Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr, Germany.
Science. 2023 Jun 9;380(6649):1043-1048. doi: 10.1126/science.adg2833. Epub 2023 May 18.
Large spin-orbit coupling (SOC) is an intrinsic property of the heavy elements that directly affects the electronic structures of the compounds. In this work, we report the synthesis and characterization of a monocoordinate bismuthinidene that features a rigid and bulky ligand. All magnetic measurements [superconducting quantum interference device (SQUID), nuclear magnetic resonance (NMR)] point to a diamagnetic compound. However, multiconfigurational quantum chemical calculations predict the ground state of the compound to be dominated (76%) by a spin triplet. The apparent diamagnetism is explained by an extremely large SOC-induced positive zero-field splitting of more than 4500 wavenumbers that leaves the M = 0 magnetic sublevel thermally isolated in the electronic ground state.
大自旋轨道耦合（SOC）是重元素的固有特性，它直接影响化合物的电子结构。在这项工作中，我们报告了一种单核铋烯的合成和表征，其特征是具有刚性和庞大的配体。所有的磁性测量[超导量子干涉仪（SQUID）、核磁共振（NMR）]都表明该化合物是抗磁性的。然而，多组态量子化学计算预测该化合物的基态主要由自旋三重态主导（76%）。明显的抗磁性可以用 SOC 引起的超过 4500 波数的正零场分裂来解释，这使得 M = 0 磁亚能级在电子基态中热隔离。
