'Sacrificial' supramolecular assembly and pressure-induced polymerization: Toward sequence-defined functionalized nanothreads

Margaret C. Gerthoffer, Sikai Wu, Bo Chen, Tao Wang, Steven Huss, Shalisa M. Oburn, Vincent H. Crespi, John V. Badding, Elizabeth Elacqua

Research output: Contribution to journalArticlepeer-review

19 Scopus citations


Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence 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 of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous -OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto-enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.

Original languageEnglish (US)
Pages (from-to)11419-11424
Number of pages6
JournalChemical Science
Issue number42
StatePublished - Nov 14 2020

All Science Journal Classification (ASJC) codes

  • General Chemistry


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