Supramolecular Loop Stitches of Discrete Block Molecules on Graphite: Tunable Hydrophobicity by Naphthalenediimide End-Capped Oligodimethylsiloxane

The noncovalent functionalization of surfaces has gained widespread interest in the scientific community, and it is progressively becoming an extremely productive research field offering brand new directions for both supramolecular and materials chemistry. As the end-groups often play a dominant role in the surface properties obtained, creating loops with end-groups only at the surface will lead to unexpected architectures and hence properties. Here we report the self-assembly of discrete block molecules—structures in-between block copolymers and liquid crystals—featuring oligodimethylsiloxanes (ODMS) end-capped with naphthalenediimides (NDIs) at the 1-phenyloctane/highly oriented pyrolytic graphite (1-PO/HOPG) interface. These structures produce unprecedented vertically nanophase-separated monolayers featuring NDI moieties that regularly arrange on the HOPG surface, while the highly dynamic ODMS segments form loops above them. Such arrangement is preserved upon drying and generates hydrophobic HOPG subst...