Dynamic Transformation of a Ag+-Coordinated Supramolecular Nanostructure from a 1D Needle to a 1D Helical Tube via a 2D Ribbon Accompanying the Conversion of Complex Structures.

Abstract

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 AgNO3 (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 1GAgNO3 complex (1G:Ag+ = 1:1) as a metastable product. Nanostructure I was then transformed into nanostructure II, which was composed of the 1G3Ag2(NO3)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 1G3Ag2(NO3)2 complex. In addition, the helical 1G3Ag2(NO3)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 1GAgNO3 complex was converted to the 1G3Ag2(NO3)2 complex, which did not involve dissociation from nanostructure I into the monomeric 1GAgNO3 complex species. In the kinetic study, the NO3- 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 metallo-supramolecular nanostructure. This study may open up new avenues to the understanding of a dynamic morphology transformation process in biological systems.