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 (An(2)N(2), An = Ac, Th, Pa, U). Each planar four-membered An(2)N(2) 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 Th(2)N(2), Pa(2)N(2) or U(2)N(2), 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 U(2)N(2) motif and other theoretically modelled An(2)N(2) clusters and is thus expected to be a general chemical bonding pattern between actinides and main-group elements.