Citation: Luo Shuchang, Liu Xiangyu, Sun Xiaoyuan. Theoretical Study on the Magnetic Properties of Asymmetric Dicopper(Ⅱ) Complexes with Mixed Pyrazole/Oxalato Ligands[J]. Chemistry, ;2019, 82(9): 842-848. shu

Theoretical Study on the Magnetic Properties of Asymmetric Dicopper(Ⅱ) Complexes with Mixed Pyrazole/Oxalato Ligands

1.
College of Chemical Engineering, Guizhou University of Engineering Science, Bijie 551700
2.
College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021

Received Date: 2 April 2019
Accepted Date: 13 May 2019

Figures(7)

The magnetic properties of the asymmetric dicopper (Ⅱ) complexes with mixed pyrazole/oxalato ligands were studied using DFT-BS by several DFT methods and basis sets. The calculated magnetic coupling constant J_calc (-127.24 cm^-1) under the B3LYP/def2-TZVP level is in agreement with the experimental parameter -129 cm^-1, which can accurately describe the magnetic properties of the titled complexes. The analyses of magnetic orbitals and the spin density demonstrated that the spin delocalization is originated from Cu(Ⅱ) ion. Magnetic orbitals are mainly composed of 3d_x²-y² orbitals of Cu(Ⅱ) ions and π molecular orbital of the oxalato ion. As the structural parameter τ increase, the square deviations of the HS and BS state spin densities of the paramagnetic center, as well as the square of the overlap integrals between the natural magnetic orbitals are simultaneously ascended. As a result, the contribution of antiferromagnetic interaction is increased, whereas the magnitudes of the magnetic coupling constants are decreased.
- Oxalato,
- Magneto-structural correlations,
- DFT-BS,
- Dinuclear copper(Ⅱ) complexes,
- Pyrazole
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沈阳化工大学材料科学与工程学院沈阳 110142