@article{d33c08d40bd7458698dc0149d62fa95f,
title = "'Sacrificial' supramolecular assembly and pressure-induced polymerization: Toward sequence-defined functionalized nanothreads",
abstract = "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.",
author = "Gerthoffer, {Margaret C.} and Sikai Wu and Bo Chen and Tao Wang and Steven Huss and Oburn, {Shalisa M.} and Crespi, {Vincent H.} and Badding, {John V.} and Elizabeth Elacqua",
note = "Funding Information: This work was funded by the Center for Nanothread Chemistry, a National Science Foundation (NSF) Center for Chemical Innovation (CHE-1832471). We acknowledge Prof. Roald Hoffmann for helpful insights and discussions throughout the project and construction of this manuscript. We sincerely thank the HPCAT beamline staff (particularly Dr Changyong Park, Dr Dmitry Popov, and Dr Jesse Smith) at the Advanced Photon Source in Argonne National Laboratory for their guidance at 16-BM-D. We thank Hemant Yennawar for his assistance in collection of the co-crystal X-ray diffraction. The Materials Characterization Laboratory in the Materials Research Institute at the Pennsylvania State University was used to collect Infrared, as well as XPS with the assistance of Jeffery Shallenberger. We acknowledge the computing resource provided by the Extreme Science and Engineering Discovery Environment (XSEDE) Comet cluster at the San Diego Supercomputer Center through allocation CHE180059. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",
year = "2020",
month = nov,
day = "14",
doi = "10.1039/d0sc03904g",
language = "English (US)",
volume = "11",
pages = "11419--11424",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "42",
}