Published in

Royal Society of Chemistry, Physical Chemistry Chemical Physics, 46(13), p. 20666, 2011

DOI: 10.1039/c1cp21952a

Links

Tools

Export citation

Search in Google Scholar

Beyond NICS: estimation of the magnetotropicity of inorganic unsaturated planar rings

Journal article published in 2011 by Stefano Pelloni, Guglielmo Monaco ORCID, Paolo Lazzeretti, Riccardo Zanasi
This paper is available in a repository.
This paper is available in a repository.

Full text: Download

Green circle
Preprint: archiving allowed
Orange circle
Postprint: archiving restricted
Red circle
Published version: archiving forbidden
Data provided by SHERPA/RoMEO

Abstract

A simple classical model of magnetic-field induced electron flow is used to evaluate the ring current strength for a few inorganic monocyclic compounds: B(3)H(3)N(3), B(3)H(3)O(3), P(6), N(6), Si(6)H(6), N, Al and H(6). It is shown that, for these neutral and charged systems, sustaining delocalized electron currents in the presence of a magnetic field B(ext) orthogonal to the σ(h) plane, the out-of-plane component of the nuclear magnetic shielding along the central axis is connected to the out-of-plane magnetizability by a simple equation, involving the radius of an average loop of current. A novel estimate of this effective radius is provided. Reliable ring current susceptibilities (that is, current strengths) can be evaluated by a simple relationship, using the out-of-plane components of nuclear shielding and magnetizability tensors. The accuracy of the current susceptibilities calculated by the classical model is established by comparison with corresponding ab initio estimates obtained by integrating the quantum mechanical current-density vector field. The out-of-plane components of nuclear shielding and magnetizability are both strongly biased by the molecular geometry. Their combined use to estimate the ring current susceptibility offers a quantifier of magnetotropicity more reliable than (i) the ξ(∥) out-of-plane component of magnetizability, (ii) the σ(∥)(CM) out-of-plane component of the magnetic shielding at the center of mass, widely reported as NICS(∥)(0) = -σ(∥)(CM). The inadequacy of these commonly adopted magnetotropicity measures is demonstrated by comparing a set of related molecules, C(6)H(6) and Si(6)H(6), N(6) and P(6).