Controlling the length of cooperative supramolecular polymers with chain-cappers

Gijs M. ter Huurne; Pongphak Chidchob; Augustin Long; Alexandre Martinez; Anja R A Palmans; Ghislaine Vantomme

doi:10.1002/chem.202001293

Controlling the length of cooperative supramolecular polymers with chain-cappers

Gijs M. ter Huurne, Pongphak Chidchob, Augustin Long, Alexandre Martinez, Anja R A Palmans, Ghislaine Vantomme (Corresponding author)

Research output: Contribution to journal › Article › Academic › peer-review

18 Citations (Scopus)

Abstract

The design and the characterization of supramolecular additives to control the chain length of benzene-1,3,5-tricarboxamide (BTA) cooperative supramolecular polymers under thermodynamic equilibrium is unraveled. These additives act as chain-cappers of supramolecular polymers and feature one face as reactive as the BTA discotic to interact strongly with the polymer-end, whereas the other face is non-reactive and therefore impedes further polymerization. Such a design requires fine tuning of the conformational pre-organization of the amides and the steric hindrance of the motif. The chain-cappers studied are monotopic derivatives of BTA, modified by partial N -methylation of the amides or by positioning of a bulky cyclotriveratrylene cage on one face of the BTA unit. This study not only clarifies the interplay between structural variations and supramolecular interactions, but it also highlights the necessity to combine orthogonal characterization methods, spectroscopy and light scattering, to elucidate the structures and compositions of supramolecular systems.

Original language	English
Pages (from-to)	9964-9970
Number of pages	7
Journal	Chemistry : A European Journal
Volume	26
Issue number	44
Early online date	29 Apr 2020
DOIs	https://doi.org/10.1002/chem.202001293
Publication status	Published - 6 Aug 2020

Funding

This work was financially supported by The Netherlands Organization for Scientific Research (NWO‐TOP PUNT Grant 10018944 and NWO‐VENI Grant 722.017.003) and the Dutch Ministry of Education, Culture and Science (Gravity Program 024.001.035). G.V. thanks Prof. Chidambar Kulkarni for assistance with the DFT calculations. The authors acknowledge Elisabeth Weyandt, Mathijs Mabesoone and Lafayette de Windt for helpful discussions and the ICMS animation studio for the illustrations.

Funders	Funder number
Nederlandse Organisatie voor Wetenschappelijk Onderzoek	10018944
Ministerie van Onderwijs, Cultuur en Wetenschap	024.001.035

Keywords

Chain cappers
cooperative effect
hydrogen bonds
noncovalent interactions
supramolecular polymers

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10.1002/chem.202001293

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abstract = "The design and the characterization of supramolecular additives to control the chain length of benzene-1,3,5-tricarboxamide (BTA) cooperative supramolecular polymers under thermodynamic equilibrium is unraveled. These additives act as chain-cappers of supramolecular polymers and feature one face as reactive as the BTA discotic to interact strongly with the polymer-end, whereas the other face is non-reactive and therefore impedes further polymerization. Such a design requires fine tuning of the conformational pre-organization of the amides and the steric hindrance of the motif. The chain-cappers studied are monotopic derivatives of BTA, modified by partial N -methylation of the amides or by positioning of a bulky cyclotriveratrylene cage on one face of the BTA unit. This study not only clarifies the interplay between structural variations and supramolecular interactions, but it also highlights the necessity to combine orthogonal characterization methods, spectroscopy and light scattering, to elucidate the structures and compositions of supramolecular systems.",

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AU - Chidchob, Pongphak

AU - Long, Augustin

AU - Martinez, Alexandre

AU - Palmans, Anja R A

AU - Vantomme, Ghislaine

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N2 - The design and the characterization of supramolecular additives to control the chain length of benzene-1,3,5-tricarboxamide (BTA) cooperative supramolecular polymers under thermodynamic equilibrium is unraveled. These additives act as chain-cappers of supramolecular polymers and feature one face as reactive as the BTA discotic to interact strongly with the polymer-end, whereas the other face is non-reactive and therefore impedes further polymerization. Such a design requires fine tuning of the conformational pre-organization of the amides and the steric hindrance of the motif. The chain-cappers studied are monotopic derivatives of BTA, modified by partial N -methylation of the amides or by positioning of a bulky cyclotriveratrylene cage on one face of the BTA unit. This study not only clarifies the interplay between structural variations and supramolecular interactions, but it also highlights the necessity to combine orthogonal characterization methods, spectroscopy and light scattering, to elucidate the structures and compositions of supramolecular systems.

AB - The design and the characterization of supramolecular additives to control the chain length of benzene-1,3,5-tricarboxamide (BTA) cooperative supramolecular polymers under thermodynamic equilibrium is unraveled. These additives act as chain-cappers of supramolecular polymers and feature one face as reactive as the BTA discotic to interact strongly with the polymer-end, whereas the other face is non-reactive and therefore impedes further polymerization. Such a design requires fine tuning of the conformational pre-organization of the amides and the steric hindrance of the motif. The chain-cappers studied are monotopic derivatives of BTA, modified by partial N -methylation of the amides or by positioning of a bulky cyclotriveratrylene cage on one face of the BTA unit. This study not only clarifies the interplay between structural variations and supramolecular interactions, but it also highlights the necessity to combine orthogonal characterization methods, spectroscopy and light scattering, to elucidate the structures and compositions of supramolecular systems.

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Controlling the length of cooperative supramolecular polymers with chain-cappers

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Keywords

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