Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 22nd May 2019 from 11:00 AM to 1:00 PM (GMT).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 38, 2018
Previous Article Next Article

Reversible π-system switching of thiophene-fused thiahexaphyrins by solvent and oxidation/reduction

Author affiliations

Abstract

The concept of chemical topology has generated considerable interest among chemists and one of the state-of-the-art topics is Möbius topology in cyclic π-conjugated molecules. In this regard, expanded porphyrins have been extensively studied because of their facile topological interconversions and attractive optoelectronic properties. A typical example involves [28]hexaphyrins: they show topological conversion between planar Hückel and twisted Möbius topologies owing to their flexible structure. With this in mind, we designed a [28]hexaphyrin where one dimethine pyrrole unit was replaced with dithieno[3,4-b:3′,4′-d]thiophene (β-DTT), aiming at a reversible switching between macrocyclic and cross-conjugated π-systems by a change in molecular topologies. Considering that the β-DTT unit can offer both macrocyclic and cross-conjugated π-circuits, we envisioned that a combination of the topological interconversion of [28]hexaphyrin with the two π-circuits of the β-DTT unit would enable a reversible switching between macrocyclic and cross-conjugated π-circuits on Möbius and Hückel topologies, respectively, by a simple conformational change. Unexpectedly, the hexaphyrin revealed a unique, unprecedented π-system switching between a Möbius cross-conjugated π-system and a Hückel antiaromatic π-system, which was fully supported by both experimental and theoretical investigations. Meanwhile, the [28]hexaphyrin was also found to be redox interconvertible with the corresponding [26]hexaphyrin with a Hückel cross-conjugated π-system. These results demonstrate that the β-DTT unit is a new effective motif to realize π-system switching by changing molecular and π-system topologies. Importantly, external stimuli, i.e., solvent, as well as oxidation/reduction can be used to trigger the topological changes in expanded porphyrins with the help of the β-DTT unit.

Graphical abstract: Reversible π-system switching of thiophene-fused thiahexaphyrins by solvent and oxidation/reduction

Back to tab navigation

Supplementary files

Publication details

The article was received on 04 Jun 2018, accepted on 07 Aug 2018 and first published on 14 Aug 2018


Article type: Edge Article
DOI: 10.1039/C8SC02448K
Chem. Sci., 2018,9, 7528-7539
  • Open access: Creative Commons BY-NC license
  •   Request permissions

    Reversible π-system switching of thiophene-fused thiahexaphyrins by solvent and oxidation/reduction

    T. Higashino, A. Kumagai, S. Sakaki and H. Imahori, Chem. Sci., 2018, 9, 7528
    DOI: 10.1039/C8SC02448K

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements