Ellipsometric, Microscopic, and Electrochemical Studies of the Electrochemical Polymerization of an Osmium Vinylpyridine Complex

Formation of polymeric films on evaporated Au electrodes by the reductive polymerization of the monomer , where bpy is 2,2'‐bipyridine and vpy is 4‐vinylpyridine, follows a polymerization mechanism characteristic of oligomer formation and precipitation. Evidence for such a mechanism is supported by information obtained from electrochemistry, ultraviolet‐visible and infrared spectroscopies performed during the electrochemical polymerization. The films grow as dense, featureless films up to ca. 100 nm, where they begin to exhibit increasing incidence of surface nodules that contain the same general chemical structures, since infrared spectroscopy of 50 and 200 nm films is the same. There is good agreement between thicknesses determined from single‐wavelength ellipsometry and electrochemistry.