Three-Dimensional Metal-Organic Network Glasses from Bridging MF₆^2- Anions and Their Dynamic Insights by Solid-State...

Glassy-state coordination polymers (CPs) are a new class of network-forming glasses. In this work, we constructed glass-forming CPs composed of both anionic and neutral ligands as network formers. With the use of hexafluoro anions (MF₆^2-) and 1,3-bis(4-pyridyl)propane (bpp), two isostructural CP crystals, [Zn(SiF₆)(bpp)₂] (ZnSi) and [Zn(TiF₆)(bpp)₂] (ZnTi), were synthesized. Solid-state ¹⁹F NMR revealed rotational motion of MF₆^2- with dissociation and re-formation of the Zn-F coordination bonds in both CP crystals, which reflects the thermodynamic parameters related to the glass formability. The mobility of SiF₆^2- is larger than that of TiF₆^2-, suggesting a higher glass formability of ZnSi. When mechanical ball milling was conducted, ZnSi completely changed into a glassy state, whereas ZnTi showed incomplete glass formation. Examination of the amorphous structures elucidated retention and partial destruction of the Zn-F coordination bonds in ball-milled ZnSi and ZnTi, respectively. These results provide the relationship between the ligand dynamics and glass formability of CPs.