The Phenalenyl Motif: A Magnetic Chameleon

Cyrański, Michał K.; Havenith, Remco W. A.; Dobrowolski, Michał A.; Gray, Benjamin R.; Krygowski, Tadeusz M.; Fowler, Patrick W.; Jenneskens, Leonardus W.

doi:10.1002/chem.200601619

Cited by 46 publications

(38 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This analysis also suggests that the corannulene dianion, observed in the 1 H‐NMR as a ‘diamagnetic’ singlet only at low temperatures, is actually a paramagnetic closed‐shell species. A similar analysis of induced ring currents was calculated for phenalenyl ions 70. It was demonstrated that both cation and anion maintain a diatropic ring current in the molecule—despite having 12 and 14 π electrons, respectively.…”

Section: Aromaticity and Antiaromaticity In Polyarene Anionssupporting

confidence: 55%

Polyarene anions: interplay between theory and experiment

Eisenberg¹,

Shenhar²

2011

WIREs Comput Mol Sci

View full text Add to dashboard Cite

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 sp 2 -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. C 2011 John Wiley & Sons, Ltd.

show abstract

Section: Aromaticity and Antiaromaticity In Polyarene Anionssupporting

confidence: 55%

Polyarene anions: interplay between theory and experiment

Eisenberg¹,

Shenhar²

2011

WIREs Comput Mol Sci

View full text Add to dashboard Cite

show abstract

“…The NICS zz -scan curve (Figure 9c) of the phenalenyl cation is typical for aromatic molecules exhibiting pure π-aromatic character. Very recently, Fowler et al [92] using the ipsocentric approach predicted the diatropicity of the phenalenyl cation which arises mainly from the contribution of the doubly degenerate 2e HOMO-2 pair. …”

Section: The Nics Zz -Scan Curves Versus the Orbital-type Of Aromaticmentioning

confidence: 99%

Diagnosis of the σ-, π- and (σ+π)-Aromaticity by the Shape of the NICSzz-Scan Curves and Symmetry-Based Selection Rules

2010

View full text Add to dashboard Cite

Abstract. The NICS zz -scan curves of aromatic organic, inorganic and "all-metal" molecules in conjunction with symmetry-based selection rules provide efficient diagnostic tools of the σ-, π-and/or double (σ + π)-aromaticity. The NICS zz -scan curves of σ-aromatic molecules are symmetric around the z-axis, having half-band widths approximately less than 3 Å with the induced diatropic ring current arising from T x,y -allowed transitions involving exclusively σ-type molecular orbitals. Broad NICS zz -scan curves (half-band width approximately higher than 3 Å) characterize double (σ + π)-aromaticity, the chief contribution to the induced diatropic ring current arising from T x,y -allowed transitions involving both σ-and π-type molecular orbitals. NICS zz -scan curves exhibiting two maxima at a certain distance above and below the molecular plane are typical for (σ + π)-aromatics where the π-diatropic ring current overwhelms the σ-type one. In the absence of any contribution from the σ-diatropic ring current, the NICS zz (0) value is close to zero and the molecule exhibits pure π-aromaticity.

show abstract

“…It is the smallest polycyclic subunit of graphene with an internal carbon atom and has peculiar and interesting electronic properties. 17,18 It has been invoked as a building block for single molecule molecular conductors, 19,20 and its high stability has led to derivatives having been observed at room temperature in solution and as crystals. 21,22 …”

Section: Introductionmentioning

confidence: 99%