Polydiacetylenes (PDAs) form a unique class of polymeric materials that couple highly aligned and conjugated backbones with tailorable pendant side-groups and terminal functionalities. They can be structured in the form of bulk materials, multilayer and monolayer films, polymerized vesicles, and even incorporated into inorganic host matrices to form nanocomposites. The resulting materials exhibit an array of spectacular properties, beginning most notably with dramatic chromogenic transitions that can be activated optically, thermally, chemically, and mechanically. Recent studies have shown that these transitions can even be controlled and observed at the nanometre scale. These transitions have been harnessed for the purpose of chemical and biomolecular sensors, and on a more fundamental level have led to new insights regarding chromogenic phenomena in polymers. Other recent studies have explored how the strong structural anisotropy that these materials possess leads to anisotropic nanomechanical behaviour. These recent advances suggest that PDAs could be considered as a potential component in nanostructured devices due to the large number of tunable properties. In this paper, we provide a succinct review of the latest insights and applications involving PDA. We then focus in more detail on our work concerning ultrathin films, specifically structural properties, mechanochromism, thermochromism, and in-plane mechanical anisotropy of PDA monolayers. Atomic force microscopy (AFM) and fluorescence microscopy confirm that films 1–3 monolayers thick can be organized into highly ordered domains, with the conjugated backbones parallel to the substrate. The number of stable layers is controlled by the head-group functionality. Local mechanical stress applied by AFM and near-field optical probes induces the chromogenic transition in the film at the nanometre scale. The transition involves substantial optical and structural changes in a highly compressed form. Thermochromism is also studied using spectroscopic ellipsometry and fluorescence intensity measurements, and reveals that ultrathin films can reversibly attain an intermediate phase before irreversibly transforming to a final stable state. Further AFM studies also reveal the relation between the highly anisotropic film structure and its nanomechanical properties. In particular, friction at the nanometre scale depends dramatically upon the angle between the polymer backbone and the sliding direction, with the maximum found when sliding perpendicular to the backbones. The observed threefold anisotropy in mechanical dissipation also leads to contrast in the phase response of intermittent-contact AFM, indicating for the first time that in-plane anisotropy of polymeric systems in general can be investigated using this technique.
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