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Zusammenfassung:
The high-spin (S = 1) tetrahedral NiII complex [Ni{iPr2P(Se)NP(Se)iPr2}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-11, 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 NiII 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.
