Year: 2026
Type: article
Abstract: ABSTRACT Hybrid ultramicroporous materials (HUMs) are comprised of combinations of inorganic and organic linker ligands as exemplified by the prototypal pcu topology variant [Zn(pyrazine) 2 (SiF 6 )] n , SIFSIX‐3‐Zn, and its recently reported first‐generation derivatives [M(3,3’‐bipyridine) 2 (SiF 6 )] n (M = Cu, Zn). Herein, we report the synthesis, structure, and sorption properties of a second‐generation family of HUMs of general formula [M(3,3’‐bipyridine) 2 (NbOF 5 )] n , NbOFFIVE‐3,3 ' ‐bpy‐M , M = Co , Ni , Cu , Zn . The four HUMs are structurally characterized by single crystal x‐ray diffraction, revealing the expected pcu topology of the isostructural as‐synthesized phases. All variants initially crystallized in large‐pore ( lp ) phases with water molecules occupying 1D channels. Upon dehydration, Cu and Zn transformed from water‐loaded lp phases into narrow‐pore ( np ) guest‐free phases, whereas Co and Ni retained their lp structures after desorption. Water vapor sorption isotherms (300 K) revealed stepped isotherms corresponding to structural transformations ( np → lp ) for Cu and Zn , and rare examples of induced‐fit ( lp → np → lp ) from guest‐free lp to np to water‐loaded lp phases for Co and Ni . The NbOFFIVE‐3,3 ' ‐bpy‐M family exhibits uncommon examples of metal‐dependent dynamic behavior in HUMs.
DOI: 10.1002/anie.9035308
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,510
OpenAlex ID: W7225348387