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On the Mechanism Behind the Instability of Isoreticular Metal–Organic Frameworks (IRMOFs) in Humid Environments
Author(s) -
Bellarosa Luca,
Castillo Juan Manuel,
Vlugt Thijs,
Calero Sofía,
López Núria
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201201212
Subject(s) - metal organic framework , terephthalic acid , chemical physics , molecular dynamics , lattice (music) , density functional theory , molecule , linker , materials science , monte carlo method , chemistry , nanotechnology , computational chemistry , physics , organic chemistry , adsorption , computer science , statistics , mathematics , acoustics , polyester , operating system
Increasing the resistance to humid environments is mandatory for the implementation of isoreticular metal–organic frameworks (IRMOFs) in industry. To date, the causes behind the sensitivity of [Zn 4 (μ 4 ‐O)(μ‐bdc) 3 ] 8 (IRMOF‐1; bdc=1,4‐benzenedicarboxylate) to water remain still open. A multiscale scheme that combines Monte Carlo simulations, density functional theory and first‐principles Born–Oppenheimer molecular dynamics on IRMOF‐1 was employed to unravel the underlying atomistic mechanism responsible for lattice disruption. At very low water contents, H 2 O molecules are isolated in the lattice but provoke a dynamic opening of the terephthalic acid, and the lattice collapse occurs at about 6 % water weight at room temperature. The ability of Zn to form fivefold coordination spheres and the increasing basicity of water when forming clusters are responsible for the displacement of the organic linker. The present results pave the way for synthetic challenges with new target linkers that might provide more robust IRMOF structures.