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Issue 11, 2013
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Helical frontier orbitals of conjugated linear molecules

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Abstract

Compounds containing allenes, cumulenes and oligoynes (polyalkynes) have attracted attention for both their conformation and reactivity. Whilst the textbook molecular orbital description explains the general electronic and molecular structure of the cumulenes, there are anomalies in both the crystal structures and cycloaddition products involving oligoynes and allenes; the understanding of these molecules is incomplete. Through a computational study we elucidate that the frontier orbitals of the allene and oligoyne families are extended helices. These orbitals are the linear analogue to the Möbius aromatic systems, which also display non-linear π interactions. The axial chirality found in allenes and oligoynes is intimately related to the topology of the frontier orbitals, and has implications for predictions of cycloaddition pathways, structure stability and spectroscopy.

Graphical abstract: Helical frontier orbitals of conjugated linear molecules

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Publication details

The article was received on 23 Jul 2013, accepted on 23 Aug 2013 and first published on 23 Aug 2013


Article type: Edge Article
DOI: 10.1039/C3SC52061G
Citation: Chem. Sci., 2013,4, 4278-4284
  • Open access: Creative Commons BY license
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    Helical frontier orbitals of conjugated linear molecules

    C. H. Hendon, D. Tiana, A. T. Murray, D. R. Carbery and A. Walsh, Chem. Sci., 2013, 4, 4278
    DOI: 10.1039/C3SC52061G

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