Metal-Hydrogen-Pi-Bonded Organic Frameworks

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).