Direct observation of very large zero-field splitting in a tetrahedral Ni(II)Se4 coordination complex

Journal article

The high-spin (S = 1) tetrahedral Ni(II) complex [Ni{(i)Pr2P(Se)NP(Se)(i)Pr2}2] was investigated by magnetometry, spectroscopic, and quantum chemical methods. Angle-resolved magnetometry studies revealed the orientation of the magnetization principal axes. The very large zero-field splitting (zfs), D = 45.40(2) cm(-1), E = 1.91(2) cm(-1), of the complex was accurately determined by far-infrared magnetic spectroscopy, directly observing transitions between the spin sublevels of the triplet ground state. These are the largest zfs values ever determined--directly--for a high-spin Ni(II) complex. Ab initio calculations further probed the electronic structure of the system, elucidating the factors controlling the sign and magnitude of D. The latter is dominated by spin-orbit coupling contributions of the Ni ions, whereas the corresponding effects of the Se atoms are remarkably smaller.

Authors: Jiang, S-D; Maganas, D; Levesanos, N; Ferentinos, E; Haas, S

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Chemical Society
• Journal: Journal of the American Chemical Society
• Volume: 137
• Issue: 40
• Pages: 12923-12928
• Publication date: 2015-09-09
• DOI: 10.1021/jacs.5b06716
• EISSN: 1520-5126
• ISSN: 0002-7863
• Language: English