Department of Chemistry and ‡Weldon School of Biomedical Engineering, Purdue University , West Lafayette, Indiana 47907, United States.
J Am Chem Soc. 2017 Aug 30;139(34):11973-11979. doi: 10.1021/jacs.7b05930. Epub 2017 Aug 18.
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.
将功能化二维材料集成到多层器件结构中，越来越需要了解非共价吸附配体在溶液处理过程中的行为。在这里，我们证明了官能化烷烃聚合单层的头基动力学可以通过控制来改变表面润湿性和环境相互作用。我们发现头基动力学对头基处可聚合二炔基团的位置敏感；因此，聚合过程（通常用于稳定非共价单层）也可用于选择性地破坏靠近头基的链链相互作用，使头基更容易接触溶剂，增加表面亲水性。相反，与二价离子的相互作用可以将头基平面内固定，降低表面亲水性。总之，这些结果表明了一种二维化学界面的合理设计策略，其中聚合步骤重新配置单层以促进所需的环境相互作用。
