Hydrogen-Bonded Framework of a Cobalt(II) Complex Showing Superior Stability and Field-Induced Slow Magnetic Relaxation

• Published in: Inorganic chemistry Vol. 61; no. 8; pp. 3754 - 3762
• Main Authors: Shao, Dong, Peng, Peng, You, Maolin, Shen, Lin-Feng, She, Shi-Yuan, Zhang, Yi-Quan, Tian, Zhengfang
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 28.02.2022
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.2c00034

A unique hydrogen-bonded organic–inorganic framework (HOIF) constructed from a mononuclear cobalt­(II) complex, [Co­(MCA)2·(H2O)2] (HMCA = 4-imidazole­carboxylic acid), via multiple hydrogen-bonding interactions was synthesized and structurally characterized. The Co­(II) center in the HOIF features a highly distorted octahedral coordination environment. Remarkably, the CoII HOIF showed permanent porosity with superior stability as established by combined thermogravimetric analysis (TGA), variable-temperature infrared spectra (IR), variable-temperature powder X-ray diffraction data (PXRD), and a CO2 isotherm. Structural studies reveal that short multiple hydrogen bonds should be responsible for the superior thermal and chemical stability of a HIOF. Magnetic investigations reveal the large easy-plane magnetic anisotropy of the Co2+ ions with the fitted D values being 22.1 (magnetic susceptibility and magnetization data) and 29.1 cm–1 (reduced magnetization data). In addition, the HOIF exhibits field-induced slow magnetic relaxation at low temperature with an effective energy barrier of U eff = 45.2 cm–1, indicative of a hydrogen-bonded framework single-ion magnet of the compound. The origin of the significant magnetic anisotropy of the complex was also understood from computational studies. In addition, BS-DFT calculations indicate that the superexchange interactions between the neighboring CoII ions are non-negligible anti­ferro­magnetism with J Co–Co = −0.5 cm–1. The foregoing results provide not only a carboxylate–imidazole ligand approach toward a stable HOIF but also a promising way to build a robust single-ion magnet via hydrogen-bond interactions.