Functionalization in flexible porous solids: Effects on the pore opening and the host-guest interactions

Thomas Devic, Patricia Horcajada, Christian Serre, Fabrice Salles, Guillaume Maurin, Béatrice Moulin, Daniela Heurtaux, Guillaume Clet, Alexandre Vimont, Jean Marc Grenéche, Benjamin Le Ouay, Florian Moreau, Emmanuel Magnier, Yaroslav Filinchuk, Jerôme Marrot, Jean Claude Lavalley, Marco Daturi, Gérard Férey

Research output: Contribution to journalArticlepeer-review

415 Citations (Scopus)


The synthesis on the gram scale and characterization of a series of flexible functionalized iron terephthalate MIL-53(Fe) type solids are reported. Chemical groups of various polarities, hydrophilicities, and acidities (-Cl, -Br, -CF3, -CH3, -NH2, -OH, -CO2H) were introduced through the aromatic linker, to systematically modify the pore surface. X-ray powder diffraction (XRPD), molecular simulations, thermogravimetric analyses, and in situ IR and 57Fe Mössbauer spectrometries indicate some similarities with the pristine MIL-53(Fe) solid, with the adoption of the narrow pore form for all solids in both the hydrated and dry forms. Combined XRPD and computational structure determinations allow concluding that the geometry of the pore opening is predominantly correlated with the intraframework interactions rather than the steric hindrance of the substituent. Only (MIL-53(Fe)-(CF3)2) exhibits a nitrogen accessible porosity (SBET ≈ 100 m2 g-1). The adsorption of some liquids leads to pore openings showing some very specific behaviors depending on the guest-MIL-53(Fe) framework interactions, which can be related to the energy difference between the narrow and large pore forms evaluated by molecular simulation.

Original languageEnglish
Pages (from-to)1127-1136
Number of pages10
JournalJournal of the American Chemical Society
Issue number3
Publication statusPublished - 2010
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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