TY - JOUR
T1 - Crystallographic and Compositional Dependence of Thermodynamic Stability of [Co(II), Cu(II), and Zn(II)] in 2-Methylimidazole-Containing Zeolitic Imidazolate Frameworks
AU - Leonel, Gerson J.
AU - Lennox, Cameron B.
AU - Marrett, Joseph M.
AU - Friščić, Tomislav
AU - Navrotsky, Alexandra
N1 - Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
PY - 2023/9/12
Y1 - 2023/9/12
N2 - We report the first systematic study experimentally investigating the effect of changes to the divalent metal node on the thermodynamic stability of three-dimensional (3D) and two-dimensional (2D) zeolitic imidazolate frameworks (ZIFs) based on 2-methylimidazolate linkers. In particular, the comparison of enthalpies of formation for materials based on cobalt, copper, and zinc suggests that the use of nodes with larger ionic radius metals leads to the stabilization of the porous sodalite topology with respect to the corresponding higher-density diamondoid (dia)-topology polymorphs. The stabilizing effect of metals is dependent on the framework topology and dimensionality. With previous works pointing to solvent-mediated transformation of 2D ZIF-L structures to their 3D analogues in the sodalite topology, thermodynamic measurements show that contrary to popular belief, the 2D frameworks are energetically stable, thus shedding light on the energetic landscape of these materials. Additionally, the calorimetric data confirm that a change in the dimensionality (3D → 2D) and the presence of structural water within the framework can stabilize structures by as much as 40 kJ·mol-1, making the formation of zinc-based ZIF-L material under such conditions thermodynamically preferred to the formation of both ZIF-8 and its dense, dia-topology polymorph.
AB - We report the first systematic study experimentally investigating the effect of changes to the divalent metal node on the thermodynamic stability of three-dimensional (3D) and two-dimensional (2D) zeolitic imidazolate frameworks (ZIFs) based on 2-methylimidazolate linkers. In particular, the comparison of enthalpies of formation for materials based on cobalt, copper, and zinc suggests that the use of nodes with larger ionic radius metals leads to the stabilization of the porous sodalite topology with respect to the corresponding higher-density diamondoid (dia)-topology polymorphs. The stabilizing effect of metals is dependent on the framework topology and dimensionality. With previous works pointing to solvent-mediated transformation of 2D ZIF-L structures to their 3D analogues in the sodalite topology, thermodynamic measurements show that contrary to popular belief, the 2D frameworks are energetically stable, thus shedding light on the energetic landscape of these materials. Additionally, the calorimetric data confirm that a change in the dimensionality (3D → 2D) and the presence of structural water within the framework can stabilize structures by as much as 40 kJ·mol-1, making the formation of zinc-based ZIF-L material under such conditions thermodynamically preferred to the formation of both ZIF-8 and its dense, dia-topology polymorph.
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U2 - 10.1021/acs.chemmater.3c01464
DO - 10.1021/acs.chemmater.3c01464
M3 - Article
AN - SCOPUS:85169931764
SN - 0897-4756
VL - 35
SP - 7189
EP - 7195
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 17
ER -