Solid State Assemblies and Photophysical Characteristics of Linear and Bent-Core π-Conjugated Oligophenylenevinylenes

Abstract

New classes of luminescent linear, bent-core, and star-shaped oligophenylenevinylenes (OPVs) having 1,4-para and 1,3-meta rigid aromatic cores were designed and developed. 3-Pentadecylphenol, a renewable resource molecule, was chosen as the flexible unit at the longitudinal or middle position of the OPV aromatic core for solid state ordering. Depending upon the nature of the π-core, the OPVs exhibited either mosaic-type liquid crystalline textures or spherulitic crystalline solids. The enthalpies of melting transitions revealed that the bent-core OPV structure showed enhanced solid state packing compared to linear or star-shaped OPVs. Small and wide-angle X-ray diffraction analysis confirmed layered-like assemblies in OPV molecules. Photophysical experiments such as excitation, emission, and time-resolved fluorescence decay dynamics were carried out to trace the molecular self-organization of OPV chromophores. Time correlated single photon counting technique (TCSPC) luminescent decay profiles and decay lifetimes (τ1 and τ2 values) revealed that the OPV chromophores showed faster exciton decay in the tightly packed bent-core structure. The weakly packed star-shaped OPV showed enhanced excited state luminescence stability up to 10 ns. A direct correlation between the OPV chemical structure, solid state ordering, and photophysical characteristics was established.