To explain peculiar effects of electron delocalization on the magnetic response of planar cyclic molecules, a basic model that accounts for their actual geometrical structure has been developed by integrating the differential Biot−Savart law. Such a model, based on a single polygonal circuit with ideal features, is shown to be applicable to electrically neutral or charged monocyclic compounds, as well as linear polycyclic condensed hydrocarbons. Two theoretical quantities, easily computed via quantum chemistry codes (the out-of-plane components of the magnetizability, ξ∥, and the magnetic shielding σ∥(h) of points P on the symmetry axis orthogonal to the molecular plane, at distance h from the center of mass) are shown to be linearly connected, for example, for monocyclic structures, via the relationship σ∥(h) = ±(μ0/2π)ξ∥D(h), where D(h) is a simple function of geometrical parameters. Equations of this type are useful to rationalize scan profiles of magnetic shielding and nucleus-independent chemical shift along the highest symmetry axis. For a regular polygon, D(h) depends approximately on the third inverse power of the distance d of the vertices from the center, and ξ∥ is proportional to the area of the polygon, that is, ∼d2; hence, the shielding σ∥(0) and the related nucleusindependent chemical shift NICS∥(0) are unsafe quantifiers of magnetotropicity; they are biased by a spurious geometrical dependence on d−1, incorrectly exhalting them in cyclic systems with smaller size. A more reliable magnetotropicity measure for a cyclic compound, in the presence of a magnetic field Bext applied at right angles to the molecular plane, is defined within the polygonal current model by the current susceptibility or current strength, ∂I/∂Bext = −ξ∥/Aeff, expressed in nanoampe re per tesla, where Aeff is a properly defined area enclosed with the polygonal circuit. An extended numerical test on a wide series of monoand polycyclic compounds and a comparison with corresponding ab initio current susceptibilities prove the superior quality of this indicator over other commonly employed aromaticity/antiaromaticity benchmarks on the magnetic criterion.
Polygonal Current Model: An Effective Quantifier of Aromaticity on the Magnetic Criterion / S., Pelloni; LAZZERETTI, Paolo. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - STAMPA. - 117(2013), pp. 9083-9092.
|Data di pubblicazione:||2013|
|Titolo:||Polygonal Current Model: An Effective Quantifier of Aromaticity on the Magnetic Criterion|
|Autore/i:||S., Pelloni; LAZZERETTI, Paolo|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1021/jp406348j|
|Codice identificativo ISI:||WOS:000329579200012|
|Codice identificativo Scopus:||2-s2.0-84884527057|
|Codice identificativo Pubmed:||23952986|
|Citazione:||Polygonal Current Model: An Effective Quantifier of Aromaticity on the Magnetic Criterion / S., Pelloni; LAZZERETTI, Paolo. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - STAMPA. - 117(2013), pp. 9083-9092.|
|Tipologia||Articolo su rivista|
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