Abstract
A series of poly(arylamine)s formulated as [-(Ar) m NR-] n (Ar = p-phenylene or pyridine-2,5-diyl; m = 2-4; R = H or alkyl) were prepared. Ni- or Pd-promoted dehalogenative polycondensation of the corresponding BOC- (tert-butoxycarbonyl-) substituted dibromo monomers afforded poly(oligo-p-phenyleneamine) s , [-(p-C 6 H 4 ) m N(BOC)-] n (m = 2-4). Deprotection of the BOC group of the polymer at 200 °C gave [-(p-C 6 H 4 NH-] n (m = 2-4). The polymer behaved as an intermediate polymer between poly(aniline) PAn and poly(p-phenylene) PPP. For example, [-(p-C 6 H 4 NH-] n , P(DPA), showed two oxidation peaks at around 0.3 and 0.65 V vs Ag + /Ag with equal intensity in its CV (cyclic voltammetry) chart, similar to PAn; in contrast, the CV chart of [-(p-C 6 H 4 ) 4 NH-] n exhibited a main oxidation peak at 0.60 V vs Ag + /Ag, similar to PPP. ESR data of iodine-doped polymers supported the formation of radical species in oxidation of the polymer. The polymers were photoluminescent and gave quantum yields of 12-46%. Polymers with the pyridine unit formed metal complexes with MX 2 (M = Cu, Ni, Co), and CD (circular dichroism) spectra of the metal complexes of the pyridine polymer having chiral side chains suggested formation of a helical structure by the metal complexation. © 2006 American Chemical Society.