Effect of 3d heterometallic ions on the magnetic properties of azido-Cu(II) with isonicotinic acid coligands: A theoretical perspective.


College of Chemical Engineering, Guizhou University of Engineering Science, Bijie, 551700, PR China. Electronic address: [Email]


Based on density functional theory and the broken-symmetry approach, the magnetic properties of an azido-Cu(II) complex with isonicotinic acid coligands were studied at the B1LYP/def2-TZVP level. According to the molecular magnetic orbitals and Mulliken spin population analysis, there are strong orbital interactions between the paramagnetic CuII/NiII ions and the bridging azide ligands and isonicotinic ions. The supposedly empty 4s/4p/4d orbitals of the MII ions are found to play an important role in the mechanism of magnetic coupling and are probed using NBO analysis. As the number of unpaired electrons on the MII ions increases, the number of electrons that occupy the empty 4d orbitals with the highest energy and overlap integrals of the magnetic orbitals in the CuIIMII (M = Cu, Ni, Co, Fe, Mn) model complexes increases accordingly, and the magnetic coupling constant gradually decreases.


3d heterometallic ions,Azido-cu(II) complex,DFT-BS,Isonicotinic acid,Theoretical calculation,

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