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

被引：45

作者：

Jiang, Shang-Da ^{[1
]}

Maganas, Dimitrios ^{[2
]}

Levesanos, Nikolaos ^{[3
]}

Ferentinos, Eleftherios ^{[3
]}

Haas, Sabrina ^{[1
]}

Thirunavukkuarasu, Komalavalli ^{[4
]}

Krzystek, J. ^{[4
]}

Dressel, Martin ^{[1
]}

Bogani, Lapo ^{[1
]}

Neese, Frank ^{[2
]}

Kyritsis, Panayotis ^{[3
]}

机构：

[1] Univ Stuttgart, Inst Phys 1, D-70550 Stuttgart, Germany

[2] Max Planck Inst Chem Energiekonvers, D-45470 Mulheim, Germany

[3] Univ Athens, Dept Chem, Panepistimiopolis, Lab Inorgan Chem, Athens 15771, Greece

[4] Florida State Univ, Natl High Magnet Field Lab, Tallahassee, FL 32310 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2015年 / 137卷 / 40期

基金：

美国国家科学基金会;

关键词：

DOMAIN MAGNETIC-RESONANCE; NI-II; HIGH-FREQUENCY; SQUARE-PLANAR; ELECTRONIC-STRUCTURE; THEORETICAL-ANALYSIS; NI(II) COMPLEXES; ANISOTROPY; SPECTROSCOPY; SPIN;

D O I：

10.1021/jacs.5b06716

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The high-spin (S = 1) tetrahedral Ni-II complex [Ni{(Pr2P)-Pr-i(Se)NP-(Se)Pr-i(2)}(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.

引用

页码：12923 / 12928

页数：6

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