Efficient, high-yield route to long, functionalized p-phenylene oligomers containing perfluorinated segments, and their cyclodimerizations by zirconocene coupling

Linear oligophenylene diynes containing 6, 9, and 12 phenylene rings were s ynthesized in high yields using the nucleophilic aromatic substitution (SNA r) of perfluoroarenes by aryllithium reagents as the key carbon-carbon bond -forming reaction. This reaction was demonstrated to proceed readily at tow temperatures with sterically hindered substrates and in the presence of ba se-sensitive silylalkynyl groups. Diynes synthesized by this methodology we re readily zirconocene-coupled into large dimeric macrocycles using the zir conocene reagent Cp2Zr(py)(Me3SiC=CSiMe3).