Syntheses, structural modulation, and slow magnetic relaxation of three dysprosium() complexes with mononuclear, dinuclear, and one-dimensional structures

• Published in: Dalton transactions : an international journal of inorganic chemistry 2021-10, Vol.5 (39), p.13728-13736
• Main Authors: Ye, Hua-Jian, Zhang, Tian, Huang, Shu-Yuan, Liu, Xiao-Ling, Chen, Wen-Bin, Zhang, Yi-Quan, Tang, Jinkui, Dong, Wen
• Format: Article
• Language: English
• Subjects: Coordination compounds; Crystal structure; Dihydroxybenzoic acid; Dysprosium; Hydroxyl groups; Ligands; Magnetic induction; Magnetic measurement; Magnetic properties; Magnetic relaxation; Single crystals; Synthesis
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d1dt02532e

Three mononuclear, dinuclear and one-dimensional dysprosium( iii ) complexes based on 3-azotriazolyl-2,6-dihydroxybenzoic acid (H 4 ATB) of [Dy(H 3 ATB) 3 ]·3H 2 O ( 1 ), [Dy 2 (H 2 ATB) 2 (H 2 DHB) 2 (H 2 O) 4 ]·2CH 3 CN·5H 2 O ( 2 ), and [Dy 2 (H 2 ATB) 2 (DCB)(DMF) 2 (H 2 O) 2 ]·4DMF ( 3 ) were synthesized and structurally characterized by X-ray single crystal diffraction (H 3 DHB = 2,6-dihydroxybenzoic acid, H 2 DCB = 1,4-dicarboxybenzene). Complex 1 was used as a precursor to synthesize complexes 2 and 3 , and 2 was further used to synthesize 3 . Complex 1 is a mononuclear complex, in which the Dy( iii ) ion is in a nine-coordinated structure surrounded by three tridentate chelate H 3 ATB − ligands. Complex 2 displays a dinuclear structure bridged by two μ 2 carboxyl groups of two H 2 DHB − ligands and two μ 1,1 -O atoms from the phenolic hydroxyl groups of two H 2 ATB 2− ligands. Complex 3 shows a one-dimensional structure formed by two bridging DCB 2− ligands. The magnetic measurements were performed on three complexes 1-3 , and they showed different magnetic behavior. Complex 1 shows a field-induced slow magnetic relaxation. Complexes 2 and 3 display distinct slow magnetic relaxation under zero dc field with energy barriers ( U eff ) of 26(2) cm −1 and 11(1) cm −1 , respectively. The magnetic behavior of three complexes 1-3 was investigated by ab initio calculations. Three mononuclear, dinuclear and one-dimensional dysprosium( iii ) complexes based on 3-azotriazolyl-2,6-dihydroxybenzoic acid displaying slow magnetic relaxation were synthesized and characterized.