Synthesis and isolation of a triplet bismuthinidene with a quenched magnetic response
Yue Pang, Nils Nöthling, Markus Leutzsch, Liqun Kang, Eckhard Bill, Maurice van Gastel, Edward J. Reijerse, Richard Goddard, Lucas Wagner, Daniel J. SantaLucia, Serena DeBeer, Frank Neese, Josep Cornellà
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 S = 0 magnetic sublevel thermally isolated in the electronic ground state.