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On the Role of Enthalpic and Entropic Contributions to the Conformational Free Energy Landscape of MIL‐101(Cr) Secondary Building Units
Author(s) -
Kollias Loukas,
Cantu David C.,
Glezakou VassilikiAlexandra,
Rousseau Roger,
Salvalaglio Matteo
Publication year - 2020
Publication title -
advanced theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.068
H-Index - 17
ISSN - 2513-0390
DOI - 10.1002/adts.202000092
Subject(s) - sbus , conformational isomerism , enthalpy , energy landscape , entropy (arrow of time) , thermodynamics , chemistry , crystallography , conformational entropy , statistical physics , materials science , metal organic framework , physics , molecule , organic chemistry , adsorption
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.