Pierre Evenou, Julien Rossignol, Gaëlle Pembouong, Adélie Gothland, Dmitri Colesnic, Renaud Barbeyron, Sergii Rudiuk, Anne‐Geneviève Marcelin, Mickaël Ménand, Damien Baigl, Vincent Calvez, Laurent Bouteiller, Matthieu Sollogoub

To imitate Nature's ability to form cooperative self-assemblies using entirely artificial molecular tools and to confer them with properties is still a true challenge. Here we show that cyclodextrins bridged with an ammonium linker which bears a hydrophobic substituent efficiently form supramolecular polymers at millimolar concentrations, avoiding the competing self-inclusion and head-to-head processes. Notably, such assembly can occur at micromolecular concentrations in the presence of genomic DNA, resulting in efficient DNA compaction that is reversible upon addition of a competitive guest, and demonstrating their highly cooperative interaction. We finally show that the supramolecular polymer also cooperatively interacts with siRNA and allows its transfection.