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Pressure-Induced Polymerization of Polycyclic Arene-Perfluoroarene Cocrystals: Single Crystal X-ray Diffraction Studies, Reaction Kinetics, and Design of Columnar Hydrofluorocarbons

Abstract: Pressure-induced polymerization of aromatic compounds leads to novel materials containing sp3 carbon-bonded networks. The choice of the molecular species and the control of their arrangement in the crystal structures via intermolecular interactions, such as the arene?perfluoroarene interaction, can enable the design of target polymers. We have investigated the crystal structure compression and pressure-induced polymerization reaction kinetics of two polycyclic 1:1 arene?perfluoroarene cocrystals, naphthalene/octafluoronaphthalene (NOFN) and anthracene/octafluoronaphthalene (AOFN), up to 25 and 30 GPa, respectively, using single-crystal synchrotron X-ray diffraction, infrared spectroscopy, and theoretical computations based on density-functional theory. Our study shows the remarkable pressure stability of the parallel arene?perfluoroarene ?-stacking arrangement and a reduction of the interplanar ?-stacking separations by ca. 19?22% before the critical reaction distance is reached. A further strong, discontinuous, and irreversible reduction along the stacking direction at 20 GPa in NOFN (18.8%) and 25 GPa in AOFN (8.7%) indicates the pressure-induced breakdown of ?-stacking by formation of ?-bonded polymers. The association of the structural distortion with the occurrence of a chemical reaction is confirmed by a high-pressure kinetic study using infrared spectroscopy, indicating one-dimensional polymer growth. Structural predictions for the fully polymerized high-pressure phases consisting of highly ordered rods of hydrofluorocarbons are presented based on theoretical computations, which are in excellent agreement with the experimentally determined unit-cell parameters. We show that the polymerization takes place along the arene?perfluoroarene ?-stacking direction and that the lateral extension of the columns depends on the extension of the arene and perfluoroarene molecules.

 Fuente: J. Am. Chem. Soc. 2020, 142, 44, 18907-18923

Editorial: American Chemical Society

 Fecha de publicación: 23/10/2020

Nº de páginas: 17

Tipo de publicación: Artículo de Revista

ISSN: 0002-7863,1520-5126

Proyecto español: MAT2016-75586-C4-1-P; PGC2018-097520-A-100

Url de la publicación: https://doi.org/10.1021/jacs.0c09021

Autores/as

FRIEDRICH, ALEXANDRA

COLLINGS, INES E.

DZIUBEK, KAMIL F.

FANETTI, SAMUELE

RADACKI, KRZYSZTOF

PELLICER-PORRES, JULIO

HANFLAND, MICHAEL

SIEH, DANIEL

BINI, ROBERTO

CLARK, STEWART J.

MARDER, TODD B.