we use enhanced sampling molecular dynamics methods to investigate these effects on the configurational landscape of metal-linker interactions in the early stages of synthesis, using MIL-101(Cr) as a prototypical example. Microsecond-long well-tempered metadynamics (WTmetaD) uncover a complex free energy structural landscape, with distinct crystal (C) and non-crystal (NC) like configurations and their equilibrium population. In presence of ions (Na+, F-), we observe a complex effect on the crystallinity of secondary building units (SBUs), by encouraging/ suppressing salt bridges between C configurations and consequently controlling the percentage of defects. Solvent effects are assessed by introducing N, N-dimethylformamide (DMF) instead of water, where SBU adducts are appreciably more stable and compact. These results shed light on how solvent nature and ionic strength impact the free energy of nucleation phenomena that ultimately control materials synthesis and defect formation.
| Type: | Article |
|---|---|
| Title: | Molecular level understanding of the free energy landscape in early stages of MOF nucleation |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/jacs.9b01829 |
| Publisher version: | https://doi.org/10.1021/jacs.9b01829 |
| Language: | English |
| Additional information: | This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions. |
| Keywords: | Metal-Organic Frameworks, Nucleation, Molecular Dynamics, Well-Tempered Metadynamics |
| 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/10070507 |
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