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 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.
Espallargas
Guillermo Mínguez
GM
Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom.
Hippler
Michael
M
Florence
Alastair J
AJ
Fernandes
Philippe
P
van de Streek
Jacco
J
Brunelli
Michela
M
David
William I F
WI
Shankland
Kenneth
K
Brammer
Lee
L
D003460:Crystallization; D005740:Gases / Q000737:chemistry*; D006851:Hydrochloric Acid / Q000737:chemistry; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D044367:Phase Transition; D016062:Porosity; D013055:Spectrophotometry, Infrared; D014867:Water / Q000737:chemistry; D014961:X-Ray Diffraction
D005740:Gases; D014867:Water; D006851:Hydrochloric Acid