Fine-Tuning of the Coordination Environment To Regulate the Magnetic Behavior in Solvent/Anion-Dependent DyIIICompounds: Synthesis, Structure, Magnetism, and Ab Initio Calculations.
It is crucial to understand and elucidate the self-assembly mechanism in solution systems for the construction of DyIII-based single-molecule magnets (SMMs). Herein, through fine-tuning of the anion and solvent, we prepared three nine-coordinate mononuclear dysprosium compounds, [Dy(2,3'-pcad)(NO3)2(CH3OH)2] (1), [Dy(2,3'-Hpcad)2(H2O)3]·3Cl·5H2O (2), and [Dy(2,3'-pcad)(NO3)(H2O)4]·NO3·H2O (3) [2,3'-Hpcad = N3-(2-pyridoyl)-3-pyridinecarboxamidrazone]. The reactions of formation for 1-3 are in situ thermodynamically monitored by isothermal titration calorimetry. Magnetic data analysis reveals that 2 shows SMM behavior under a zero direct-current (dc) field, whereas 1 and 3 exhibit distinct slow magnetic relaxation processes upon a 1200 Oe dc field. To deeply understand the different magnetic behaviors, the magnetic anisotropy of 1-3 has been systematically studied by ab initio calculations, which is consistent with the experimental observations. Moreover, the semiconductor behaviors of 1-3 have been investigated by experimental measurements of UV-vis spectroscopy.
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University , Xi'an, Shaanxi 710127, China.
Lin
L
Sun
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University , Xi'an, Shaanxi 710127, China.|College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences , Baoji 721013, China.
Sheng
S
Zhang
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University , Xi'an, Shaanxi 710127, China.|Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, College of Chemical Engineering and Modern Materials, Shangluo University , Shangluo 726000, P. R. China.
Chengfang
C
Qiao
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University , Xi'an, Shaanxi 710127, China.
Sanping
S
Chen
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University , Xi'an, Shaanxi 710127, China.
Bing
B
Yin
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University , Xi'an, Shaanxi 710127, China.
Wenyuan
W
Wang
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University , Xi'an, Shaanxi 710127, China.
Qing
Q
Wei
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University , Xi'an, Shaanxi 710127, China.
Gang
G
Xie
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University , Xi'an, Shaanxi 710127, China.
Shengli
S
Gao