- Main
Amine Dynamics in Diamine-Appended Mg2(dobpdc) Metal-Organic Frameworks.
- Author(s): Xu, Jun
- Liu, Yifei Michelle
- Lipton, Andrew S
- Ye, Jinxing
- Hoatson, Gina L
- Milner, Phillip J
- McDonald, Thomas M
- Siegelman, Rebecca L
- Forse, Alexander C
- Smit, Berend
- Long, Jeffrey R
- Reimer, Jeffrey A
- et al.
Published Web Location
https://doi.org/10.1021/acs.jpclett.9b02883Abstract
Variable-temperature 15N solid-state NMR spectroscopy is used to uncover the dynamics of three diamines appended to the metal-organic framework Mg2(dobpdc) (dobpdc4- = 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.