Multiconfigurational actinide nitrides assisted by double Möbius aromaticity DOI Creative Commons
Xuhui Lin,

Xiao-Li Lu,

Shenghui Tang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(21), P. 8216 - 8226

Published: Jan. 1, 2024

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

Language: Английский

[Co3@Ge6Sn18]5–: A Giant σ-Aromatic Cluster Analogous to H3+ and Li3+ DOI

Ya‐Shan Huang,

Hong‐Lei Xu, Wen‐Juan Tian

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(11), P. 9407 - 9414

Published: March 5, 2025

Aromaticity is one of the most important concepts in chemistry and has been successfully extended to all-metal clusters. However, study all-metallic aromatic clusters remains its early stages, with σ-aromatic mostly limited small sizes (≤12) that often require external stabilization. In this work, we report first Ge/Sn-based trimer, [Co3@Ge6Sn18]5–, which can be rationalized as fusion three [Co–@Ge3Sn64–] units via a Ge3 face. Theoretical studies have revealed two σ-electrons are delocalized across entire spherical aromaticity each [Co@Ge3Sn6] unit global σ-aromaticity [Co3@Ge6Sn18]5– further supported by electron delocalization magnetic behavior. As result, trimer viewed giant counterpart triatomic H3+ Li3+. Our findings suggest potential for synthesizing cluster-of-cluster analogs discrete species, such Al42–, enhance our understanding chemical bonding.

Language: Английский

Citations

1
A bridge between silicon and gold structures. Resemblance between W@Si162+ and W@Au12 clusters DOI
Peter L. Rodríguez‐Kessler, Alvaro Muñoz‐Castro

Chemical Physics Letters, Journal Year: 2025, Volume and Issue: unknown, P. 142042 - 142042

Published: March 1, 2025

Language: Английский

Citations

0
A computational study of planar tetracoordinated carbon species CAl4X5 (X = Te, Po) with One X–X Bond DOI
Yaxuan Cheng, Mesías Orozco‐Ic, Jin‐Chang Guo

et al.

Journal of Molecular Structure, Journal Year: 2025, Volume and Issue: 1334, P. 141827 - 141827

Published: Feb. 24, 2025

Language: Английский

Citations

0
Planar tetracoordinate beryllium in σ-aromatic Li4Be and Na4Be clusters: A missing member in first-octal row planar tetracoordinate family DOI

Lin-hong Miao,

Li-juan Cui,

H. C. Zhang

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(24)

Published: Dec. 23, 2024

While planar tetracoordinate (pt) centers have been extensively explored from carbon to other octal-row elements or their heavier analogs, counterparts involving alkali (A) and alkaline-earth metals (Ae) remain elusive due the large atomic radius absence of p orbitals. In this work, we found six hitherto unknown anionic ptA (A4A−) neutral ptAe (A4Ae) through an extensive exploration potential energy surfaces. The D4h-symmetry ptBe structures in Li4Be Na4Be emerge as lowest-energy configurations, all ptA/ptAe are higher saddle points. global-minimum structure can be described Be− with a 2s12px12py1 electronic configuration, forming three σ electron sharing interactions quartet Li4+/Na4+ motifs. delocalized orbitals contribute aromaticity, thereby enhancing overall stability these intriguing title species. Furthermore, systems encapsulated within [n]cycloparaphenylene nanoloop (n = 7, 8) thermochemically spontaneously, without any disturbance planarity moiety, where get stabilized by predominant electrostatic interaction between Li4/Na4 nanoloop.

Language: Английский

Citations

2
InnTl4–nH+ (n = 0∼4): Tetracoordinate Hydrogen in a Planar Fashion? DOI

Li-juan Cui,

Xinbo Liu, H. C. Zhang

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(30), P. 13938 - 13947

Published: July 12, 2024

The recent report of planar tetracoordinate hydrogen (ptH) in In

Language: Английский

Citations

1
Metal–Metal Bonding in Tri‐Actinide Clusters: A DFT Study of [An3Cl6] z (z = 1–6) and [An3Cl6Cp3] z (z = −2– +3; An = Ac, Th, Pa, U, Np, Pu) DOI Creative Commons
Josef Tomeček, Stephen T. Liddle, Nikolas Kaltsoyannis

et al.

ChemPhysChem, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 5, 2024

The actinide-actinide bonding in tri-actinide clusters [An₃Cl₆]

Language: Английский

Citations

1
Multiconfigurational actinide nitrides assisted by double Möbius aromaticity DOI Creative Commons
Xuhui Lin,

Xiao-Li Lu,

Shenghui Tang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(21), P. 8216 - 8226

Published: Jan. 1, 2024

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

Language: Английский

Citations

0