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Configurational entropy driven high‐pressure behaviour of a flexible metal‐organic framework

DOI: 10.1002/anie.202011004 DOI Help

Authors: Pia Vervoorts (Technical University of Munich) , Julian Keupp (Ruhr University Bochum) , Andreas Schneemann (Technical University Dresden) , Claire L. Hobday (The University of Edinburgh) , Dominik Daisenberger (Diamond Light Source) , Roland A. Fischer (Technical University Munich) , Rochus Schmid (Ruhr University Bochum) , Gregor Kieslich (Technical University of Munich)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Angewandte Chemie International Edition

State: Published (Approved)
Published: September 2020
Diamond Proposal Number(s): 19187

Abstract: Flexible metal‐organic frameworks (MOFs) show large structural flexibility as a function of temperature or (gas)pressure variation, a fascinating property of high technological and scientific relevance. The targeted design of flexible MOFs demands control over macroscopic thermodynamics as determined by microscopic chemical interactions and remains an open challenge. Here we apply high‐pressure powder X‐ray diffraction and molecular dynamics simulations to gain insight into the microscopic chemical factors that determine the high‐pressure macroscopic thermodynamics of two flexible pillared‐layer MOFs. For the first time we identify configurational entropy that originates from side chain modifications of the linker as the key factor determining the thermodynamics in a flexible MOF. The study shows that configurational entropy is an important yet largely overlooked parameter, providing an intriguing perspective of how to chemically access the underlying free energy landscape in MOFs.

Journal Keywords: flexible metal-organic frameworks; high pressure properties; Molecular Dynamics; vibrational & configurational entropy

Subject Areas: Chemistry, Materials

Instruments: I15-Extreme Conditions