Helical frontier orbitals of conjugated linear molecules

Thumbnail Image
C3SC52061G.pdf(464.25 KB)
Published version
Hendon, Christopher H.
Tiana, Davide
Murray, Alexander T.
Carbery, David R.
Walsh, Aron
Journal Title
Journal ISSN
Volume Title
Royal Society of Chemistry (RSC)
Published Version
Research Projects
Organizational Units
Journal Issue
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 Mobius aromatic systems, which also display non-linear pi 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.
Metal-organic frameworks , One hundred years , Acetylenedicarboxylic acid , Stereoselective syntheses , Electronic-properties , 2+2 cycloaddition , Excited-state , Allene , Carbohelicenes , Conservation
Hendon, C. H., Tiana, D., Murray, A. T., Carbery, D. R. and Walsh, A. (2013) 'Helical frontier orbitals of conjugated linear molecules', Chemical Science, 4(11), pp. 4278-4284. doi: 10.1039/c3sc52061g