We report a unique dynamic morphology transformation of a Ag +coordinated supramolecular nanostructure accompanying the conversion of complex structures in aqueous solution. In the presence of AgNO 3 (1.0 equiv), the achiral bipyridine-based ligand 1G, possessing hydrazine and glycine moieties, preferentially generated a 1D needle-like structure (nanostructure I) based on the 1GAgNO 3 complex (1G:Ag + = 1:1) as a metastable product. Nanostructure I was then transformed into nanostructure II, which was composed of the 1G 3 Ag 2 (NO 3 ) 2 complex (1G:Ag + = 3:2) as the thermodynamically stable product. This nanostructure exhibited a 1D helical tubular structure with a uniform diameter via a 2D ribbon as an intermediator, which led to the generation of a circular dichroism (CD) signal with right-handed (P-type) helicity. The observed dynamic transformation was attributed to formation of the thermodynamically favored helical 1G 3 Ag 2 (NO 3 ) 2 complex. In addition, the helical 1G 3 Ag 2 (NO 3 ) 2 complex acted as an initiator in the transformation from the 1D needle-like structure to the 1D helical tube via a 2D ribbon. The enhanced ΔG°value of nanostructure II compared to that of nanostructure I confirmed that nanostructure II is thermodynamically stable. More importantly, the transformation of supramolecular nanostructure I to nanostructure II occurred via an "on" pathway, even though the 1GAgNO 3 complex was converted to the 1G 3 Ag 2 (NO 3 ) 2 complex, which did not involve dissociation from nanostructure I into the monomeric 1GAgNO 3 complex species. In the kinetic study, the NO 3 − anion was found to act as an accelerator for the dynamic transformation from nanostructure I to nanostructure II. This result provides the first example of a dynamic transformation of a 1D needle-like structure into a 1D tubular structure via a 2D ribbon structure, accompanied by the conversion of a complex structure and the generation of a large CD signal for the metallosupramolecular nanostructure. This study may open up new avenues to the understanding of a dynamic morphology transformation process in biological systems.
We report the unique synthesis of chiral supramolecular tri‐ and penta‐BCPs with controllable chirality using kinetically adjusted seeded supramolecular copolymerization in THF and DMSO (99 : 1, v/v). Tetraphenylethylene (d‐ and l‐TPE) derivatives bearing d‐ and l‐alanine side chains formed thermodynamically favored chiral products via a kinetically trapped in monomeric state with a long lag phase. In contrast, achiral TPE‐G containing glycine moieties did not form a supramolecular polymer owing to the energy barrier in its kinetically trapped state. We show that the copolymerization of the metastable states of TPE‐G not only enables the generation of supramolecular BCPs by the seeded living growth method, but also transfers chirality at the seed ends. This research demonstrates the generation of chiral supramolecular tri‐ and penta‐BCPs with B‐A‐B, A‐B‐A‐B‐A, and C‐B‐A‐B‐C block patterns accompanying chirality transfer via seeded living polymerization.
We report the unique synthesis of chiral supramolecular tri-and penta-BCPs with controllable chirality using kinetically adjusted seeded supramolecular copolymerization in THF and DMSO (99 : 1, v/v). Tetraphenylethylene (D-and L-TPE) derivatives bearing D-and L-alanine side chains formed thermodynamically favored chiral products via a kinetically trapped in monomeric state with a long lag phase. In contrast, achiral TPE-G containing glycine moieties did not form a supramolecular polymer owing to the energy barrier in its kinetically trapped state. We show that the copolymerization of the metastable states of TPE-G not only enables the generation of supramolecular BCPs by the seeded living growth method, but also transfers chirality at the seed ends. This research demonstrates the generation of chiral supramolecular tri-and penta-BCPs with B-A-B, A-B-A-B-A, and C-B-A-B-C block patterns accompanying chirality transfer via seeded living polymerization.
The copolymerization of kinetically trapped states of tetraphenylethylene containing glycine (TPE‐G) and/or D‐/L‐alanine moieties leads to the formation of supramolecular multi‐block copolymers, such as B‐A‐B, A‐B‐A‐B‐A, and C‐B‐A‐B‐C patterns (BCPs; tri‐ and penta‐blocks) by a chain‐growth process. The chirality of the supramolecular BCPs was not only successfully controlled by the chiral seed, but it also transferred to an achiral component during the chain‐growth polymerization, as reported Sung Ho Jung, Jong Hwa Jung et al. in their Research Article (e202300913).
The copolymerization of kinetically trapped states of tetraphenylethylene containing glycine (TPE‐G) and/or D‐/L‐alanine moieties leads to the formation of supramolecular multi‐block copolymers, such as B‐A‐B, A‐B‐A‐B‐A, and C‐B‐A‐B‐C patterns (BCPs; tri‐ and penta‐blocks) by a chain‐growth process. The chirality of the supramolecular BCPs was not only successfully controlled by the chiral seed, but it also transferred to an achiral component during the chain‐growth polymerization, as reported Sung Ho Jung, Jong Hwa Jung et al. in their Research Article (e202300913).
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