The homotropenylium cation: a system with a pinched π ring current

文献情報

出版日 2014-04-25

DOI 10.1039/C4CP01075B

インパクトファクター 3.676

著者

Mark Lillington, Patrick W. Fowler, Jon Baker, Leonardus W. Jenneskens

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要旨

The homotropenylium cation (1, C8H9+) is a key species in the discussion of homoaromaticity. Constrained optimisations around the minimum structure have been performed, varying the size of the gap spanned by the CH2-bridge and optimising all other geometrical parameters. At each bridging distance, ab initio current-density maps have been calculated and plotted using the ipsocentric approach. Analysis of the maps, including decomposition into localised orbital contributions, gives a clear indication of a global diatropic ring current passing through the gap. The change in pπ–pπ interaction, from conventional π overlap around the conjugated seven-carbon perimeter to σ overlap (pσ–pσ) in the gap, results in a distinctive pinched topology, with two streams of current pinched down into one for part of the circuit. This ring current is diatropic and therefore the species 1 is aromatic on the magnetic criterion.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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