Domain-selective thermal decomposition within supramolecular nanoribbons

Self-assembly of small molecules in water provides a powerful route to nanostructures with pristine molecular organization and small dimensions (<10 nm). Such assemblies represent emerging high surface area nanomaterials, customizable for biomedical and energy applications. However, to exploit self-assembly, the constituent molecules must be sufficiently amphiphilic and satisfy prescribed packing criteria, dramatically limiting the range of surface chemistries achievable. Here, we design supramolecular nanoribbons that contain: (1) inert and stable internal domains, and (2) sacrificial surface groups that are thermally labile, and we demonstrate complete thermal decomposition of the nanoribbon surfaces. After heating, the remainder of each constituent molecule is kinetically trapped, nanoribbon morphology and internal organization are maintained, and the nanoribbons are fully hydrophobic. This approach represents a pathway to form nanostructures that circumvent amphiphilicity and packing parameter constraints and generates structures that are not achievable by self-assembly alone, nor top-down approaches, broadening the utility of molecular nanomaterials for new targets. Molecular self-assembly in water is conventionally limited to amphiphilic molecules. This study harnesses sacrificial surface groups and a post-assembly chemical reaction to form nanostructures unachievable by spontaneous self-assembly alone.

Automated summary

By designing supramolecular nanoribbons with inert internal domains and thermally labile sacrificial surface groups, it is possible to achieve thermal decomposition and post-assembly chemical reactions, bypassing traditional amphiphilic constraints and expanding the application range of molecular nanomaterials.