Issue 3, 2016

Switchable π-electronic network of bis(α-oligothienyl)-substituted hexaphyrins between helical versus rectangular circuit

Abstract

The switching phenomena of conformation with π-electronic network through deprotonation–protonation processes were investigated by employing a series of 5,20-bis(α-oligothienyl) substituted hexaphyrins(1.1.1.1.1.1). They showed significant changes in the absorption and emission spectra with deprotonation, and returned to the initial state with protonation. Through NMR measurements and single crystal X-ray diffraction analysis, we found that the 5,20-bis(α-oligothienyl) substituted hexaphyrins, which possess acyclic, helical electronic networks involving oligothienyl chains in dumbbell conformations (type-I) in a neutral form, underwent effective deprotonation upon treatment with tetrabutylammonium fluoride (TBAF) to generate the corresponding dianions, which display cyclic electronic networks with enhanced aromaticity in rectangular conformations (type-II). Our quantum calculation results provide an unambiguous description for the switchable conformation and π-conjugation, which revealed that a deprotonation-induced enhanced aromatic conjugation pathway is involved in the switchable π-electronic network.

Graphical abstract: Switchable π-electronic network of bis(α-oligothienyl)-substituted hexaphyrins between helical versus rectangular circuit

Supplementary files

Article information

Article type
Edge Article
Submitted
09 Nov 2015
Accepted
03 Dec 2015
First published
08 Dec 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2016,7, 2239-2245

Switchable π-electronic network of bis(α-oligothienyl)-substituted hexaphyrins between helical versus rectangular circuit

J. Oh, H. Mori, Y. M. Sung, W. Kim, A. Osuka and D. Kim, Chem. Sci., 2016, 7, 2239 DOI: 10.1039/C5SC04263A

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements