Al Said Tarek, Spinnato Davide, Holldack Karsten, Neese Frank, Cornella Josep, Schnegg Alexander
Helmholtz-Zentrum Berlin für Materialien und Energie, Albert-Einstein-Strasse 15, 12489 Berlin, Germany.
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
J Am Chem Soc. 2025 Jan 8;147(1):84-87. doi: 10.1021/jacs.4c14795. Epub 2024 Dec 16.
Stable monocoordinated organobismuthinidenes were only recently isolated and analyzed toward their chemical and electronic structure. Quantum chemical calculations on Bu-MFluind-Bi(I) () predicted an unusual electronic structure dominated by a triplet ground state and a spectacular zero-field splitting (ZFS) > 4500 cm. However, experimental evidence for these predictions remained elusive due to limitations in the available magnetic characterization techniques. Herein, we determine an axial ZFS of = 5422 cm for , by direct detection of triplet electron paramagnetic resonance using magneto-optical infrared spectroscopy. To date, this represents the largest ZFS experimentally measured.
稳定的单配位有机铋烯直到最近才被分离出来，并对其化学和电子结构进行了分析。对Bu-MFluind-Bi(I)（）的量子化学计算预测了一种不寻常的电子结构，其基态为三重态，具有高达4500 cm以上的显著零场分裂（ZFS）。然而，由于现有磁表征技术的限制，这些预测的实验证据仍然难以获得。在此，我们通过磁光红外光谱直接检测三重态电子顺磁共振，确定了的轴向ZFS为5422 cm。迄今为止，这是实验测量到的最大ZFS。
