Light-controlled self-assembly and conductance: from nanoribbons to nanospheres

Abstract

Photoswitchable azobenzene (AZO) chromophores were introduced to the bay-position of the traditional n-type perylene diimide (PDI). Photocontrolled self-assembly behaviours and the influence of the azobenzene substitution on the assembly structure were investigated by UV/vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and atomic force microscopy (AFM). Controlled morphological evolution of the nanostructures from ribbons to spheres was facilely realized by driving the azobenzene switching unit with 365 nm light irradiation. The nanoribbons demonstrated highly ordered structures while the order of the molecular arrangement was destroyed in the nanospheres, as a result of the curved molecular conformation induced by photoisomerization. In addition, the conductivity of the single nanoribbon was investigated. Thanks to the one-dimensional long-range ordered π–π stacking of the PDI cores, the nanoribbon showed good semiconducting properties with a conductance in the range of 2 × 10⁻⁵ S m⁻¹ in air. Furthermore, the conductivity decreased with UV light irradiation, mainly due to the increased randomness within the nanostructures, representing the light-induced switching of conductance in the supramolecular systems that is extremely interesting for molecular devices.