Multiconfigurational actinide nitrides assisted by double Möbius aromaticity

Abstract

Understanding the bonding nature between actinides and main-group elements remains a key challenge in actinide chemistry due to the involvement of f orbitals. Herein, we propose a unique “aromaticity-assisted multiconfiguration” (AAM) model to elucidate the bonding nature in actinide nitrides (An₂N₂, An = Ac, Th, Pa, U). Each planar four-membered An₂N₂ with equivalent An–N bonds possesses four delocalized π electrons and four delocalized σ electrons, forming a new family of double Möbius aromaticity that contributes to the molecular stability. The unprecedented aromaticity further supports actinide nitrides to exhibit multiconfigurational characters, where the unpaired electrons (2, 4 or 6 in naked Th₂N₂, Pa₂N₂ or U₂N₂, respectively) either are spin-free and localized on metal centres or form metal–ligand bonds. High-level multiconfigurational computations confirm an open-shell singlet ground state for actinide nitrides, with small energy gaps to high spin states. This is consistent with the antiferromagnetic nature observed experimentally in uranium nitrides. The novel AAM bonding model can be authenticated in both experimentally identified compounds containing a U₂N₂ motif and other theoretically modelled An₂N₂ clusters and is thus expected to be a general chemical bonding pattern between actinides and main-group elements.