Year: 2024
Type: article
Abstract: Physicochemical properties of polymers strongly depend on the arrangement and distribution of attached monomers. Templated polymerization using porous crystalline materials appears as a promising route to gain control on the process. Thus, we demonstrate here the potential of metal–organic frameworks as scaffolds with a versatile and very regular porosity, well adapted for the regioselective oxidative polymerization of pyrene. This photoresponsive monomer was first encapsulated within the one-dimensional (1D) microporosity of the robust zirconium(IV) carboxylate metal–organic framework (MOF) (MIL-140D) to, later, undergo in situ oxidative polymerization, enabling the growth of a highly selective polypyrene (PPyr) regioisomer over other potential polymer configurations. To confirm the polymerization and the geometry control of pyrene, the resulting composites were exhaustively characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), N 2 sorption measurements, scanning transmission electron microscopy coupled with energy-dispersive X-ray (STEM-EDX) spectroscopy, and fluorescence spectroscopy. Among others, photoluminescence quenching and emission shift in the solid state demonstrated the presence of PPyr inside the MOF porosity. Furthermore, an in-depth joint analysis combining solid-state, magic-angle spinning (MAS) 1 H and 13 C NMR spectroscopy, Fourier transform infrared (FTIR) spectroscopy, matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS), and molecular simulations (grand canonical Monte Carlo (GCMC) and density functional theory (DFT)) allowed the elucidation of the spatial, host–guest interactions driving the polymerization reaction.
Institutions: Madrid Institute for Advanced Studies, IMDEA Energy Institute, Instituto de Tecnología Química, Universitat Politècnica de València, Centre National de la Recherche Scientifique, Université de Versailles Saint-Quentin-en-Yvelines, Université Paris-Saclay, Institut Lavoisier de Versailles, Universidad Complutense de Madrid, École Nationale Supérieure de Chimie de Montpellier, Université de Montpellier, Institut Charles Gerhardt Montpellier
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Awards: G1096179202, G1175115578, G139723338, G1622782223, G18271642, G1982809881, G2262748287, G2815556424, G300979063, G3255805299, G34346518, G3480869486, G410571670, G425668148, G451917667, G499442816, G504940491, G5080475149, G5539308778, G5967599077, G6033112984, G6698331501, G6826425064, G7084143925, G7459900469, G929308097
OpenAlex ID: W4401696146