Orthogonal Supramolecular Assemblies Using Side-Chain Functionalized Helical Poly(isocyanide)s

Mimicking the structure of proteins using synthetic polymersrequiresbuilding blocks with structural similarity and the use of variousnoncovalent and dynamic covalent interactions. We report the synthesisof helical poly-(isocyanide)-s bearing diaminopyridine and pyridineside-chains and the multistep functionalization of the polymers'side-chains using hydrogen bonding and metal coordination. The orthogonalityof the hydrogen bonding and metal coordination was proved by varyingthe sequence of the multistep assembly. The two side-chain functionalizationsare reversible through the use of competitive solvents and/or competingligands. Throughout the assembly and disassembly, the helical conformationof the polymer backbone is sustained as proved by circular dichroismspectroscopy. These results open the possibility to incorporate helicaldomains into complex polymer architectures and create a helical scaffoldfor smart materials.