TY - JOUR
T1 - Experimental Investigation of Thermodynamic Stabilization in Boron Imidazolate Frameworks (BIFs) Synthesized by Mechanochemistry
AU - Leonel, Gerson J.
AU - Lennox, Cameron B.
AU - Scharrer, Manuel
AU - Jayanthi, K.
AU - Friščic, Tomislav
AU - Navrotsky, Alexandra
N1 - Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
PY - 2023/9/14
Y1 - 2023/9/14
N2 - This study experimentally explores the energetics for the formation of boron-imidazolate frameworks (BIFs), which are synthesized by mechanochemistry. The topologically similar frameworks employ the same tetratopic linker based on tetrakis(imidazolyl)boric acid but differ in the monovalent cation metal nodes. This permits assessment of the stabilizing effect of metal nodes in frameworks with sodalite (SOD) and diamondoid (dia) topologies. The enthalpy of formation from endmembers (metal oxide and linker), which define thermodynamic stability of the structures, has been determined by use of acid solution calorimetry. The results show that heavier metal atoms in the node promote greater energetic stabilization of denser structures. Overall, in BIFs the relation between cation descriptors (ionic radius and electronegativity) and thermodynamic stability depends on framework topology. Thermodynamic stability increases with the metallic character of the cation employed as the metal node, independent of the framework topology. The results suggest unifying aspects for thermodynamic stabilization across MOF systems.
AB - This study experimentally explores the energetics for the formation of boron-imidazolate frameworks (BIFs), which are synthesized by mechanochemistry. The topologically similar frameworks employ the same tetratopic linker based on tetrakis(imidazolyl)boric acid but differ in the monovalent cation metal nodes. This permits assessment of the stabilizing effect of metal nodes in frameworks with sodalite (SOD) and diamondoid (dia) topologies. The enthalpy of formation from endmembers (metal oxide and linker), which define thermodynamic stability of the structures, has been determined by use of acid solution calorimetry. The results show that heavier metal atoms in the node promote greater energetic stabilization of denser structures. Overall, in BIFs the relation between cation descriptors (ionic radius and electronegativity) and thermodynamic stability depends on framework topology. Thermodynamic stability increases with the metallic character of the cation employed as the metal node, independent of the framework topology. The results suggest unifying aspects for thermodynamic stabilization across MOF systems.
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U2 - 10.1021/acs.jpcc.3c04164
DO - 10.1021/acs.jpcc.3c04164
M3 - Article
AN - SCOPUS:85171787923
SN - 1932-7447
VL - 127
SP - 17754
EP - 17760
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 36
ER -