'Sacrificial' supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized...

Area of Science:

• Supramolecular Chemistry
• Polymer Science
• Materials Science

Background:

• Supramolecular strategies are underutilized for synthesizing sequence-defined polymers.
• Noncovalent interactions are crucial in advanced materials design.
• Developing methods for precise polymer synthesis is essential for new material functionalities.

Purpose of the Study:

• To demonstrate the use of sacrificial aryl-perfluoroaryl supramolecular synthons for synthesizing sequence-defined polymers.
• To create sp³-hybridized nanothreads from sp²-enriched reactants with controlled sequences.
• To introduce exogenous functional groups into nanothread structures.

Main Methods:

• Utilized a phenol:pentafluorophenol co-crystal as an A-B reactant pair for preorganized polymerization.
• Initiated polymerization at high pressure (12 GPa).
• Employed IR spectroscopy to confirm functionalization and elucidate reaction mechanisms.

Main Results:

• Successfully synthesized an alternating copolymer (nanothread) with exogenous -OH functionalities.
• Confirmed external substitution via IR spectroscopy.
• Observed keto-enol tautomerization during cycloaddition, providing mechanistic insights.

Conclusions:

• This work presents the first example of a functionalized nanothread synthesized using supramolecular preorganization.
• The strategy achieves sequence definition through sacrificial synthons.
• The approach offers a new pathway for the *de novo* design of complex nanothreads.