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

28 May 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

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.

Keywords

supramolecular
sequence-defined
polymerization
pressure-induced polymerization
carbon nanothreads
Diels-Alder
polymer

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.