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Kinetically controlled Ag+-coordinated chiral supramolecular polymerization accompanying a helical inversion

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Abstract

We report kinetically controlled chiral supramolecular polymerization based on ligand–metal complex with a 3 : 2 (L : Ag+) stoichiometry accompanying a helical inversion in water. A new family of bipyridine-based ligands (D-L1, L-L1, D-L2, and D-L3) possessing hydrazine and D- or L-alanine moieties at the alkyl chain groups has been designed and synthesized. Interestingly, upon addition of AgNO3 (0.5–1.3 equiv.) to the D-L1 solution, it generated the aggregate I composed of the D-L1AgNO3 complex (D-L1 : Ag+ = 1 : 1) as the kinetic product with a spherical structure. Then, aggregate I (nanoparticle) was transformed into the aggregate II (supramolecular polymer) based on the (D-L1)3Ag2(NO3)2 complex as the thermodynamic product with a fiber structure, which led to the helical inversion from the left-handed (M-type) to the right-handed (P-type) helicity accompanying CD amplification. In contrast, the spherical aggregate I (nanoparticle) composed of the D-L1AgNO3 complex with the left-handed (M-type) helicity formed in the presence of 2.0 equiv. of AgNO3 and was not additionally changed, which indicated that it was the thermodynamic product. The chiral supramolecular polymer based on (D-L1)3Ag2(NO3)2 was produced via a nucleation–elongation mechanism with a cooperative pathway. In thermodynamic study, the standard ΔG° and ΔHe values for the aggregates I and II were calculated using the van't Hoff plot. The enhanced ΔG° value of the aggregate II compared to that of the formation of aggregate I confirms that aggregate II was thermodynamically more stable. In the kinetic study, the influence of concentration of AgNO3 confirmed the initial formation of the aggregate I (nanoparticle), which then evolved to the aggregate II (supramolecular polymer). Thus, the concentration of the (D-L1)3Ag2(NO3)2 complex in the initial state plays a critical role in generating aggregate II (supramolecular polymer). In particular, NO3 acts as a critical linker and accelerator in the transformation from the aggregate I to the aggregate II. This is the first example of a system for a kinetically controlled chiral supramolecular polymer that is formed via multiple steps with coordination structural change.

Graphical abstract: Kinetically controlled Ag+-coordinated chiral supramolecular polymerization accompanying a helical inversion

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Publication details

The article was received on 02 Oct 2019, accepted on 11 Nov 2019 and first published on 14 Nov 2019


Article type: Edge Article
DOI: 10.1039/C9SC04958D
Chem. Sci., 2020, Advance Article
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Kinetically controlled Ag+-coordinated chiral supramolecular polymerization accompanying a helical inversion

    H. Choi, S. Heo, S. Lee, K. Y. Kim, J. H. Lim, S. H. Jung, S. S. Lee, H. Miyake, J. Y. Lee and J. H. Jung, Chem. Sci., 2020, Advance Article , DOI: 10.1039/C9SC04958D

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