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

Pang, Yue; Nöthling, Nils; Leutzsch, Markus; Kang, Liqun; Bill, Eckhard; van Gastel, Maurice; Reijerse, Edward; Goddard, Richard et al. · Science · 2023

basic_science · Level V

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Abstract

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<i><sub>S</sub></i> = 0 magnetic sublevel thermally isolated in the electronic ground state.