3 years ago

Transient Porosity in Densely Packed Crystalline Carbazole–(p-Diethynylphenylene)–Carbazole Rotors: CO2 and Acetone Sorption Properties

Transient Porosity in Densely Packed Crystalline Carbazole–(p-Diethynylphenylene)–Carbazole Rotors: CO2 and Acetone Sorption Properties
Elı́ Sánchez-González, J. Raziel Álvarez, Mario Rodríguez, Arian E. Roa, Andrés Aguilar-Granda, Joelis Rodríguez-Hernández, Ilich A. Ibarra, Braulio Rodríguez-Molina, Salvador Pérez-Estrada, Simón Hernández-Ortega
We report for the first time the high sorption properties of a molecular rotor with no permanent voids or channels in its crystal structure. Such crystalline phase originates from THF, DCM, or the irreversible desolvation of entrapped benzene molecules. From these, the benzene in its solvate form acts as rotation stopper, as supported by dynamic characterization using solid-state 2H NMR experiments. In the solvent-free form, the diffusion of small quantities of iodine vapors caused a significant change in the intramolecular rotation, increasing the known activation energy to rotation from 8.5 to 10.6 kcal mol–1. Notably, those results paved the way for the discovery of the high CO2 uptake (201.6 cm3 g–1 at 196 K, under 1 atm) and acetone (5 wt %), a sorption property that was attributed to both, the restriction of the molecular rotation at low temperatures and the flexibility of the molecular axle made of conjugated p-(ethynylphenylene), surrounded by carbazole.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b02015

DOI: 10.1021/jacs.7b02015

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