Journal
CHEMICAL SCIENCE
Volume 8, Issue 2, Pages 1040-1045Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6sc02640k
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Funding
- CSIR, India
- CSIR [02(0177)/14/EMR-II]
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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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