Metallo-Supramolecular Helical Fibres from Chiral Phenylacetylene Monomers: Cation Induced Self-Assembly

Angew Chem Int Ed Engl. 2024 Feb 19;63(8):e202318454. doi: 10.1002/anie.202318454. Epub 2024 Jan 18.

Abstract

Chiral metallo-supramolecular fibres can be easily obtained by mixing a chloroform solution of a phenylacetylene monomer (PA) that bears a chiral sulfoxide group as pendant, with different equivalents of a methanolic solution of AgClO4 . Thus, while the PA is found molecularly dissolved in chloroform, the addition of Ag+ ions induce its aggregation through the formation of an axially chiral metallo-supramolecular aggregate with high thermal stable properties. In this case, the ability of the metal ion to coordinate the PA triple bond, combined with the argentophilicity of the metal ion and the planarity of the phenylacetylene drives to the formation of a helical coordination polymer, whose P or M axial chirality is determined by the chirality of the sulfoxide used as substituent of the PA. Depending on the PA/Ag+ (mol/mol) ratio, it is possible to tune the morphology of the metallo-supramolecular aggregate from chiral fibers to chiral gel.

Keywords: Axial Chirality; Chirality; Circular Dichroism; Coordination Polymer; Metallo-Supramolecular Aggregate.