Direct Visualization of Pyrrole Reactivity upon Confinement within a Cyclodextrin Metal–Organic Framework. Issue 27 (28th May 2019)

• Record Type: Journal Article
• Authors: Nuñez‐Lopez, Alejandro; Galbiati, Marta; Padial, Natalia M.; Ganivet, Carolina R.; Tatay, Sergio; Pardo, Emilio; Armentano, Donatella; Martí‐Gastaldo, Carlos
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 27(2019)
• Page Start: 9179
• Page End: 9183
• Publication Date: 2019-05-28
• Subjects: metal–organic frameworks -- noncovalent interactions -- oxidation -- structure elucidation -- supramolecular chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201904890
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Metal–organic frameworks can be used as porous templates to exert control over polymerization reactions. Shown here are the possibilities offered by these crystalline, porous nanoreactors to capture highly‐reactive intermediates for a better understanding of the mechanism of polymerization reactions. By using a cyclodextrin framework the polymerization of pyrrole is restricted, capturing the formation of terpyrrole cationic intermediates. Single‐crystal X‐ray diffraction is used to provide definite information on the supramolecular interactions that induce the formation and stabilization of a conductive array of cationic complexes. Abstract : Reactivity in confinement : Compared to its uncontrolled polymerization in solution, shown here is that chemical oxidation of pyrrole can be regulated when confined to the channels of a cyclodextrin (CD) framework. Supramolecular interactions with the CD rings restrict the mobility and reactivity of pyrrole and enable the stabilization of terpyrrole cationic intermediates.