Self-assembly of organoarsonic acid functionalized polyoxovanadate cage from cap-like building block

• Published in: Inorganica Chimica Acta 2024-11, Vol.572, p.122271, Article 122271
• Main Authors: Chu, Luyao, Dong, Jing, Zhen, Ni, Zhang, Di, Guo, Xin, Hu, Jiesheng, Chi, Yingnan
• Format: Article
• Language: English
• Subjects: Cage-like structure; Cap-like building block; Magnetism; Organoarsonic acid functionalization; Polyoxovanadates
• ISSN: 0020-1693
• DOI: 10.1016/j.ica.2024.122271

[Display omitted] •Self-assembly of organoarsonic acid functionalized polyoxovanadate cages.•Isolation of a cap-like organoarsonic acid functionalized {AsV4As4} intermediate.•Transformation of {AsV4As4} building block to polyoxovanadate cage. The cap-like {AsV4As4} is a commonly appearing building block in the assembly of organoarsonic acid functionalized polyoxovanadate cages, but to the best of our knowledge, the isolated {AsV4As4} has not been obtained until now. Herein, we have successfully synthesized the cap-like [(CH3)2NH2]2[DMF⊂V4O5(C6H5AsO3)3(C6H5AsO3H)2] ({AsV4As4}) for the first time. A cage-like [(CH3)2NH2]H3[CH3OH⊂V12O14(OH)4(C6H5AsO3)10]·7H2O ({(V2)2(AsV4As4)2}) composed of two {AsV4As4} caps and two {V2} units was obtained by reacting {AsV4As4} with an additional V source. In addition, a similar cage-like H6[CH3OH, H2O⊂V12O14(OH)4(O3AsC6H4-2-NH2)10]SO4·DMF ({(V2)2(AsV4As4-NH2)2}) was obtained by using 2-aminophenylarsonic acid instead of phenylarsonic acid. The three organoarsonic acid functionalized polyoxovanadates have been characterized by single crystal X-ray diffraction, elemental analysis, powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. In addition, magnetic property studies indicate that there is antiferromagnetic coupling interaction between V centers of the three compounds.