Increased luminescence efficiency by synergistic exploitation of lipo/hydrophilic co-solvency and supramolecular design

We use steady-state and time-resolved photoluminescence (PL) spectroscopy to investigate the luminescent properties of a sulfonated poly(diphenylenevinylene) lithium salt (PDV.Li) in water/propanol solutions at different concentrations, with a view to assessing its aggregation behavior. In particular, we compare results from uninsulated PDV.Li and cyclodextrin-threaded PDV.Li polyrotaxane (PDV.Li⊂β-CD). We find that addition of 1-propanol (≥20 weight%) leads to a significant blue-shift (of ∼0.20 eV) of the PL spectra, that we assign to suppressed interchain aggregation in PDV.Li solutions, with a concomitant fourfold increase in the fluorescence quantum efficiency (i.e. from 14 to 60%). Surprisingly, a moderate concentration of propanol increases further the luminescence efficiency even for PDV.Li⊂β-CD, whose supramolecular encapsulation already provides a shield against aggregation. Indeed, addition of propanol reduces the solvent polarity, and therefore helps solubilizing these materials that are still largely aromatic in nature. Interestingly, however, both uninsulated PDV.Li and polyrotaxane solutions exhibit signs of aggregation at high propanol fraction (>70%) with a distinctively weaker coupling than that of interchain states in PDV.Li at high water concentration and in pure water in particular. While we ascribe such behavior to a poor solvation of the polar moieties, we also report a different strength of aggregation for PDV.Li and PDV.Li⊂β-CD that can be attributed to the presence of the cyclodextrin rings. In PDV.Li⊂β-CD hydrogen bonding between the cyclodextrin rings may lead to closer packing between the polymer chains. We therefore suggest that a content of propanol between 30 and 70% provides a good balance of hydrophobic and hydrophilic interactions both for PDV.Li and PDV.Li⊂β-CD.