Citation: Hui-Ting XU, Yang LIU, Liu-Lei QIN, Huan-Huan QI, Zun-Qi LIU. Synthesis, Phase Transition and Dielectric Properties of 1, 4-Diazabicyclo[2.2.2]octane-Cyanide Cobalt(Ⅲ) Three-Dimensional Framework Hydrogen-Bonding Crystal[J]. Chinese Journal of Inorganic Chemistry, ;2021, 37(11): 1950-1960. doi: 10.11862/CJIC.2021.218 shu

Synthesis, Phase Transition and Dielectric Properties of 1, 4-Diazabicyclo[2.2.2]octane-Cyanide Cobalt(Ⅲ) Three-Dimensional Framework Hydrogen-Bonding Crystal

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  • A Dabco-cobalt cyanide hydrogen-bonding framework crystal material, (H3O)(H2Dabco)[Co(CN)6]·H2O (1), has been synthesized by solvent evaporation in the mixed solution of methanol and water with 1, 4-diazabicyclo[2.2.2]octane (Dabco) and cobalt cyanide. The structure, thermal energy and electrical properties of the crystal were characterized by single crystal X-ray diffraction, infrared spectroscopy, elemental analysis, X-ray powder diffraction, thermogravimetric analysis, differential scanning calorimetry and variable temperature-frequency dielectric constant test. The space group of the crystal is P21/c, which belongs to the monoclinic system at low and room temperature. The structure shows that the cobalt cyano anion, water molecules and protonated water molecules are mutually connected through hydrogen bonds in the crystal to form a three-dimensional network framework, and the protonated (H2Dabco)2+ cations are embedded in it forming a molecular motor-type cystic structure. With the increase of temperature, the (H2Dabco)2+ cations are twisted, which causes a phase transition in the crystal structure near 254 K. Dielectric anomalies occurs along the three axes of the crystal, showing obvious dielectric anisotropy at the same temperature.
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