Design strategies to synthesize sequence-defined polymers remain fairly limited for industrial-scale applications, often due to complex multi-step syntheses with low reaction tolerances. Recently, a supramolecular approach enabled the synthesis of a sequence-defined sp<sup>3</sup>-saturated copolymer, the diamond nanothread. Alternating copolymer nanothreads are synthesized by the pressure-induced polymerization of stacks of eclipsed aromatic cores to 10s of GPa. Polymerization proceeds through a one-dimensional cycloaddition with reaction outcomes dependent on monomer design. Here, we will discuss efforts to polymerize supramolecular monomers into one-dimensional sp<sup>3</sup> architectures using guided noncovalent interactions to achieve sequence definition. The effort designed monomer pairs favoring nanothread formation through preorganizing desired external functionalities using combined aryl:perfluoroaryl synthons and intermolecular hydrogen bonding of phenol and pentafluorophenol. Our approach realized polymerization being initiated at lower pressures compared to the individual components. The polymerization of supramolecular monomers lends insight toward the further design of complex sequence-specific polymeric nanothreads, with potential toward large-scale industrial syntheses.

Formation of Sequence-Defined Nanothreads through Solid-State Design

ACS Fall 2021

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