TY - JOUR
T1 - Linker Substituents Control the Thermodynamic Stability in Metal-Organic Frameworks
AU - Novendra, Novendra
AU - Marrett, Joseph M.
AU - Katsenis, Athanassios D.
AU - Titi, Hatem M.
AU - Arhangelskis, Mihails
AU - Friščić, Tomislav
AU - Navrotsky, Alexandra
N1 - Funding Information:
Dr Filip Topić is acknowledged for help with crystal structure analysis. We thank Prof. A. J. Howarth, Concordia University, for help in acquiring nitrogen sorption data and Dr. R. S. Stein, McGill University, for acquiring solid state NMR data. The calorimetric work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, grant no. DE-FG02-03ER46053. We acknowledge financial support of the NSERC Discovery Grant (RGPIN-2017-06467) and Discovery Supplement Award (RGPAS 507837–17). M.A. acknowledges the support of National Science Center (NCN) of Poland Sonata grant (2018/31/D/ST5/03619). Periodic DFT calculations were performed on a Prometheus supercomputer (Cyfronet, Krakow) for which access was granted via PLGrid consortium.
PY - 2020/12/30
Y1 - 2020/12/30
N2 - We report the first systematic experimental and theoretical study of the relationship between the linker functionalization and the thermodynamic stability of metal-organic frameworks (MOFs) using a model set of eight isostructural zeolitic imidazolate frameworks (ZIFs) based on 2-substituted imidazolate linkers. The frameworks exhibit a significant (30 kJ·mol-1) variation in the enthalpy of formation depending on the choice of substituent, which is accompanied by only a small change in molar volume. These energetics were readily reproduced by density functional theory (DFT) calculations. We show that these variations in the enthalpy of MOF formation are in linear correlation to the readily accessible properties of the linker substituent, such as the Hammett σ-constant or electrostatic surface potential. These results provide the first quantifiable relationship between the MOF thermodynamics and the linker structure, suggesting a route to design and tune MOF stability.
AB - We report the first systematic experimental and theoretical study of the relationship between the linker functionalization and the thermodynamic stability of metal-organic frameworks (MOFs) using a model set of eight isostructural zeolitic imidazolate frameworks (ZIFs) based on 2-substituted imidazolate linkers. The frameworks exhibit a significant (30 kJ·mol-1) variation in the enthalpy of formation depending on the choice of substituent, which is accompanied by only a small change in molar volume. These energetics were readily reproduced by density functional theory (DFT) calculations. We show that these variations in the enthalpy of MOF formation are in linear correlation to the readily accessible properties of the linker substituent, such as the Hammett σ-constant or electrostatic surface potential. These results provide the first quantifiable relationship between the MOF thermodynamics and the linker structure, suggesting a route to design and tune MOF stability.
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U2 - 10.1021/jacs.0c09284
DO - 10.1021/jacs.0c09284
M3 - Article
C2 - 33326738
AN - SCOPUS:85098890394
VL - 142
SP - 21720
EP - 21729
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 52
ER -