Syntheses, structures and magnetic properties of mononuclear, dinuclear and tetranuclear dysprosium() complexes based on azotetrazole-3-hydroxy-2-naphthoic acid

• Published in: CrystEngComm 2022-12, Vol.24 (48), p.8488-8495
• Main Authors: Zhong, Yun-Jing, Zhu, Yu-Ying, Mo, Jin-Lin, Ye, Sheng-Lan, Luo, Wen-Dan, Huang, Xin, Chen, Wen-Bin, Dong, Wen
• Format: Article
• Language: English
• Subjects: Crystallography; Dimethylformamide; Dysprosium; Hydrazones; Hydroxyl groups; Hydroxynaphthoic acid; Ligands; Magnetic induction; Magnetic properties; Magnetic relaxation; Molecular structure; Tautomers
• ISSN: 1466-8033; 1466-8033
• DOI: 10.1039/d2ce01303g

A new compound of azotetrazole-3-hydroxy-2-naphthoic acid (H 3 ATNA) has been successfully synthesized and characterized. By controlling the ratio of metal ions to the ligand and the pH value of solution, mononuclear, dinuclear and tetranuclear dysprosium( iii ) complexes [Et 3 NH] 3 [Dy(HATNA) 3 ]·5H 2 O ( 1 ), [Dy 2 (HATNA) 3 (DMF)(H 2 O)]2DMF·CH 3 OH·2H 2 O ( 2 ) and [Et 3 NH] 6 [Dy 4 (ATNA) 6 (H 2 O) 2 ]·DMF·2CH 3 CN·8H 2 O ( 3 ) were synthesized and characterized by X-ray diffraction crystallography (DMF = N , N -dimethylformamide). Crystallographic data demonstrate that the neutral H 3 ATNA exists as a hydrazone tautomer. Complex 1 is a mononuclear structure, in which the Dy( iii ) ion is a nine-coordinated ion surrounded by three tridentate HATNA − ligands. Complex 2 shows a dinuclear structure, which is bridged by three μ 1,1 -hydroxyl groups of three HATNA − ligands. In complex 2 , the Dy( iii )1 ion is a nine-coordinated ion surrounded by three tridentate HATNA − ligands, while Dy( iii )2 is an eight coordinated atom with three tridentate HATNA − ligands, one DMF and one water molecule. Complex 3 displays a tetranuclear structure, which can be approximately considered as two μ 1,3 -carboxyl groups of ATNA 3− ligands linking complex 2 . The magnetic properties of 1-3 were investigated. Complexes 2 and 3 display slow magnetic relaxation in a zero dc field. Mononuclear, dinuclear and tetranuclear dysprosium( iii ) complexes [Et 3 NH] 3 [Dy(HATNA) 3 ]5H 2 O ( 1 ), [Dy 2 (HATNA) 3 (DMF)(H 2 O)]2DMFCH 3 OH2H 2 O ( 2 ) and [Et 3 NH] 6 [Dy 4 (ATNA) 6 (H 2 O) 2 ]DMF2CH 3 CN8H 2 O ( 3 ) were synthesized and characterized.