Title: A unified orbital model of delocalised and localised currents in monocycles, from annulenes to azabora-heterocycles
Authors: Soncini, Alessandro ×
Domene, C
Engelberts, JJ
Fowler, PW
Rassat, A
van Lenthe, JH
Havenith, RWA
Jenneskens, LW #
Issue Date: Jan-2005
Publisher: Wiley-v c h verlag gmbh
Series Title: Chemistry - a European Journal vol:11 issue:4 pages:1257-1266
Abstract: Why are some (4n+2)pi systems aromatic, and some not? The ipsocentric approach to the calculation of the current density induced in a molecule by an external magnetic field predicts a four-electron diatropic (aromatic) ring current for (4n+2)pi carbocycles and a two-electron paratropic (antiaromatic) current for (4n)pi carbocycles. With the inclusion of an electro-negativity parameter, an ipsocentric frontier-orbital model also predicts the transition from delocalised currents in carbocycles to nitrogen-localised currents in alternating azabora-heterocy-cles, which rationalises the differences in (magnetic) aromaticity between these isoelectronic pi-conjugated systems. Ab initio valence-bond calculations confirm the localisation predicted by the naive model, and coupled-Hartree-Fock calculations give current-density maps that exhibit the predicted delocalised-to-localised/carbocycle-heterocycle transition.
ISSN: 0947-6539
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
× corresponding author
# (joint) last author

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