Synthesis and Properties of Conjugated Cyclopolymers Bearing Fluorene Derivatives

摘要

Fluorene-containing,spiro-type,conjugated polymers were synthesized via the cyclopolymerization of dipropargylfluorenes (2-substituted,X=H,Br,Ac,NO_2) with various transition metal catalysts.The polymerization of dipropargylfluorenes proceeded well using Mo-based catalysts to give a high polymer yield.The catalytic activities of the Mo-based catalysts were found to be more effective than those of W-based catalysts.The palladium (II) chloride also increased the polymer yield of the polymerization.The polymer structure of poly(dipropargylfluo-rene)s was characterized by such instrumental methods as NMR (~1H-,~(13)C-),1R,UV-visible spectroscopies,and elemental analysis as having the conjugated polymer backbone bearing fluorene moieties.The ~(13)C-NMR spectral data on the quaternary carbon atoms in polymers indicated that the conjugated cyclopolymers have the six-membered rings majorly.The poly(dipropargylfluorene) derivatives were completely soluble in halogenated and aromatic hydrocarbons such as methylene chloride,chloroform,benzene,toluene,and chlorobenzene.The poly(dipropar-gylfluorene) derivatives were thermally more stable than poly(dipropargylfluorene) itself,and X-ray diffraction analyses revealed that the polymers are mostly amorphous.The photoluminescence peaks of the polymers were observed at about 457-491 nm,depending on the substituents of fluorene moieties.