Capturing the elusive aromaticity of bicalicene

W. P. Oziminski; M. Palusiak; J. Dominikowska; T. M. Krygowski; R. W. A. Havenith; C. M. Gibson; P. W. Fowler

doi:10.1039/c2cp43426a

Capturing the elusive aromaticity of bicalicene

W. P. Oziminski^*, M. Palusiak, J. Dominikowska, T. M. Krygowski, R. W. A. Havenith, C. M. Gibson, P. W. Fowler^*

^*Corresponding author for this work

Theoretical Chemistry

Research output: Contribution to journal › Article › Academic › peer-review

14 Citations (Scopus)

Abstract

The ring-current aromaticity of the bicalicene molecule arises, in spite of the 16 p carbon perimeter, from strong local diatropic circulations on the two pentagonal rings, as shown by current-density maps computed at the ipsocentric RHF/6-311G** and DFT/6-311G** levels of theory. Conjugated-circuit models cannot capture this pattern of circulation as it arises from 'ionic' contributions in a valence-bond picture. Canonical molecular-orbital analysis reveals a cancellation of paratropic and diatropic frontier-orbital contributions, which explains the difficulties that Huckel-based models have in producing qualitatively correct current-density maps for this molecule. Other measures of aromaticity reflect, to different extents, the dominance of the 'tetraionic' contribution to the aromaticity of this species.

Original language	English
Pages (from-to)	3286-3293
Number of pages	8
Journal	Physical Chemistry Chemical Physics
Volume	15
Issue number	9
DOIs	https://doi.org/10.1039/c2cp43426a
Publication status	Published - 2013

Keywords

RING CURRENTS
MAGNETIC-PROPERTIES
CONJUGATED HYDROCARBONS
CYCLIC BICALICENE
PI-SYSTEMS
MOLECULES
POLYACENES
RESONANCE
DENSITY

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@article{73e4cb3f6c3c4e9db72e6043b01680c0,

title = "Capturing the elusive aromaticity of bicalicene",

abstract = "The ring-current aromaticity of the bicalicene molecule arises, in spite of the 16 p carbon perimeter, from strong local diatropic circulations on the two pentagonal rings, as shown by current-density maps computed at the ipsocentric RHF/6-311G** and DFT/6-311G** levels of theory. Conjugated-circuit models cannot capture this pattern of circulation as it arises from 'ionic' contributions in a valence-bond picture. Canonical molecular-orbital analysis reveals a cancellation of paratropic and diatropic frontier-orbital contributions, which explains the difficulties that Huckel-based models have in producing qualitatively correct current-density maps for this molecule. Other measures of aromaticity reflect, to different extents, the dominance of the 'tetraionic' contribution to the aromaticity of this species.",

keywords = "RING CURRENTS, MAGNETIC-PROPERTIES, CONJUGATED HYDROCARBONS, CYCLIC BICALICENE, PI-SYSTEMS, MOLECULES, POLYACENES, RESONANCE, DENSITY",

author = "Oziminski, {W. P.} and M. Palusiak and J. Dominikowska and Krygowski, {T. M.} and Havenith, {R. W. A.} and Gibson, {C. M.} and Fowler, {P. W.}",

year = "2013",

doi = "10.1039/c2cp43426a",

language = "English",

volume = "15",

pages = "3286--3293",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "ROYAL SOC CHEMISTRY",

number = "9",

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TY - JOUR

T1 - Capturing the elusive aromaticity of bicalicene

AU - Oziminski, W. P.

AU - Palusiak, M.

AU - Dominikowska, J.

AU - Krygowski, T. M.

AU - Havenith, R. W. A.

AU - Gibson, C. M.

AU - Fowler, P. W.

PY - 2013

Y1 - 2013

N2 - The ring-current aromaticity of the bicalicene molecule arises, in spite of the 16 p carbon perimeter, from strong local diatropic circulations on the two pentagonal rings, as shown by current-density maps computed at the ipsocentric RHF/6-311G** and DFT/6-311G** levels of theory. Conjugated-circuit models cannot capture this pattern of circulation as it arises from 'ionic' contributions in a valence-bond picture. Canonical molecular-orbital analysis reveals a cancellation of paratropic and diatropic frontier-orbital contributions, which explains the difficulties that Huckel-based models have in producing qualitatively correct current-density maps for this molecule. Other measures of aromaticity reflect, to different extents, the dominance of the 'tetraionic' contribution to the aromaticity of this species.

AB - The ring-current aromaticity of the bicalicene molecule arises, in spite of the 16 p carbon perimeter, from strong local diatropic circulations on the two pentagonal rings, as shown by current-density maps computed at the ipsocentric RHF/6-311G** and DFT/6-311G** levels of theory. Conjugated-circuit models cannot capture this pattern of circulation as it arises from 'ionic' contributions in a valence-bond picture. Canonical molecular-orbital analysis reveals a cancellation of paratropic and diatropic frontier-orbital contributions, which explains the difficulties that Huckel-based models have in producing qualitatively correct current-density maps for this molecule. Other measures of aromaticity reflect, to different extents, the dominance of the 'tetraionic' contribution to the aromaticity of this species.

KW - RING CURRENTS

KW - MAGNETIC-PROPERTIES

KW - CONJUGATED HYDROCARBONS

KW - CYCLIC BICALICENE

KW - PI-SYSTEMS

KW - MOLECULES

KW - POLYACENES

KW - RESONANCE

KW - DENSITY

U2 - 10.1039/c2cp43426a

DO - 10.1039/c2cp43426a

M3 - Article

SN - 1463-9076

VL - 15

SP - 3286

EP - 3293

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 9

ER -