Near-Infrared Circularly Polarized Luminescence through Intramolecular Excimer Formation of Oligo(p-phenyleneethynylene)-Based Double Helicates.

Carbon-based double helicates consisting of two anthracene-containing oligo(p-phenyleneethynylene) units and two flexible chiral 1,1'-binaphthyl units or two rigid chiral 9,9'-spirobifluorene units were developed. The curved oligo(p-phenyleneethynylene) fragments in the double helicates were successfully constructed by tin-mediated reductive aromatization. Helical oligo(p-phenyleneethynylene) double strands fixed by two rigid spirobifluorene units showed little structural change under photoirradiation, thereby emitting circularly polarized luminescence (CPL) in the visible region with a high quantum yield (ΦPL =0.93). In contrast, flexible binaphthyl units induced dynamic structural change of the oligo(p-phenyleneethynylene) luminophores under photoirradiation, leading to strong CPL (|glum |=1.1×10-2 ) in the near-infrared (NIR) region. UV/Vis, circular dichroism (CD), CPL and NMR spectroscopic analyses of the binaphthyl-hinged double helicate suggested excimer formation between two π-conjugated strands in the excited state. Theoretical calculations highlight the importance of the tightly interlocked excimer structure of the carbon-based double helicate in controlling the angle between the electric and magnetic transition dipole moments for strong NIR CPL generation.