Lamellar phases of alkyldiacetylenes in which the alkyl chains lie parallel to the substrate represent a straightforward means for scalable 1‐nm‐resolution interfacial patterning. This capability has the potential for substantial impacts in nanoscale electronics, energy conversion, and biomaterials design. Polymerization is required to set the 1‐nm functional patterns embedded in the monolayer, making it important to understand structure–function relationships for these on‐surface reactions. Polymerization can be observed for certain monomers at the single‐polymer scale using scanning probe microscopy. However, substantial restrictions on the systems that can be effectively characterized have limited utility. Here, using a new multi‐scale approach, we identify a large, previously unreported difference in polymerization efficiency between the two most widely used commercial diynoic acids. We further identify a core design principle for maximizing polymerization efficiency in these on‐surface reactions, generating a new monomer that also exhibits enhanced polymerization efficiency.
Integrating functionalized 2D materials into multilayer device architectures increasingly requires understanding the behavior of noncovalently adsorbed ligands during solution processing. Here, we demonstrate that the headgroup dynamics of polymerized monolayers of functional alkanes can be controlled to modify surface wetting and environmental interactions. We find that headgroup dynamics are sensitive to the position of the polymerizable diyne group; thus, the polymerization process, typically used to stabilize the noncovalent monolayer, can also be used to selectively destabilize chain-chain interactions near the headgroups, making the headgroups more solvent-accessible and increasing surface hydrophilicity. Conversely, interactions with divalent ions can be used to tether headgroups in-plane, decreasing surface hydrophilicity. Together, these results suggest a strategy for the rational design of 2D chemical interfaces in which the polymerization step reconfigures the monolayer to promote the desired environmental interactions.
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