Issue 21, 2024

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.

Graphical abstract: Multiconfigurational actinide nitrides assisted by double Möbius aromaticity

Supplementary files

Transparent peer review

To support increased transparency, we offer authors the option to publish the peer review history alongside their article.

View this article’s peer review history

Article information

Article type
Edge Article
Submitted
05 Mar 2024
Accepted
25 Apr 2024
First published
26 Apr 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 8216-8226

Multiconfigurational actinide nitrides assisted by double Möbius aromaticity

X. Lin, X. Lu, S. Tang, W. Wu and Y. Mo, Chem. Sci., 2024, 15, 8216 DOI: 10.1039/D4SC01549E

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements