Direct Observation of Very Large Zero-Field Splitting in a Tetrahedral NiIISe4 Coordination Complex

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• 作者：Shang-Da Jiang ; Dimitrios Maganas ; Nikolaos Levesanos ; Eleftherios Ferentinos ; Sabrina Haas ; Komalavalli Thirunavukkuarasu ; J. Krzystek ; Martin Dressel ; Lapo Bogani ; Frank Neese ; Panayotis Kyritsis
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：October 14, 2015
• 年：2015
• 卷：137
• 期：40
• 页码：12923-12928
• 全文大小：413K
• ISSN：1520-5126

文摘

The high-spin (S = 1) tetrahedral Ni^II 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^鈭?, E = 1.91(2) cm^鈭?, 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鈥攄irectly鈥攆or 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鈭抩rbit coupling contributions of the Ni ions, whereas the corresponding effects of the Se atoms are remarkably smaller.