Reversible Gas Uptake by a Nonporous Crystalline Solid Involving Multiple Changes in Covalent Bonding

Hydrogen chloride gas (HCl) is absorbed (and reversibly released) by a nonporous crystalline solid, [CuCl2(3-Clpy)2] (3-Clpy = 3-chloropyridine), under ambient conditions leading to conversion from the blue coordination compound to the yellow salt (3-ClpyH)2[CuCl4]. These reactions require substanti...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2007-12, Vol.129 (50), p.15606-15614
Main Authors: Mínguez Espallargas, Guillermo, Hippler, Michael, Florence, Alastair J, Fernandes, Philippe, van de Streek, Jacco, Brunelli, Michela, David, William I. F, Shankland, Kenneth, Brammer, Lee
Format: Article
Language:English
Subjects:
Crystallization
Gases - chemistry
Hydrochloric Acid - chemistry
Kinetics
Models, Molecular
Molecular Conformation
Phase Transition
Porosity
Spectrophotometry, Infrared
Water - chemistry
X-Ray Diffraction
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Summary:Hydrogen chloride gas (HCl) is absorbed (and reversibly released) by a nonporous crystalline solid, [CuCl2(3-Clpy)2] (3-Clpy = 3-chloropyridine), under ambient conditions leading to conversion from the blue coordination compound to the yellow salt (3-ClpyH)2[CuCl4]. These reactions require substantial motions within the crystalline solid including a change in the copper coordination environment from square planar to tetrahedral. This process also involves cleavage of the covalent bond of the gaseous molecules (H−Cl) and of coordination bonds of the molecular solid compound (Cu−N) and formation of N−H and Cu−Cl bonds. These reactions are not a single-crystal-to-single-crystal transformation; thus, the crystal structure determinations have been performed using X-ray powder diffraction. Importantly, we demonstrate that these reactions proceed in the absence of solvent or water vapor, ruling out the possibility of a water-assisted (microscopic recrystallization) mechanism, which is remarkable given all the structural changes needed for the process to take place. Gas-phase FTIR spectroscopy has permitted us to establish that this process is actually a solid−gas equilibrium, and time-resolved X-ray powder diffraction (both in situ and ex situ) has been used for the study of possible intermediates as well as the kinetics of the reaction.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja075265t