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Communication

Cross-Conjugated Oligothiophenes Derived from the (C₂S)_n Helix: Asymmetric Synthesis and Structure of Carbon−Sulfur [11]Helicene

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Makoto Miyasaka,^† Andrzej Rajca,*^† Maren Pink,^‡ and Suchada Rajca^†

Department of Chemistry, University of Nebraska, Lincoln, Nebraska 68588-0304, and IUMSC, Department of Chemistry, Indiana University, Bloomington, Indiana 47405

J. Am. Chem. Soc., 2005, 127 (40), pp 13806–13807

DOI: 10.1021/ja055414c

Publication Date (Web): September 20, 2005

, †

University of Nebraska.

, *

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, ‡

Indiana University.

Abstract

(−)-Sparteine-mediated asymmetric synthesis of di-n-octyl-substituted carbon−sulfur [11]helicene, a helical (C₂S)_n β-undecathiophene, is described. The atom-efficient routes rely on one-step tri-annelation or two-step di- and mono-annelation to provide enantiomeric excess of (+)- or (−)-[11]helicene, respectively. X-ray structures for homologous [11] and [7]helicenes indicate similar helical curvatures. The optical band gap, E_g ≈ 3.5 eV, is estimated for the (C₂S)_n helix polymer, with onset of electron localization at n ≤ 7.

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History

Published In Issue October 12, 2005
Received August 8, 2005

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Communication

Cross-Conjugated Oligothiophenes Derived from the (C₂S)_n Helix: Asymmetric Synthesis and Structure of Carbon−Sulfur [11]Helicene

Abstract