Unraveling the origin of the cooperative adsorption of carbon monoxide in an Fe(ii) metal–organic framework

Abstract

Using periodic DFT calculations, we have established the mechanism of the unusual cooperative adsorption of CO gas in an Fe-bistriazolate MOF observed previously. The binding of one CO molecule to Fe^II triggers structural alteration of the neighbouring Fe centres, reducing the steric energy penalty and aiding cooperative adsorption. This is similar to the entatic state concept proposed for metalloenzymes, and offers novel strategies for selective gas adsorption.