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

TLDR

For neutral and charged planar rings, the out‑of‑plane nuclear shielding and magnetizability along the central axis are linked by a simple equation involving the average current‑loop radius, but both properties are strongly influenced by molecular geometry. The study introduces a new estimate of the effective radius of the average current loop in planar inorganic rings. Using a simple classical model of magnetic‑field induced electron flow, the authors evaluate ring‑current strengths and susceptibilities for several inorganic monocyclic rings and validate the.

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).