Search

In the current work, the authors analyzed and compared the chemical behavior of some (anti)aromatic compounds. The species selected are benzene and cyclobutadiene as the aromatic and antiaromatic classical examples, respectively. Next, the anion Al42−, which is the first all‐metal molecule catalogued as aromatic and its non‐metallic isoelectronic analog, B42− were also analyzed. The antiaromatic clusters Al44− and B44− were studied in form of lithium salts. And the end, the non‐planar B12 boron cluster and its isoelectronic analogs (B11Be− and B11C+) were considered for being analyzed under the same criterium. The analysis was realized employing the following descriptors: molecular electrostatic potential and local hyper‐softness to get insights concerning local reactivity when facing reagents leading to ionic or covalent interactions. The results show that all the molecules analyzed presented some specific variations in their respective local reactivity despite being labeled as aromatic compounds. This analysis provides a notion that the local reactivity is more based on the nature of the atoms and the molecular geometry than the aromatic character by itself. [ABSTRACT FROM AUTHOR]

In this work, the induced magnetic field is analyzed for a series of substituted benzenes dications with formula C6R62+ (R=I, At, SeH, SeCH3, TeH, TeCH3), presumably exhibiting concentric aromaticity. Previous studies concluded that in the carbon skeleton, just π‐electrons are delocalized. However, our results support that both the σ‐ and π‐electrons are delocalized in the carbon skeleton, combined with a σ‐delocalization in the external ring. The role of the relativistic effects in these dications is discussed in detail. [ABSTRACT FROM AUTHOR]

Inspired by carbo-benzene and its inorganic analogues, in the current work, the viability of extended systems (called carbomers) formed from aromatic small rings was studied. The aluminum aromatic cluster, Al42−, and its isoelectronic carbon analogue, C42+, were employed as starting point. The insertion of alkynyl units into the Al-Al and C-C bonds results in the extended molecules named carbomers. These molecules were compared with the global minima structures, which were searched employing the genetic algorithm program, GEGA. The electronic delocalization (aromaticity) of the isomers was studied with the induced magnetic field (Bind). The results showed that global minimum of C122+ (formed from C42+) was an unexpected diatropic structure which presented a similar magnetic response to the C42+ cluster. Also, optical properties of C122+ were computed. [ABSTRACT FROM AUTHOR]

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 Al4n–; molecular stars Si5Lin6–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. [ABSTRACT FROM AUTHOR]

Various isomers of the trigonal dianion metal clusters, X32-, X = Be, Mg, Ca, and their mono- and disodium complexes are optimized at the B3LYP/6-311+G(d) level. Different conceptual density functional theory based reactivity descriptors as well as the induced magnetic field values are calculated to understand the stability and aromaticity of these systems. Possibility of bond stretch isomerism is explored. Genetic algorithm results lend additional insights into the structures of these isomers. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 [ABSTRACT FROM AUTHOR]

The authors discuss the role of the σ and π 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 σ electrons is short-ranged, the π 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 π electrons, they are shielded by the total induced magnetic field. The induced magnetic field of the π electrons support Pople's model on the basis of first-principles calculations. © 2006 Wiley Periodicals, Inc. J Comput Chem 2007 [ABSTRACT FROM AUTHOR]

Abstract: Theoretical investigation on planar and rings has been performed. The aromaticity of the rings has been analyzed through their nucleus independent chemical shift (NICS) values as well as the σ- and π-contribution of the Z-component of the induced magnetic field. Counter to a previously reported result [Chem. Phys. Lett. 432 (2006) 331], the ring is found to be a local minimum and aromatic with planar D6h symmetry. The ring exhibits conflicting aromaticity like . Both the and rings can be stabilized in presence of suitable counter cations and systems like N6Ca2 and N4Li2 can trap molecular hydrogen. [Copyright &y& Elsevier]