Citation: BIAN Jiang-Yu, YUE Shu-Mei, ZHANG Min, ZHANG Jing-Ping. Effects of Azido Bridge on Magnetic Properties of Dinuclear Nickel Complexes: Density Functional Theory Studies[J]. Acta Physico-Chimica Sinica, ;2015, 31(6): 1086-1092. doi: 10.3866/PKU.WHXB201504162 shu

Effects of Azido Bridge on Magnetic Properties of Dinuclear Nickel Complexes: Density Functional Theory Studies

1.
1 Department of Chemistry, Changchun Normal University, Changchun 130032, P. R. China;
2 Department of Chemistry, Northeast Normal University, Changchun 130024, P. R. China

Received Date: 15 January 2015
Available Online: 16 April 2015
Fund Project: 长春师范学院自然科学基金(长师院自科合字[2009]第009 号, 长师院自科合字政策[2010]第030 号) (长师院自科合字[2009]第009 号, 长师院自科合字政策[2010]第030 号)规划项目(吉教科合字[2011]第192 号)资助 (吉教科合字[2011]第192 号)

The magnetic properties of the antiferromagnetic complex μ-1,3-N₃-Ni(II)[LNi₂(N₃)](ClO₄)₂ (L= pyrazolate) were investigated using density functional theory (DFT) calculations combined with the broken symmetry approach. The calculation results obtained using the hybrid density functional theory (HDFT) agree well with the experimental data, and accurately describe the magnetic properties of complex. The large energy splitting, 0.93-0.99 eV, between singly occupied molecular orbitals indicates that there is strong non-degeneracy between them, and the two coupling paths (azido and pyrazolate) in the complex show that there is overlap between the p orbitals of the N atoms. All these factors contribute to the antiferromagnetism of the complex. The magnetic properties of the complex are also closely related to the dihedral angle τ of Ni-N-N-N-Ni. The antiferromagnetism of the complex increases as τ decreases from -55.38° to -1.5°; the maximum absolute value of magnetic coupling constant (J_ab) occurs at -11.95° (J_ab=-151.02 cm^-1). During this process, the coplanarity of the seven-membered ring, which consists of two Ni(II), one azido, and two bridging nitrogen atoms (N(4) and N(5)), is enhanced, i.e., coplanarity increases the antiferromagnetism of the complex.
- Density functional theory-broken symmetry (DFT-BS) method,
- Azido complex,
- Magnetic coupling constant,
- Anti-ferromagnetic interaction
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