Tuning Intrachain versus Interchain Photophysics via Control of the Threading Ratio of Conjugated Polyrotaxanes

Effective nanoscale control of intermolecular interactions in conjugated polymers is needed for the optimal development and exploitation of the latter in low-cost, large-area consumer electronics items, such as light-emitting and photovoltaic diodes, or transistors. Here we report our investigations on insulated molecular wires constituted by conjugated polymers threaded into cyclodextrin rings. Until now, there has been no detailed quantitative understanding of the role of progressive cyclodextrin encapsulation (quantifiable by the so-called threading ratio, TR, or number of cyclodextrins per repeat unit) in tailoring the photophysics of the conjugated polymeric wires. We combine spectroscopic, electrical and surface analysis techniques to elucidate how the TR of cyclodextrin-threaded molecular wires controls formation of interchain species and related physical properties (0 < TR <= 2.3; the maximum theoretical TR for close-packed CDs is 2.8). Increasing TR enhances the solid-state photoluminescence (PL) and electroluminescence quantum efficiency. To unravel the effect of progressive encapsulation on the intrachain decay kinetics of the polymer backbone, we added an electron-accepting quenching agent, methyl viologen (MV), to the polymer solutions. MV predominantly quenches the aggregate PL, thus enabling measurement of the decay kinetics of the intrinsic exciton even for low-TR polyrotaxanes, for which the different contributions are otherwise difficult to disentangle.