Iodoperfluoroalkanes as structure-directing agents for polymer self-assembly

Supramolecular polymers are formed by self-assembly of tailored building blocks through noncovalent interactions. The choice of strong unidirectional interactions can lead to shape-persistent nanostructures with a high degree of internal order and new functionalities respect to similar covalent polymers. Recently, halogen bonding (XB) has proven to be one of the most effective way to assemble halogenated organic compounds and polymers with suitable electron-donor groups into stable macromolecular structures. Fluorination of the molecular backbone of certain halogenated building blocks enhances their ability to work as halogen bonding donors, giving rise to particularly strong interactions. Herein, we show that XB strength and directionality, coupled with the segregation tendency of perfluoroalkyl and alkyl chains, might open the way to several new possibilities for structure control and molecular imprinting of polymeric materials, as well as for the tuning of their functional properties. Moreover, fluorinated XB-donors can be highly effective also for light-induced surface patterning applications, showing potential for numerous applications in photonics and nanotechnology.