Examining the Effects of Different Ring Configurations and Equatorial Fluorine Atom Positions on CO2 Sorption in [Cu(bpy)2SiF6]

Simulations of CO2 sorption were performed in a metal–organic material (MOM) that is part of a “SIFSIX” family of compounds that has remarkable carbon dioxide capture and separation properties. The MOM considered here has the formula [Cu(bpy)2SiF6] (bpy = 4,4′-bipyridine). This hydrophobic MOM is both water-stable and CO2-specific with significant sorption capacity under ambient conditions. The crystal structure reveals bpy rings and equatorial fluorine atoms in multiple possible orientations; the static disorder has been modeled based on single-crystal X-ray diffraction data revealing several possible relatives of atoms in the crystal structure. With regards to the bpy rings, the structure can be interpreted as two pyridyl rings with coplanar configurations within a unit cell (configuration 1), a twisted bpy ring conformation in which orthogonal pyridyl rings have C4 symmetry about the Cu2+ ion (configuration 2), and a twisted bpy ring conformation in which the two orthogonal pyridyl rings are facing one...