AI Article Synopsis
- - The study explores the [N···I···N] type halogen bond for creating supramolecular helical polymers using an Ag(I) coordination process, which leads to adjustable supramolecular chirality.
- - Pyridine segments were linked to an asymmetric ferrocene structure to form 1D double helices and 2D helicates, which then organized into 3D porous frameworks with chiral channels and variable pore sizes.
- - The research highlights how changes in solvent can alter the helicity of these polymers, influenced by the movement of the ferrocenyl core and the disruption of intramolecular hydrogen bonds, thus offering techniques for controlling helicity through ionic exchange and solvent conditions.
Article Abstract
The [N···I···N] type halogen bond has been utilized to synthesize supramolecular architectures, while the applications in constructing helical motifs and modulating supramolecular chirality have been unexplored so far. In this work, the [N···I···N] halogen bond was introduced to drive the formation of supramolecular helical polymers via a Ag(I) coordination intermediate, showing tunable supramolecular chirality. Pyridine segments were conjugated to the asymmetric ferrocene skeleton, which show "" and "" geometry depending on the N positions. Coordination with Ag(I) generated one-dimensional (1D) double helices and 2D helicates featured the [Ag(O)···I···Ag(O)] bond, which further stacked into 3D porous frameworks with chiral channels and adjustable pore sizes. Ionic exchange afforded 1D supramolecular helical polymers in solution phases driven by the [N···I···N] type halogen bonds, which was evidenced by the experimental results and density functional theory calculation. exclusively demonstrated tunable supramolecular chirality in the formation of coordinated and halogen bonded polymers. In addition, solvent change would further inverse the helicity of halogen bonded supramolecular helical polymers depending on the rotation of the ferrocenyl core whose "" and "" states were accompanied by the breakage of intramolecular hydrogen bonds. This work introduces a [N···I···N] type ionic halogen bond to prepare supramolecular helical polymers, providing multiple protocols in regulating helicity by ion exchange and solvent environments.
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| http://dx.doi.org/10.1021/acsnano.2c08506 | DOI Listing |
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