Issue 22, 2019
From the journal:

Chemical Science

Synthesis of aminyl biradicals by base-induced Csp3–Csp3 coupling of cationic azo dyes†

Yizhu Liu,a   Paul Varava,a   Alberto Fabrizio,a   Léonard Y. M. Eymann,a   Alexander G. Tskhovrebov,a   Ophélie Marie Planes,a   Euro Solari,a   Farzaneh Fadaei-Tirani, ORCID logo a   Rosario Scopelliti,a   Andrzej Sienkiewicz, ORCID logo b   Clémence Corminboeuf ORCID logo a  and  Kay Severin ORCID logo *a  

* Corresponding authors

a Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland
E-mail: kay.severin@epfl.ch

b Institute of Physics, EPFL, Switzerland

Abstract

The synthesis of the industrially important polymer parylene is achieved by polymerization of p-quinodimethane (p-QDM). The polymerization is thought to proceed via a biradical p-QDM dimer, but isolation or characterization of such a biradical has remained elusive. Here, we describe the synthesis of an aza-analogue of this p-QDM dimer. The biradical is formed by base-induced dimerization of an azoimidazolium dye. Due to the presence of sterically shielded aminyl radicals instead of terminal H2Ċ groups, the stability of this dimer is sufficient for analyses by ESR spectroscopy and X-ray crystallography. A similar Csp3–Csp3 coupling was observed for an azotriazolium dye, suggesting that base-induced C–C coupling reactions can be realized for different types of azo dyes.

Graphical abstract: Synthesis of aminyl biradicals by base-induced Csp3–Csp3 coupling of cationic azo dyes

About
Cited by
Related
Download options Please wait...

Supplementary files

Article information

DOI
https://doi.org/10.1039/C9SC01502G
Article type
Edge Article
Submitted
27 Mar 2019
Accepted
01 May 2019
First published
09 May 2019
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., 2019,10, 5719-5724

Permissions

Request permissions

Synthesis of aminyl biradicals by base-induced Csp3–Csp3 coupling of cationic azo dyes

Y. Liu, P. Varava, A. Fabrizio, L. Y. M. Eymann, A. G. Tskhovrebov, O. M. Planes, E. Solari, F. Fadaei-Tirani, R. Scopelliti, A. Sienkiewicz, C. Corminboeuf and K. Severin, Chem. Sci., 2019, 10, 5719 DOI: 10.1039/C9SC01502G

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