Synthesis,Structure,and Nonlinear Optical Properties of Cross-Conjugated Perphenylated wo-Polydiacetylenes

摘要

Monodisperse,cross-conjugated perphenylated wo-polydiacety-lene(iso-PDA)oligomers,ranging from monomer 15 to pentadecamer 25,have been synthesized by using a palladium-catalyzed cross-coupling protocol.Structural characteristics elucidated by X-ray crystallographic analysis demonstrate a non-planar backbone conformation for the oligomers due to the steric interactions between alkylidene phenyl groups.The electronic absorption spectra of the oligomers show a slight red-shift of the maximum absorption wavelength as the chain length increases from dimer 17 b to pentadecamer 25,a trend that has saturated by the stage of nonamer 22.Fluorescence spectroscopy confirms that the pendent phenyl groups present on the oligomer framework enhance emission,and the relative emission intensity consistently increases as a function of chain length n.The molecular third-order nonlinear-ities,y,for this oligomer series have been measured via differential optical Kerr effect(DOKE)detection and show a superlinear increase as a function of the oligomer chain length n.Molecular modeling and spectroscopic studies suggest that iso-PDA oligomers(">7)adopt a coiled,helical conformation in solution.