Molecular organization and doping in poly(2-methoxyaniline)/Ni(dmit)2 films obtained with the Langmuir–Blodgett technique

The control of the properties of materials at the molecular level is pursued for many applications, especially those associated with nanostructures. In this paper, we show that the coordination compound [Ni(dmit)2], where (dmit) is the 1,3-dithiole-2-thione-4,5-dithiolate ligand, can induce doping of poly(2-methoxyaniline) (POMA) in molecularly ordered Langmuir and Langmuir–Blodgett (LB) films. Doping was associated with interactions between the components and the compression of the Langmuir film at the air–water interface, according to polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) data. Taking these results together with in situ UV-Vis absorption measurements, we could identify the molecular groups involved in the interaction, including the way they were reoriented upon film compression. The Langmuir films were sufficiently stable to be transferred as Y-type LB films, while the hybrid POMA/[Ni(dmit)2] films remain doped in the solid state. As expected, the molecular charges affected the film morphology, as observed from combined atomic and electric force microscopy measurements. In summary, with adequate spectroscopy and microscopy tools we characterized molecular-level interactions, which may allow one to design molecular electronic devices with controlled electrical properties.