期刊
POLYMER CHEMISTRY
卷 13, 期 10, 页码 1359-1368出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1py01387d
关键词
-
资金
- Center for Nanothread Chemistry, a National Science Foundation (NSF) Center for Chemical Innovation [CHE-1832471]
Recently discovered diamond nanothreads offer a stiff backbone formed through the solid-state pressure-induced polymerization of simple aromatics, which is unachievable in conventional polymer synthesis. The compression of co-crystals containing -OH and -CHO functional groups reveals the influence of functional group interactions and parallel stacking on the pressure-induced polymerization to form nanothreads.
Recently discovered diamond nanothreads offer a stiff, sp(3)-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 pi-pi stacking 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 pi-pi stacking distance. Nevertheless, the recovered solid with the larger centroid : centroid and centroid : plane pi-pi stacking 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.
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