Lawrence Berkeley National Laboratory

Variable-temperature ¹⁵N solid-state NMR spectroscopy is used to uncover the dynamics of three diamines appended to the metal-organic framework Mg₂(dobpdc) (dobpdc^4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), an important family of CO₂ capture materials. The results imply both bound and free amine nitrogen environments exist when diamines are coordinated to the framework open Mg²⁺ sites. There are rapid exchanges between two nitrogen environments for all three diamines, the rates and energetics of which are quantified by ¹⁵N solid-state NMR data and corroborated by density functional theory calculations and molecular dynamics simulations. The activation energy for the exchange provides a measure of the metal-amine bond strength. The unexpected negative correlation between the metal-amine bond strength and CO₂ adsorption step pressure reveals that metal-amine bond strength is not the only important factor in determining the CO₂ adsorption properties of diamine-appended Mg₂(dobpdc) metal-organic frameworks.