‘Sacrificial’ Supramolecular Assembly and Pressure-Induced Polymerization: Toward Sequence-Defined Functionalized Nanothreads

Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the high utility of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp3-hybridized nanothreads from sp2-enriched reactants. Our strategy features A-B reactant pairs in the form a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The nanothread polymer exhibits crystallinity, as evidenced by a hexagonal X-ray diffraction pattern. The presence of the external substitution is confirmed through IR and Raman spectroscopy. Our approach realizes the first example of a functionalized sequence-defined nanothread through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.