Theoretical study of phenylbismuth anion as a blueprint for main-group single-molecule magnets

Abstract

The hypothetical [BiPh]⁻ anion obtained by a one-electron reduction from the respective bismuthinidene is proposed as a basis for constructing single-molecule magnets (SMMs) consisting purely of main-group elements. Based on high-level quantum-chemical calculations, the [BiPh]⁻ anion is predicted to be a SMM with an effective barrier of 6418 cm⁻¹ for the relaxation of magnetization. This barrier is much larger than any effective barrier observed so far in any experimentally characterized SMM. The reduction potential for the [BiPh]⁻/BiPh couple is calculated as −1.5 V, which implies that the [BiPh]⁻ moiety is accessible from stable bismuthinidenes containing a BiPh moiety and sufficient steric protection for the reactive Bi atom. Thus, [BiPh]⁻ provides a blueprint for the realization of purely main-group SMMs which can surpass in their properties the best known dysprosium-based SMMs.