Synthesis and isolation of a triplet bismuthinidene with a quenched magnetic response

• 成果类型: Article
• 署名作者: Pang, Yue; Noethling, Nils; Leutzsch, Markus; Kang, Liqun; Bill, Eckhard; van Gastel, Maurice; Reijerse, Edward; Goddard, Richard; Wagner, Lucas; SantaLucia, Daniel; DeBeer, Serena; Neese, Frank; Cornella, Josep
• 署名单位: Max Planck Society; Max Planck Society
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-8838
• DOI: 10.1126/science.adg2833
• 发表日期: 2023-06-08
• 页码: 1043-1048
• 关键词: trivalent carbon; persistent; spectrum; ELEMENTS; series; rings; radii; ions; bi

摘要

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 MS = 0 magnetic sublevel thermally isolated in the electronic ground state.