Prev. Article Next Article Table of Contents

Communication

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

Supporting Info

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

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.

View: Full Text HTML | Hi-Res PDF

Available Supporting Information for This Article

Crystallographic Information File

PDF

ja055414csi20050902_024022.pdf (619 KB)

Electronic Supporting Information files are available without a subscription to ACS Web Editions. All files are copyrighted by the American Chemical Society. Files may be downloaded for personal use only. Users are not permitted to reproduce, republish, redistribute, or resell any Supporting Information, either in whole or in part, in either machine-readable form or any other form without permission from the American Chemical Society. For permission to reproduce this material, requesters must process their own requests via the Rightslink permission system. Information about how to use the Rightslink permission system can be found at http://pubs.acs.org/page/copyright/permissions.html. Please read only the part about Rightslink.

Tools

SciFinder Links

Explore by:

Author of this Article Any Author Research Topic

History

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

Recommend & Share

Related Content

Helically Annelated and Cross-Conjugated Oligothiophenes: Asymmetric Synthesis, Resolution, and Characterization of a Carbon−Sulfur [7]HeliceneJournal of the American Chemical Society
- Helically Annelated and Cross-Conjugated Oligothiophenes: Asymmetric Synthesis, Resolution, and Characterization of a Carbon−Sulfur [7]Helicene
  Andrzej Rajca, Makoto Miyasaka, Maren Pink, Hua Wang, and Suchada Rajca
  Journal of the American Chemical Society 2004 126 (46), pp 15211–15222
  Abstract: The synthesis and characterization of a novel oligothiophene, in which the thiophene rings are annelated into a [7]helicene with cross-conjugated π-system, are described. Such [7]helicenes may be viewed as fragments of the unprecedented carbon−sulfur (C₂S)...
  Abstract | Full Text HTML | Hi-Res PDF
Helically Annelated and Cross-Conjugated β-Oligothiophenes: A Fourier Transform Raman Spectroscopic and Quantum Chemical Density Functional Theory StudyThe Journal of Physical Chemistry C
- Helically Annelated and Cross-Conjugated β-Oligothiophenes: A Fourier Transform Raman Spectroscopic and Quantum Chemical Density Functional Theory Study
  Reyes Malavé Osuna, Rocío Ponce Ortiz, Víctor Hernández, Juan Teodomiro Lpez Navarrete, Makoto Miyasaka, Suchada Rajca, Andrzej Rajca, and Rainer Glaser
  The Journal of Physical Chemistry C 2007 111 (12), pp 4854–4860
  Abstract: This article describes Fourier transform Raman/infrared spectroscopic studies to determine the conjugational properties of novel β-oligothiophenes, in which thiophene rings are helically annelated, forming a cross-conjugated π-system. These helicenes may ...
  Abstract | Full Text HTML | Hi-Res PDF
π-Conjugated Conjoined Double Helicene via a Sequence of Three Oxidative CC- and NN-HomocouplingsJournal of the American Chemical Society
- π-Conjugated Conjoined Double Helicene via a Sequence of Three Oxidative CC- and NN-Homocouplings
  Kouichi Shiraishi, Andrzej Rajca, Maren Pink, and Suchada Rajca
  Journal of the American Chemical Society 2005 127 (26), pp 9312–9313
  Abstract: Dimerization of planarized diamine 2 using benzoyl peroxide gave dihydrazine 1 in about 70% yield; that is, three dehydrogenations (one CC- and two NN-homocouplings) and two ring closures were attained in one synthetic step. Dihydrazine 1 may be viewed as ...
  Abstract | Full Text HTML | Hi-Res PDF

Communication

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

Abstract