On the mechanism behind the instability of isoreticular metal-organic frameworks (IRMOFs) in humid environments

Luca Bellarosa, Juan Manuel Castillo, Thijs Vlugt, Sofía Calero, Núria López

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64 Citations (Scopus)


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 44-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 2O 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.

Original languageEnglish
Pages (from-to)12260-12266
Number of pages7
JournalChemistry : A European Journal
Issue number39
Publication statusPublished - 24 Sept 2012
Externally publishedYes


  • metal-organic frameworks
  • molecular dynamics
  • Monte Carlo simulations
  • multiscale modeling
  • water chemistry


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