Living and stereoselective polymerization of [2.2]‐paracyclophan‐2‐ENE derivatives

Paracyclophene based monomers can be polymerized in a living fashion using the alkylidene initiator Mo(NAr)(CHCMe 2 Ph)(OCMe(CF 3 ) 2 ) 2 . The cis ‐specific nature of the polymerization is critical, since small amounts of trans olefin in the backbone renders the material insoluble. These polymers have complex photophysical behavior, probably a consequence of the close proximity of chromophores along the polymer backbone. Polymerization of 9‐( tert ‐butyldimethylsilyloxy)‐[2.2]‐paracyclophan‐1‐ene produces a new precursor material which furnishes PPV under remarkably mild conditions.