Cooperative adsorption of carbon disulfide in diamine-appended metal–organic frameworks

Over one million tons of CS(2) are produced annually, and emissions of this volatile and toxic liquid, known to generate acid rain, remain poorly controlled. As such, materials capable of reversibly capturing this commodity chemical in an energy-efficient manner are of interest. Recently, we detailed diamine-appended metal–organic frameworks capable of selectively capturing CO(2) through a cooperative insertion mechanism that promotes efficient adsorption–desorption cycling. We therefore sought to explore the ability of these materials to capture CS(2) through a similar mechanism. Employing crystallography, spectroscopy, and gas adsorption analysis, we demonstrate that CS(2) is indeed cooperatively adsorbed in N,N-dimethylethylenediamine-appended M(2)(dobpdc) (M = Mg, Mn, Zn; dobpdc(4-) = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate), via the formation of electrostatically paired ammonium dithiocarbamate chains. In the weakly thiophilic Mg congener, chemisorption is cleanly reversible with mild thermal input. This work demonstrates that the cooperative insertion mechanism can be generalized to other high-impact target molecules.