Aromaticity is indispensable for explaining a variety of chemical behaviors, including reactivity, structural features, relative energetic stabilities, and spectroscopic properties. When interpreted as the spatial delocalization of π-electrons, it represents the driving force for the stabilization of many planar molecular structures. A delocalized electron system is sensitive to an external magnetic field; it responds with an induced magnetic field having a particularly long range. The shape of the induced magnetic field reflects the size and strength of the system of delocalized electrons and can have a large influence on neighboring molecules. In 2004, we proposed using the induced magnetic field as a means of estimating the degree of electron delocalization and aromaticity in planar as well as in nonplanar molecules. We have since tested the method on aromatic, antiaromatic, and nonaromatic compounds, and a refinement now allows the individual treatment of core-, σ-, and π-electrons. In this Account, we describe the use of the induced magnetic field as an analytical probe for electron delocalization and its application to a large series of uncommon molecules. The compounds include borazine; all-metal aromatic systems Al(4)(n-); molecular stars Si(5)Li(n)(6-n); electronically stabilized planar tetracoordinate carbon; planar hypercoordinate atoms inside boron wheels; and planar boron wheels with fluxional internal boron cluster moieties. In all cases, we have observed that planar structures show a high degree of electron delocalization in the π-electrons and, in some examples, also in the σ-framework. Quantitatively, the induced magnetic field has contributions from the entire electronic system of a molecule, but at long range the contributions arising from the delocalized electronic π-system dominate. The induced magnetic field can only indirectly be confirmed by experiment, for example, through intermolecular contributions to NMR chemical shifts. We show that calculating the induced field is a useful method for understanding any planar organic or inorganic system, as it corresponds to the intuitive Pople model for explaining the anomalous proton chemical shifts in aromatic molecules. Indeed, aromatic, antiaromatic, and nonaromatic molecules show differing responses to an external field; that is, they reduce, augment, or do not affect the external field at long range. The induced field can be dissected into different orbital contributions, in the same way that the nucleus-independent chemical shift or the shielding function can be separated into component contributions. The result is a versatile tool that is particularly useful in the analysis of planar, densely packed systems with strong orbital contributions directly atop individual atoms.

The electronic structure of the recently synthesized (3 × 3) reconstructed silicene on (4 × 4) Ag(111) is investigated by first-principles calculations. New states emerge due to the strong hybridization between silicene and Ag. Analyzing the nature and composition of these hybridized states, we show that (i) it is possible to clearly distinguish them from states coming from the Dirac cone of free-standing silicene or from the sp bands of bulk Ag and (ii) assign their contribution to the description of the linearly dispersing band observed in photoemission. Furthermore, we show that silicene atoms contribute to the Fermi level, which leads to similar scanning tunneling microscopy patterns as observed below or above the Fermi level. Our findings are crucial for the proper interpretation of experimental observations.

Aromaticity of borazine, which has been subject of controversial discussions, is addressed. Beside a short review on aromaticity of borazine we report a detailed analysis of two molecular fields, the induced magnetic field (B ind ) and the electron localization function (ELF). The induced magnetic field of borazine shows a long-range shielding cone perpendicular to the molecular plane, as in benzene, but lower in magnitude. Contrary to benzene, borazine shows two weakly paratropic regions, one of them inside the ring, and the second one enveloping the boron atoms. It is necessary to separate r and p contributions to identify whether borazine exhibits p-aromatic character comparable to benzene. Nucleus-independent chemical shift (NICS) isolines show that the r electrons are much stronger localized than p electrons, their local paramagnetic contributions generate a short-range response and a paratropic (deshielding) region in the ring center (similar to an anti-aromatic response). Three regions can be identified as chemically meaningful domains exhibiting an internally strong electron delocalization (ELF = 0.823). Borazine may be described as a p aromatic compound, but it is not a globally aromatic species, as the electronic system is not as delocalized as in benzene.

Abstract:The authors discuss the role of the and contributions to the induced magnetic field for simple hydrocarbons containing a double or a triple bond, as well as for benzene and cyclobutadiene. While the magnetic field induced by the electrons is short-ranged, the system is responsible for the formation of long-range cones. These cones influence the chemical shift of atoms by additional shielding (for aromatic) or deshielding (for antiaromatic molecules) contributions. While the hydrogen atoms of benzene are found to lie within the deshielded region of the magnetic field induced by the electrons, they are shielded by the total induced magnetic field. The induced magnetic field of the electrons support Pople's model on the basis of first-principles calculations.