Metal-Hydrogen-Pi-Bonded Organic Frameworks

17 December 2021, Version 1


We report the synthesis and characterization of a new series of permanently porous, three-dimensional metal-organic frameworks (MOFs), M-HAF-2 (M= Fe, Ga or In), constructed from tetratopic, hydroxamate-based, chelating linkers. The structure of M-HAF-2 was determined by three-dimensional electron diffraction (3DED), revealing a unique interpenetrated hcb-a net topology. This unusual topology is enabled by the presence of free hydroxamate groups, which lead to the formation of a diverse network of cooperative interactions comprising single metal-hydroxamate nodes, staggered π–π interactions between linkers and H-bonding interactions between metal-coordinated and free hydroxamate groups. Such extensive, multimodal interconnectivity is reminiscent of the complex noncovalent interaction networks of proteins and endows M-HAF-2 frameworks with good thermal and exceptionally high chemical stability and allows them to readily undergo post-synthetic metal exchange (PSE). We demonstrate that M-HAF-2 can serve as versatile porous materials for ionic separations, likely aided by one-dimensional channels lined by continuously π-stacked aromatic groups and H-bonding hydroxamate functionalities. As a new addition to the small group of hydroxamate-based MOFs, M-HAF-2 represents a structural merger between MOFs and hydrogen-bonded organic frameworks (HOFs).


Supplementary materials

Supporting Information for Metal-Hydrogen-Pi-Bonded Organic Frameworks
Supporting Information for Metal-Hydrogen-Pi-Bonded Organic Frameworks


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.