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We present a [Ru(bpy)₂(dmbpy)]²⁺- and pyrene-based photocatalytic PMMA that enables photoredox-energy transfer to achieve the C–H arylation of electron deficient aryl bromides.

 

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 π–π 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 π–π stacking distance. Nevertheless, the recovered solid with the larger centroid : centroid and centroid : plane π–π 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. 

A halogen-bonded eight-fold interpenetrated diamondoid net was constructed employing a node generated in the solid state. Specifically, co-crystallization of a tetrahedral-like tecton, rctt -tetrakis(4-pyridyl)cyclobutane (4,4′-TPCB), combined with a rigid halogen-bond donor, 1,4-diiodoperchlorobenzene, achieved a diamondoid architecture. In the co-crystal, 4,4′-TPCB is found to form three types of linkages based on one cis - and two trans -orientations enabled by the intrinsic rctt -stereochemisty of the central cyclobutane ring. Thus, 4,4′-TPCB is able to adapt to the constraints of the diamondoid net owing to the flexibility of the pendant 4-pyridyl groups. 

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 sp 3 -hybridized nanothreads from sp 2 -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.