PERYLENE POLYETHER HYBRIDS - HIGHLY SOLUBLE, LUMINESCENT, REDOX-ACTIVE DYES

A new class of hybrid redox polyether melts has been prepared by coval ent attachment of short polyethylene oxide ''tails'' to perylene, resu lting in highly viscous materials with improved solubility in common s olvents ranging from alcohols to toluene. Solid-state voltammetry of t he neat, undiluted materials is made possible by dissolution of LiClO4 supporting electrolyte in them. The perylene(0/1-) electron self-exch ange rate constants (k(EX)) are large. Temperature studies show that t he energy barrier is also large but that the reactions are adiabatic. The ionic conductivity of the melts was measured to assess the effects of electron migration. The absorption and fluorescence properties of the perylene derivatives in dilute solution are independent of polyeth er tail length, while the fluorescence of thin undiluted films of the hybrids is red-shifted (relative to dilute solution) by ca. 125 nm and is dominated by excimer emission.