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

(2014) PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 16(23). p.11566-11572
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Abstract
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 p(pi)-p(pi) interaction, from conventional p overlap around the conjugated seven-carbon perimeter to s overlap (p(sigma)-p(sigma)) 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.
Keywords
MOLECULES, AROMATICITY, AB-INITIO, CHEMICAL-SHIFTS, ELECTRONIC-STRUCTURE, CURRENT DENSITIES, MAGNETIC-PROPERTIES, HOMOAROMATICITY, HYDROCARBONS, NONPLANAR

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Citation

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MLA
Lillington, Mark, Remco Havenith, Patrick W Fowler, et al. “The Homotropenylium Cation : a System with a Pinched π Ring Current.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 16.23 (2014): 11566–11572. Print.
APA
Lillington, M., Havenith, R., Fowler, P. W., Baker, J., & Jenneskens, L. W. (2014). The homotropenylium cation : a system with a pinched π ring current. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 16(23), 11566–11572.
Chicago author-date
Lillington, Mark, Remco Havenith, Patrick W Fowler, Jon Baker, and Leonardus W Jenneskens. 2014. “The Homotropenylium Cation : a System with a Pinched π Ring Current.” Physical Chemistry Chemical Physics 16 (23): 11566–11572.
Chicago author-date (all authors)
Lillington, Mark, Remco Havenith, Patrick W Fowler, Jon Baker, and Leonardus W Jenneskens. 2014. “The Homotropenylium Cation : a System with a Pinched π Ring Current.” Physical Chemistry Chemical Physics 16 (23): 11566–11572.
Vancouver
1.
Lillington M, Havenith R, Fowler PW, Baker J, Jenneskens LW. The homotropenylium cation : a system with a pinched π ring current. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 2014;16(23):11566–72.
IEEE
[1]
M. Lillington, R. Havenith, P. W. Fowler, J. Baker, and L. W. Jenneskens, “The homotropenylium cation : a system with a pinched π ring current,” PHYSICAL CHEMISTRY CHEMICAL PHYSICS, vol. 16, no. 23, pp. 11566–11572, 2014.
@article{5782570,
  abstract     = {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 p(pi)-p(pi) interaction, from conventional p overlap around the conjugated seven-carbon perimeter to s overlap (p(sigma)-p(sigma)) 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.},
  author       = {Lillington, Mark and Havenith, Remco and Fowler, Patrick W and Baker, Jon and Jenneskens, Leonardus W},
  issn         = {1463-9076},
  journal      = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS},
  keywords     = {MOLECULES,AROMATICITY,AB-INITIO,CHEMICAL-SHIFTS,ELECTRONIC-STRUCTURE,CURRENT DENSITIES,MAGNETIC-PROPERTIES,HOMOAROMATICITY,HYDROCARBONS,NONPLANAR},
  language     = {eng},
  number       = {23},
  pages        = {11566--11572},
  title        = {The homotropenylium cation : a system with a pinched π ring current},
  url          = {http://dx.doi.org/10.1039/c4cp01075b},
  volume       = {16},
  year         = {2014},
}

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