Temperature dependent CO(2) behavior in microporous 1-D channels of a metal-organic framework with multiple interaction sites

The MOF with the encapsulated CO(2) molecule shows that the CO(2) molecule is ligated to the unsaturated Cu(II) sites in the cage using its Lewis basic oxygen atom via an angular η(1)-(O(A)) coordination mode and also interacts with Lewis basic nitrogen atoms of the tetrazole ligands using its Lewis acidic carbon atom. Temperature dependent structure analyses indicate the simultaneous weakening of both interactions as temperature increases. Infrared spectroscopy of the MOF confirmed that the CO(2) interaction with the framework is temperature dependent. The strength of the interaction is correlated to the separation of the two bending peaks of the bound CO(2) rather than the frequency shift of the asymmetric stretching peak from that of free CO(2). The encapsulated CO(2) in the cage is weakly interacting with the framework at around ambient temperatures and can have proper orientation for wiggling out of the cage through the narrow portals so that the reversible uptake can take place. On the other hand, the CO(2) in the cage is restrained at a specific orientation at 195 K since it interacts with the framework strong enough using the multiple interaction sites so that adsorption process is slightly restricted and desorption process is almost clogged.