Center for Molecular Modeling - S. Billiet

Design of a thermally controlled sequence of triazolinedione-based click and transclick reactions

wim — Mon, 27 Mar 2017 07:43:57 +0000

H.A. Houck, K. De Bruycker, S. Billiet, B. Dhanis, H. Goossens, S. Catak, V. Van Speybroeck, J.M. Winne, F. Du Prez

Chemical Science

8 (4), 3098-3108

2017

Abstract

The reaction of triazolinediones (TADs) and indoles is of particular interest for polymer chemistry applications, as it is a very fast and irreversible additive-free process at room temperature, but can be turned into a dynamic covalent bond forming process at elevated temperatures, giving a reliable bond exchange or ‘transclick’ reaction. In this paper, we report an in-depth study aimed at controlling the TAD – indole reversible click reactions through rational design of modified indole reaction partners. This has resulted in the identification of a novel class of easily accessible indole derivatives that give dynamic TAD-adduct formation at significantly lower temperatures. We further demonstrate that these new substrates can be used to design a directed cascade of click reactions of a functionalized TAD moiety from an initial indole reaction partner to a second indole, and finally to an irreversible reaction partner. This controlled sequence of click and transclick reactions of a single TAD reagent between three different substrates has been demonstrated both on small molecule and macromolecular level, and the factors that control the reversibility profiles have been rationalized and guided by mechanistic considerations supported by theoretical calculations.

Open Access version available at UGent repository

Green Open Access

DOI

http://dx.doi.org/10.1039/c7sc00119c

Private attachment

Hannes2017.pdf

Triazolinediones enabling ultrafast and reversible click chemistry for facile design of healable and reshapable polymers

michel — Fri, 27 Jun 2014 13:56:44 +0000

S. Billiet, K. De Bruycker, F. Driessen, H. Goossens, V. Van Speybroeck, J. Winne, F. Du Prez

Nature Chemistry

6 (9), 815-821

2014

Abstract

With its focus on synthetic reactions that are highly specific and reliable, ‘click’ chemistry has become a valuable tool for many scientific research areas and applications. Combining the modular, covalently bonded nature of click-chemistry linkages with an ability to reverse these linkages and reuse the constituent reactants in another click reaction, however, is a feature that is not found in most click reactions. Here we show that triazolinedione compounds can be used in click-chemistry applications. We present examples of simple and ultrafast macromolecular functionalization, polymer–polymer linking and polymer crosslinking under ambient conditions without the need for a catalyst. Moreover, when triazolinediones are combined with indole reaction partners, the reverse reaction can also be induced at elevated temperatures, and the triazolinedione reacted with a different reaction partner, reversibly or irreversibly dependent on its exact nature. We have used this ‘transclick’ reaction to introduce thermoreversible links into polyurethane and polymethacrylate materials, which allows dynamic polymer-network healing, reshaping and recycling.

DOI

http://dx.doi.org/10.1038/nchem.2023

Private attachment

14_NatureChemistry_6(9)815_Billiet.pdf

Click/transclick reactions in combination with CRP: 'TAD's the spirit'

samuel — Thu, 06 Feb 2020 09:46:32 +0000

F. Du Prez, S. Billiet, K. De Bruycker, F. Driessen, H. Goossens, V. Van Speybroeck, J. Winne

ISBN/ISSN:

Talk

Conference / event / venue

248th National Meeting of the American-Chemical-Society (ACS 2014 )

San Francisco, CA

Sunday, 10 August, 2014 to Thursday, 14 August, 2014

Triazolinediones enable ultrafast and reversible click chemistry for the design of dynamic polymer systems

lore — Wed, 03 Dec 2014 14:45:29 +0000

S. Billiet, H. Goossens

ISBN/ISSN:

Talk

Conference / event / venue

Annual IAP meeting

Louvain-la-Neuve, Belgium

Friday, 19 September, 2014

Triazolinediones enabling click and transclick reactions

wim — Mon, 13 Oct 2014 07:13:00 +0000

H. Goossens, S. Billiet, K. De Bruycker, F. Driessen, J.M. Winne, F. Du Prez, V. Van Speybroeck

ISBN/ISSN:

Talk

Conference / event / venue

WATOC 2014

Santiago de Chile, Chile

Sunday, 5 October, 2014 to Friday, 10 October, 2014

Abstract (private)

Abstract_WATOC_2014_HG.pdf

Conference reference

WATOC 2014

Triazolinediones for Irreversible and Reversible Linking in polymers: Theoretical Rationalization

wim — Thu, 26 Sep 2013 13:14:44 +0000

H. Goossens, S. Billiet, K. De Bruycker, F. Driessen, J.M. Winne, F. Du Prez, V. Van Speybroeck

ISBN/ISSN: -

Poster

Conference / event / venue

Annual IAP Meeting

Ghent, Belgium

Wednesday, 18 September, 2013

Conference reference

Annual IAP Meeting (2013)