Supramolecular “sergeants”: in situ and multi-level induction of chirality in helical assemblies of triarylamine trisamide monomers

Abstract

The induction and transmission of chirality across multiple length scales is fundamental to many (bio)chemical processes. For the majority of macromolecular and supramolecular structures adopting a helical configuration, this is harnessed by means of a monomer embedding a stereogenic element, also called a “sergeant” because of its ability to transfer its chirality preference to achiral monomers. Herein, we devise a triarylamine trisamide (TATA) monomer embedding a (thio)urea unit able to interact with a chiral phosphate anion through hydrogen bonding. Thanks to the orthogonal nature of the amide and (thio)urea functions, the anion specifically binds to the (thio)urea unit, thus yielding a supramolecular monomer acting as a “sergeant” i.e. allowing efficient chirality induction in amide-bonded TATA helical copolymers composed of various types of achiral TATA monomers. Unlike covalent “sergeants”, chirality can be induced in situ by binding of the chiral anion to pre-formed coassemblies. In addition, the catalytic performance of TATA coassemblies embedding intrinsically achiral phosphine-functionalized TATA monomers has been evaluated: higher enantioselectivities are reached with the supramolecular versus covalent “sergeant”. Our work may facilitate the design and development of supramolecular “sergeants” as a modular approach to induce chirality in supramolecular helical copolymers and catalysts.