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Issue 18, 2016
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Contorted aromatics via a palladium-catalyzed cyclopentannulation strategy

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We show that a new class of contorted polycyclic aromatic hydrocarbons (PAHs) containing five-membered rings can be prepared via a palladium-catalyzed cyclopentannulation followed by Scholl cyclodehydrogenation. The annulation chemistry can be accomplished between a di-arylethynylene and an appropriate aryl-dibromide to form 1,2,6,7-tetraarylcyclopenta[hi]aceanthrylenes and 1,2,6,7-tetraaryldicyclopenta[cd,jk]pyrenes. Scholl cyclodehydrogenation to close the externally fused aryl groups was accomplished only with properly arranged alkoxy substitutions and provides access to the pi-extended 2,7,13,18-tetraalkoxytetrabenzo[f,h,r,t]rubicenes and 2,7,13,18-tetraalkoxydibenzo[4,5:6,7]indeno[1,2,3-cd]dibenzo[4,5:6,7]indeno[1,2,3-jk]pyrenes. The final compounds each possess apparent [4]helicene-like arrangements with fused five-membered rings; however, only the 2,7,13,18-tetraalkoxytetrabenzo[f,h,r,t]rubicenes contort out of planarity owing to an additional [5]helicene like arrangement. Single crystal analysis of the contorted aromatic shows the PAHs stack in a lock-and-key like arrangement and pi-stack in a columnar arrangement. Solution-phase aggregation, as well as liquid crystalline mesophases, were found for derivatives with suitably attached solubilizing chains.

Graphical abstract: Contorted aromatics via a palladium-catalyzed cyclopentannulation strategy

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The article was received on 27 Jul 2015, accepted on 01 Sep 2015 and first published on 02 Sep 2015

Article type: Paper
DOI: 10.1039/C5TC02305J
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Citation: J. Mater. Chem. C, 2016,4, 3963-3969

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    Contorted aromatics via a palladium-catalyzed cyclopentannulation strategy

    S. R. Bheemireddy, P. C. Ubaldo, A. D. Finke, L. Wang and K. N. Plunkett, J. Mater. Chem. C, 2016, 4, 3963
    DOI: 10.1039/C5TC02305J

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