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WIREs Comput Mol Sci
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Polyarene anions: interplay between theory and experiment

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Polyarenes, or polycyclic aromatic hydrocarbons (PAHs), represent a ubiquitous and heavily studied type of compounds, appealing for their interesting spectroscopic, supramolecular, organometallic, and other properties. A major branch of research is concerned with polyarene anions: their electronic and structural properties, reactivity, aromaticity, and spectroscopy. This review describes the major role of computational investigations in complementing, explaining, and guiding experimental research, and thus providing invaluable contribution to our understanding of polyarene anions. The scope of this review focuses on polyarenes composed only from sp2‐hybridized carbons and limits the discussion to the quantum‐mechanical method of calculation. The topics covered include computation‐assisted characterization; choice of methods; transformations induced by reduction, including anistropic charge redistributions, reorganization of bonding structure, flattening of curved polyarenes (buckybowls), and Jahn–Teller distortion; aromaticity topics such as ring currents and aromaticity measures; reactivity, for example, toward electrophilic substitution or ring closure, acidity and basicity, and self‐assembly interactions in solution and in the gas phase; and finally, spectroscopy, mainly for astrochemical research, ranging from the mid‐infrared to the far‐ultraviolet spectral ranges. © 2011 John Wiley & Sons, Ltd.

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  • Structure and Mechanism > Molecular Structures
Figure 1.

Some of the polyarenes discussed in this review.

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Figure 2.

Some of the polyarenes, whose anions were studied by Rabinovitz et al.

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Figure 3.

The skeleton of corannulene, the archetypal buckybowl, plotted on the surface of C60 buckminsterfullerene.

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Figure 4.

Schematic illustrations of the lower adiabatic potential energy surfaces for the Jahn–Teller distortion of (a) corannulene and (b) coronene monoanions. (Reprinted with permission from Ref 58. Copyright 2003 Elsevier).

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Figure 5.

Some of the polyarenes, whose dianions were studied by Mallion et al.

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Figure 6.

(a) The annulene‐within‐an‐annulene model of ring currents in corannulene and its anions. (b) Maps of probability current density induced in the π‐system of the respective species by a perpendicular external magnetic field pointing toward the viewer, based on the full orbital set, calculated at the CTOCD‐DZ2/6‐31G**//B3LYP/6‐31G* level and plotted on a surface having the molecular shape at 1 Bohr inside the bowl. (Adapted with permission from Ref 69. Copyright 2008 American Chemical Society.)

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Figure 7.

Polyarenes composed of fused five‐membered rings.47

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Figure 8.

Aromaticity continuums studied in the groups of (a) Rabinovitz,81 (b) Mills,82,83 and (c) Agranat.84 In each case, aromaticity is estimated by different criteria (magnetic, energetic) using a combination of experimental data and calculation results. In the case of (c), different criteria produced a different order of aromaticity.

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Figure 9.

Semi‐empirically‐calculated highest occupied molecular orbital coefficients of the polyarene dianions (black and white circles). The primary positions for electrophilic attack, as obtained from reactions with fluoroalkanes, are marked by arrows.91

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Figure 10.

Acid deprotonation with alkali metal (M) affords anthracene dianion (above) and 7,14‐dihydrodibenzo[a,h]anthracene dianion (below).95,98

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Figure 11.

Some self‐assembled aggregates of polyarene anions: corannulene tetraanion dimers, 2,5,8,11‐tetra‐tert‐butylcycloocta[1,2,3,4‐def;5,6,7,8‐def′]bisbiphenylene tetraanion tetramers (Adapted with permission from Ref 101. Copyright 2008 American Chemical Society) and hemifullerene hexaanion tetramer (Adapted with permission from Ref 102. Copyright 2006 Wiley‐VCH Verlag GmbH & Co. KgaA).

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Figure 12.

Anionic formation of polyarenes.112,114

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Figure 13.

Qualitative representation of the size and charge of the polyarenes producing the prominent emission features in the Orion Bar. (Adapted with permission from Ref 133. Copyright 2009 American Astronomical Society.)

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