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

Chakraborty, Saptarshi ; Kar, Haridas ; Sikder, Amrita ; Ghosh, Suhrit (2017) Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization Chemical Science, 8 (2). pp. 1040-1045. ISSN 2041-6520

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Official URL: http://doi.org/10.1039/C6SC02640K

Related URL: http://dx.doi.org/10.1039/C6SC02640K

Abstract

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 Ka 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 (TDA ≫ TAA or TDD), 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 TAA following the nucleation-elongation model.

Item Type:Article
Source:Copyright of this article belongs to Royal Society of Chemistry
ID Code:126109
Deposited On:17 Oct 2022 11:35
Last Modified:17 Oct 2022 11:35

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