Magnetic crossovers in group 15 M20 cages: The interplay of hybridization breakdown, energetic destabilization, and scalar relativistic effects

Al-Yassiri MA, Puchta R (2026)

Publication Type: Journal article

Publication year: 2026

Journal

Computational and Theoretical Chemistry Elsevier BV

Book Volume: 1265

Article Number: 116018

DOI: 10.1016/j.comptc.2026.116018

Abstract

While Ih symmetry suggest uniform spherical aromaticity, the constraints of M20 dodecahedra (M = N, P, As, Sb, and Bi) cause a significant deviation from this norm. Structural and natural bond orbital analyses indicate a gradual breakdown of classical hybridization caused by internal orbital strain. Such structural strain destabilizes frontier molecular orbitals and induces progressive energetic destabilization down group 15. These consequences were magnetically evaluated by multidimensional magnetic mapping at ωB97X-D/def2-TZVP. The magnetic calculations disclosed functional-independent (ωB97X-D, B3LYP-D3, and M06-2X) and verified higher stability for def2-TZVP over def2-TZVPD for these systems. While N20-As20 cages display localized surface aromaticity with isolated paratropic cores, the increased overlap causes a magnetic crossover at Sb20 where the diatropic domains merged into a continuous magnetic field at cage cavity. Beyond this threshold, Bi20 exhibits pronounced p-orbital strain and strong scalar relativistic effects disrupt its classical bonding and force returning to a diffuse and paratropic state.

Authors with CRIS profile

Ralph Puchta Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

University of Baghdad IQ Iraq (IQ)

How to cite

APA:

Al-Yassiri, M.A., & Puchta, R. (2026). Magnetic crossovers in group 15 M20 cages: The interplay of hybridization breakdown, energetic destabilization, and scalar relativistic effects. Computational and Theoretical Chemistry, 1265. https://doi.org/10.1016/j.comptc.2026.116018

MLA:

Al-Yassiri, Muntadar A.H., and Ralph Puchta. "Magnetic crossovers in group 15 M20 cages: The interplay of hybridization breakdown, energetic destabilization, and scalar relativistic effects." Computational and Theoretical Chemistry 1265 (2026).

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