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Synthesis of New Poly(arylamine)s (Aryl = Oligo-p-phenyl or Pyridyl) by Organometallic Polycondensation and Chemical Properties of the Polymers

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journal contribution
posted on 31.10.2006, 00:00 by Masaki Horie, Isao Yamaguchi, Takakazu Yamamoto
A series of poly(arylamine)s formulated as [−(Ar)mNR−]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-phenylene-amine)s, [−(p-C6H4)mN(BOC)−]n (m = 2−4). Deprotection of the BOC group of the polymer at 200 °C gave [−(p-C6H4)mNH−]n (m = 2−4). The polymer behaved as an intermediate polymer between poly(aniline) PAn and poly(p-phenylene) PPP. For example, [−(p-C6H4)2NH−]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-C6H4)4NH-]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 MX2 (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.

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