Citation: Luo Shuchang, Sun Xiaoyuan, Zheng Pengfei, Liu Xiangyu, Huang Renyi. Magnetic Studies of Isomorphous Replacement of M^II Ions in {Gd^IIIM^II}(M=Cu, Ni, Co, Fe, Mn) Complexes: A Theoretical Perspective[J]. Chemistry, ;2020, 83(5): 464-471. shu

Magnetic Studies of Isomorphous Replacement of M^II Ions in {Gd^IIIM^II}(M=Cu, Ni, Co, Fe, Mn) Complexes: A Theoretical Perspective

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: 13 November 2019
Accepted Date: 10 December 2019

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The magnetic properties was studied for a series of {Gd^IIIM^II}(M=Cu, Ni, Co, Fe, Mn) heterobinuclear complexes by the combination of DFT calculations, using the different functional methods and basis sets, with the broken-symmetry approach. The results showed that the calculated values at the level of PBE0/TZVP (Gd is SARC-ZDRA-TZVP) are consistent with the experimental values, and this method can be used to describe its magnetic properties. There is a strong orbital interaction between the paramagnetic centers Cu^II and Gd^III and bridged coordination oxygen atoms. The molecular magnetic orbital of the complex[Cu^IIGd^III{PyCO(OEt)Py C(OH)(OEt)Py}₃]²⁺ are mainly contributed by 4f_z³, 4f_z(x²-y²) orbitals of the paramagnetic center Gd^III, 3d_x²-y² orbital of Cu^II ion and p orbitals of the bridging oxygen atoms. Due to the compensation of spin delocalization from Cu^II ion and spin polarization from Gd^III ion, the effect of spin delocalization from Cu^II ion on bridged oxygen atoms is greater than the spin polarization effect of paramagnetic center Gd^III ion. Model calculations were used to examine the influence of the electronic configuration of the M^II ions on the magnetic coupling constants. As a result, the increase of unpaired electrons of M^II ions, the ρ_HS²-ρ_BS² of the paramagnetic centers Gd^III/M^IIincreases, the contribution of antiferromagnetic coupling increases, whereas the values of the magnetic coupling constant decreases.
- Gd^IIIM^II heterobinuclear complexes,
- M^II ions,
- Magnetic coupling constant,
- DFT-BS
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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Magnetic Studies of Isomorphous Replacement of MII Ions in {GdIIIMII}(M=Cu, Ni, Co, Fe, Mn) Complexes: A Theoretical Perspective

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通讯作者: 陈斌, bchen63@163.com

Magnetic Studies of Isomorphous Replacement of M^II Ions in {Gd^IIIM^II}(M=Cu, Ni, Co, Fe, Mn) Complexes: A Theoretical Perspective