title: Functionalization in flexible porous solids: effects on the pore opening and the host-guest interactions.
abstract: 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, -CF(3), -CH(3), -NH(2), -OH, -CO(2)H) 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 (57)Fe 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)-(CF(3))(2)) exhibits a nitrogen accessible porosity (S(BET) approximately 100 m(2) 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.
authors.affiliation: Institut Lavoisier, UMR CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, 45 avenue des Etats-Unis, 78035 Versailles cedex, France. devic@chimie.uvsq.fr
authors.forename: Thomas
authors.initials: T
authors.lastname: Devic
authors.forename: Patricia
authors.initials: P
authors.lastname: Horcajada
authors.forename: Christian
authors.initials: C
authors.lastname: Serre
authors.forename: Fabrice
authors.initials: F
authors.lastname: Salles
authors.forename: Guillaume
authors.initials: G
authors.lastname: Maurin
authors.forename: Béatrice
authors.initials: B
authors.lastname: Moulin
authors.forename: Daniela
authors.initials: D
authors.lastname: Heurtaux
authors.forename: Guillaume
authors.initials: G
authors.lastname: Clet
authors.forename: Alexandre
authors.initials: A
authors.lastname: Vimont
authors.forename: Jean-Marc
authors.initials: JM
authors.lastname: Grenèche
authors.forename: Benjamin
authors.initials: B
authors.lastname: Le Ouay
authors.forename: Florian
authors.initials: F
authors.lastname: Moreau
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Magnier
authors.forename: Yaroslav
authors.initials: Y
authors.lastname: Filinchuk
authors.forename: Jerôme
authors.initials: J
authors.lastname: Marrot
authors.forename: Jean-Claude
authors.initials: JC
authors.lastname: Lavalley
authors.forename: Marco
authors.initials: M
authors.lastname: Daturi
authors.forename: Gérard
authors.initials: G
authors.lastname: Férey