SynopsisTwo closely related series of polyesters that contain mesogenic units interconnected by flexible spacers along the main chain were prepared and characterized for their liquid crystal properties. All of these polymers showed theotropic behavior, which was examined by DSC, hot-stage microscopy on a polarizing microscope, small-angle light and wide-angle x-ray scattering methods, and visual observation of stir-opalescence of the polymer melts. The effect of the length of the flexible spacer and the nature of the substituent, which is on the central aromatic ring of the mesogenic unit, on the stability and molecular order of the mesophase for each of the polymers was investigated and the results are discussed on the basis of the thermodynamic data obtained.
Interfacial chemistry at organic-inorganic contact critically determines the function of a wide range of molecular and organic electronic devices and other systems. The chemistry is, however, difficult to understand due to the lack of easily accessible in-operando spectroscopic techniques that permit access to interfacial structure on a molecular scale. Herein, we compare two analogous junctions formed with identical organic thin film and different liquid top-contacts (water droplet vs eutectic gallium indium alloy) and elucidate the puzzling interfacial characteristics. Specifically, we fine-tune the surface topography of the organic surface using mixed self-assembled monolayers (SAMs): single component SAM composed of rectifier (2,2'-bipyridyl-terminated n-undecanethiolate; denoted as SCBIPY) is systematically diluted with nonrectifying n-alkanethiolates of different lengths (denoted as SC where n = 8, 10, 12, 14, 16, 18). Characterization of the resulting mixed SAMs in wettability and tunneling currents with the two separate liquid top-contacts allows us to investigate the role of phase segregation and gauche defect in the SAM//liquid interfaces. The results reported here show the difference in length between SCBIPY and SC is translated into nanoscopic pits and gauche-conformer defects on the surface, and the difference in contact force-hydrostatic vs user pressures-and hence conformity of contact account for the difference in wettability and rectification behaviors. Our work provides an insight into the role of molecule-electrode interfacial defects in performance of molecular-scale electronic devices.
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