title: How linker's modification controls swelling properties of highly flexible iron(III) dicarboxylates MIL-88.
abstract: A series of organically modified iron(III) terephthalate MIL-88B and iron(III) 4,4'-biphenyl dicarboxylate MIL-88D flexible solids have been synthesized and characterized through a combination of X-ray diffraction, IR spectroscopy, and thermal analysis (MIL stands for Material from Institut Lavoisier). The swelling amplitude of the highly flexible MOFs tuned by introducing functional groups onto the phenyl rings shows a clear dependence on the steric hindrance and on the number of groups per aromatic ring. For instance, while the introduction of four methyl groups per spacer in dried MIL-88B results in a large permanent porosity, introducing two or four methyl groups in MIL-88D allows an easier pore opening in the presence of liquids without drastically decreasing the swelling magnitude. The influence of the degree of saturation of the metal center and the nature of the solvent on the swelling is also discussed. Finally, a computationally assisted structure determination has led to a proposal of plausible structures for the closed (dried) and open forms of modified MIL-88B and MIL-88D and to evaluation of their framework energies subject to the nature of the functional groups.
authors.affiliation: Institut Lavoisier, (UMR CNRS 8180), Université de Versailles, 45, Avenue des Etats-Unis, 78035, Versailles Cedex, France. horcajada@chimie.uvsq.fr
authors.forename: Patricia
authors.initials: P
authors.lastname: Horcajada
authors.forename: Fabrice
authors.initials: F
authors.lastname: Salles
authors.forename: Stefan
authors.initials: S
authors.lastname: Wuttke
authors.forename: Thomas
authors.initials: T
authors.lastname: Devic
authors.forename: Daniela
authors.initials: D
authors.lastname: Heurtaux
authors.forename: Guillaume
authors.initials: G
authors.lastname: Maurin
authors.forename: Alexandre
authors.initials: A
authors.lastname: Vimont
authors.forename: Marco
authors.initials: M
authors.lastname: Daturi
authors.forename: Olivier
authors.initials: O
authors.lastname: David
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Magnier
authors.forename: Norbert
authors.initials: N
authors.lastname: Stock
authors.forename: Yaroslav
authors.initials: Y
authors.lastname: Filinchuk
authors.forename: Dmitry
authors.initials: D
authors.lastname: Popov
authors.forename: Christian
authors.initials: C
authors.lastname: Riekel
authors.forename: Gérard
authors.initials: G
authors.lastname: Férey
authors.forename: Christian
authors.initials: C
authors.lastname: Serre
mesh_terms: D005290:Ferric Compounds / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010795:Phthalic Acids / Q000737:chemistry*
chemical_list: D005290:Ferric Compounds; D010795:Phthalic Acids