Synthesis, Photophysics, and Langmuir Films of Polyfluorene/Permodified Cyclodextrin Polyrotaxanes

In the present study, we investigated the effect of permodified 2,3,6-tri-O-trimethylsilyl β- and γ-cyclodextrin (TMS·β-CD, TMS·γ-CD) encapsulation on the optical, electrochemical, morphological, and supramolecular arrangements of a poly­[2,7′-(9,9-dioctylfluorene-alt-2′,7-fluorene)] PF copolymer. For this purpose, the photophysical properties and Langmuir monolayer formation of PF·TMS·β-CD and PF·TMS·γ-CD polyrotaxanes were investigated and compared with those of the reference PF. Surface pressure–area isotherms and Brewster angle microscopy studies indicated the capability of both polyrotaxanes to organize into larger and homogeneous 2D supramolecular assemblies at the air–water interface. The obtained results suggest that the presence of the surrounding TMS·β-CD and TMS·γ-CD macrocycles on the PF backbones leads to changes in the conformation and hydrophobicity of the film surfaces. Our investigation offers a method to assess the impact of TMS-CD encapsulation on the control of 2D monolayer formation, with particular attention on the generation of stable PF monolayers for organic electronic devices.