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Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization

The presence of a bulky peripheral wedge destabilizes the homo-assembly of an amide functionalized acceptor (A) monomer and thereby enables the formation of an alternating supramolecular copolymer with an amide appended donor (D) monomer via the synergistic effect of H-bonding and the charge-transfe...

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Autores principales: Chakraborty, Saptarshi, Kar, Haridas, Sikder, Amrita, Ghosh, Suhrit
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5356505/
https://www.ncbi.nlm.nih.gov/pubmed/28451242
http://dx.doi.org/10.1039/c6sc02640k
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author Chakraborty, Saptarshi
Kar, Haridas
Sikder, Amrita
Ghosh, Suhrit
author_facet Chakraborty, Saptarshi
Kar, Haridas
Sikder, Amrita
Ghosh, Suhrit
author_sort Chakraborty, Saptarshi
collection PubMed
description The presence of a bulky peripheral wedge destabilizes the homo-assembly of an amide functionalized acceptor (A) monomer and thereby enables the formation of an alternating supramolecular copolymer with an amide appended donor (D) monomer via the synergistic effect of H-bonding and the charge-transfer (CT) interaction with a remarkably high K (a) of 31 000 M(–1). In sharp contrast, H-bonding driven homo-polymers of A and D are formed by just replacing the bulky chains of the A monomer with linear hydrocarbons. By taking advantage of the clear difference in the critical temperature for the onset of the AA or DD homo-assemblies and DA co-assembly (T (DA) ≫ T (AA) or T (DD)), the supramolecular polymerization pathway of the NDI-monomer could be fully diverted from isodesmic to cooperative in the presence of a small amount of DAN which helped the in situ production of nucleating sites involving the D–A CT-complex at a relatively higher temperature and the subsequent chain growth at T (AA) following the nucleation-elongation model.
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spelling pubmed-53565052017-04-27 Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization Chakraborty, Saptarshi Kar, Haridas Sikder, Amrita Ghosh, Suhrit Chem Sci Chemistry The presence of a bulky peripheral wedge destabilizes the homo-assembly of an amide functionalized acceptor (A) monomer and thereby enables the formation of an alternating supramolecular copolymer with an amide appended donor (D) monomer via the synergistic effect of H-bonding and the charge-transfer (CT) interaction with a remarkably high K (a) of 31 000 M(–1). In sharp contrast, H-bonding driven homo-polymers of A and D are formed by just replacing the bulky chains of the A monomer with linear hydrocarbons. By taking advantage of the clear difference in the critical temperature for the onset of the AA or DD homo-assemblies and DA co-assembly (T (DA) ≫ T (AA) or T (DD)), the supramolecular polymerization pathway of the NDI-monomer could be fully diverted from isodesmic to cooperative in the presence of a small amount of DAN which helped the in situ production of nucleating sites involving the D–A CT-complex at a relatively higher temperature and the subsequent chain growth at T (AA) following the nucleation-elongation model. Royal Society of Chemistry 2017-02-01 2016-09-19 /pmc/articles/PMC5356505/ /pubmed/28451242 http://dx.doi.org/10.1039/c6sc02640k Text en This journal is © The Royal Society of Chemistry 2016 http://creativecommons.org/licenses/by/3.0/ This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Chakraborty, Saptarshi
Kar, Haridas
Sikder, Amrita
Ghosh, Suhrit
Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization
title Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization
title_full Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization
title_fullStr Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization
title_full_unstemmed Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization
title_short Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization
title_sort steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5356505/
https://www.ncbi.nlm.nih.gov/pubmed/28451242
http://dx.doi.org/10.1039/c6sc02640k
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