NDLI: Helical Oligoenes: Conformations, Bond Alternation, and Competing Through-Bond and Through-Space Transmission

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Helical Oligoenes: Conformations, Bond Alternation, and Competing Through-Bond and Through-Space Transmission

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Tsuji, Yuta Hoffmann, Roald
Description	Author Affiliation: Tsuji Y ( Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, NY, 14853, USA.); Hoffmann R ( Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, NY, 14853, USA. rh34@cornell.edu.)
Abstract	There is a consensus that long-range electron transfer/transport occurs by a through-bond rather than through-space mechanism. In helical all-Z, all-s-cis oligoenes, one can set up an interesting competition in the medium-separation regime between a closer (in distance) through-space path and a more distant through-bond one. Although such oligoene conformations/isomers are unstable (by around $4 kcal mol^{−1}$ per double bond relative to all-E, all-s-trans isomers), recent synthetic efforts on truncated helicenes and oligothiophenes have provided related molecules. On the way to transmission calculations with electrodes attached to the termini of helical oligoenes, we uncover an interesting conformational ambiguity in all-Z, all-s-cis oligoenes, the existence of a broad conformational minimum for helical compression, with hints of end-to-end frontier-orbital-caused stabilization. There is relationship between helical oligoene structures and the corresponding substructure of a helicene, but there are also significant differences in the number of olefin subunits per helix turn. In Hückel transport calculations, the role of TB or TS mechanisms is obscured to an extent by variations in bond alternation and dihedral angle along the oligomer chain. However, the operation of a dominant through bond mechanism emerges clearly in local transmission plots. In moving the electrodes to carbon position related by quantum interference, it is possible to uncover a through space mechanism.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	14
Volume Number	22
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2016-03-24
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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