Direct Observation of Very Large Zero-Field Splitting in a Tetrahedral Ni(II)Se4 Coordination Complex.
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.
1. Physikalisches Institut, Universität Stuttgart , Pfaffenwaldring 57, D-70550, Stuttgart, Germany.
Shang-Da
SD
Jiang
Max-Planck-Institut für Chemische Energiekonversion , Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
Dimitrios
D
Maganas
Laboratory of Inorganic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens , Panepistimiopolis, Athens, 157 71 Greece.
Nikolaos
N
Levesanos
Laboratory of Inorganic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens , Panepistimiopolis, Athens, 157 71 Greece.
Eleftherios
E
Ferentinos
1. Physikalisches Institut, Universität Stuttgart , Pfaffenwaldring 57, D-70550, Stuttgart, Germany.
Sabrina
S
Haas
National High Magnetic Field Laboratory, Florida State University , Tallahassee, Florida 32310, United States.
Komalavalli
K
Thirunavukkuarasu
National High Magnetic Field Laboratory, Florida State University , Tallahassee, Florida 32310, United States.
J
J
Krzystek
1. Physikalisches Institut, Universität Stuttgart , Pfaffenwaldring 57, D-70550, Stuttgart, Germany.
Martin
M
Dressel
1. Physikalisches Institut, Universität Stuttgart , Pfaffenwaldring 57, D-70550, Stuttgart, Germany.
Lapo
L
Bogani
Max-Planck-Institut für Chemische Energiekonversion , Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
Frank
F
Neese
Laboratory of Inorganic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens , Panepistimiopolis, Athens, 157 71 Greece.
Panayotis
P
Kyritsis