title: Impact of the Nature of the Organic Spacer on the Crystallization Kinetics of UiO-66(Zr)-Type MOFs.
abstract: The influence of the constitutive dicarboxylate linkers (size, functional group) over the crystallization kinetics of a series of porous Zr metal-organic frameworks with the UiO-66 topology has been investigated by in situ time-resolved energy dispersive X-ray diffraction (EDXRD). Both large aromatic spacers (2,6-naphthalene-, 4,4'-biphenyl- and 3,3'-dichloro-4,4'-azobenzene-dicarboxylates) and a series of X-functionalized terephthalates (X=NH2 , NO2 , Br, CH3 ) were investigated in dimethylformamide (DMF) at different temperatures and compared with the parent UiO-66. Using different crystallization models, rate constants and further kinetic parameters (such as activation energy) have been extracted. Finally, the impact of the replacement of the toxic DMF by water on the crystallization kinetics was studied through the synthesis of the functionalized UiO-66-NO2 solid.
authors: Institut Lavoisier (UMR CNRS 8180), CNRS-Université de Versailles Saint-Quentin-en-Yvelines, 45 avenue des États-Unis, 78035 Versailles cedex (France).
authors: Florence
authors: F
authors: Ragon
authors: Hubert
authors: H
authors: Chevreau
authors: Thomas
authors: T
authors: Devic
authors: Christian
authors: C
authors: Serre
authors: Patricia
authors: P
authors: Horcajada
keywords: UiO-66; crystal growth; functionalization; isoreticularity; metal-organic frameworks