Synthesis, Structure, and Magnetic Properties of Two {Co16 IICo4 III} Supertetrahedral T4 Clusters Formed from the In Situ Dissociation of a Tertiary N‑Containing Ligand

• Published in: Crystal growth & design 2023-04, Vol.23 (4), p.3019-3025
• Main Authors: Xu, Mei-Yu, Zhang, Tong-Wei, Xian, Zhong-Mei, Yang, Jie, Xiang, Zeng-Ni, Long, Ji-Lan, Xu, Lei, Liang, Guang-Ming, Xiong, Peng, Wang, Xiu-Jian
• Format: Article
• Language: English
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/acs.cgd.3c00094

Two mixed-valent cobalt clusters {[(CoII)16(CoIII)4(μ6-O)4(μ3-OH)12(OCH3)12(H2O)8(BMBC)4]·(NO3)8} (1) and {[(CoII)16(CoIII)4(μ3-OH)20(OCH2CH3)4(HOCH2CH3)8(BMBC)4]·(NO3)8} (2) were synthesized and constructed by a semiflexible dicarboxylic ligand 4′,4′-[ammoniobis­(methylene)]-bis­[(1,1′-biphenyl)-2-carboxylate] (BMBC–) with Co­(NO3)2·6H2O under solvothermal systems. Interestingly, the ligand BMBC‑ is afforded from the in situ dissociation reaction of tertiary N-containing organic carboxylic acid ligands. The complexes present a beautiful supertetrahedral T4 cluster formed by an interior Co4 IIIO4 cubane and four exterior Co4 IIO4 cubanes bridged via μ6 -O2 and μ3-OH– ions and stabilized by four BMBC– organic ligands. The complexes were confirmed by single-crystal X-ray diffraction (XRD), elemental analysis, infrared spectroscopy, and thermogravimetric analysis. Furthermore, the magnetic analyses reveal that the [Co20] cluster exhibits an antiferromagnetic behavior.