Mechanistic insights into the pressure-induced polymerization of aryl/perfluoroaryl co-crystals

Margaret C. Gerthoffer, Bohan Xu, Sikai Wu, Jordan Cox, Steven Huss, Shalisa M. Oburn, Steven A. Lopez, Vincent H. Crespi, John V. Badding, Elizabeth Elacqua

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

Recently discovered diamond nanothreads offer a stiff, sp3-hybridized backbone unachievable in conventional polymer synthesis that is formed through the solid-state pressure-induced polymerization of simple aromatics. This method enables monomeric A-B alternation to fully translate from co-crystal design to polymer backbone in a sequence-defined manner. Here, we report the compression of aryl:perfluoroaryl (Ar/ArF) co-crystals containing -OH and -CHO functional groups. We analyze the tolerance of these functional groups to polymerization, explore the possibility of keto-enol tautomerization, and compare the reaction outcomes of targeted solid-state Ar/ArF design on nanothread formation. Two new co-crystals comprising phenol:pentafluorobenzaldehyde (ArOH:ArFCHO) and benzaldehdye:pentafluorophenol (ArCHO:ArFOH) were synthesized through slow solvent evaporation. Analysis of the single-crystal structures revealed different hydrogen bonding patterns between the -OH and -CHO in each solid (tape and orthogonal dimers, respectively), in addition to markedly different π-πstacking distances within the Ar/ArF synthons. In situ Raman spectroscopy was used to monitor the compression of each co-crystal to 21 GPa and illustrated peak shifts for the -OH and -CHO stretching regions during compression. Photoluminescence corresponding to polymerization appeared at a lower pressure for the co-crystal with the smallest π-πstacking distance. Nevertheless, the recovered solid with the larger centroid: centroid and centroid: plane π-πstacking distances featured a diffraction ring consistent with the anticipated dimensions of a co-crystal-derived nanothread packing, indicating that both functional group interactions and parallel stacking affect the pressure-induced polymerization to form nanothreads. IR spectroscopy of the recovered samples revealed large shifts in the -OH & -CHO stretching regions, particularly noticable for ArCHO:ArFOH, which may reflect geometrical constraints associated with forming a rigid thread backbone under pressure. Simulation suggests that hydrogen bonding networks may affect the relative compressibility of the co-crystal along a thread-forming axis to modulate the propensity for nanothread formation.

Original languageEnglish (US)
Pages (from-to)1359-1368
Number of pages10
JournalPolymer Chemistry
Volume13
Issue number10
DOIs
StatePublished - Feb 3 2022

All Science Journal Classification (ASJC) codes

  • Bioengineering
  • Polymers and Plastics
  • Biochemistry
  • Organic Chemistry

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