Synthesis, structures, and photophysical properties of silicon and carbon-bridged ladder oligo(p-phenylenevinylene)s and related π-electron systems

A series of partially or fully fused ladder oligo(p-phenylenevinylene)s (LOPVs) and related π-electron systems has been synthesized. Thus, the intramolecular reductive cyclization of o-silyl-substituted bis(phenylethynyl)benzenes with lithium naphthalenide produces partially silicon-bridged bis(styryl)benzenes consisting of silaindene or disilaindacene skeletons. By combining this cyclization with the Friedel–Crafts type electrophilic cyclization, a homologous series of the fully fused LOPVs and related compounds, bearing silicon and carbon bridges, has been synthesized in fairly good yields. The longest example of the LOPVs is the 13-ring-fused system that has a nearly flat π-conjugated framework with a length of 2.9 nm, as proven by X-ray crystallography. All the produced ladder π-electron systems show intense fluorescence in the visible region with high quantum yields as well as relatively small Stokes shifts. As the silicon contents increase or the disilaindacene skeleton is incorporated, the emission maxima shift to the longer wavelengths and the fluorescent quantum yields slightly decrease. These trends can be rationalized as due to the σ* effect of silicon, wherein the silicon bridges contribute to the electronic structure through σ*–π* orbital interaction that cause the red-shifts in the emission maxima and suppress the radiative decay process from the singlet excited state.