| Abstract
| - Preparation and properties of poly(arylamine)sprepared by organometallic polycondensationare described. Dehalogenative polycondensation of4,4‘-dibromodiphenylamine, Br−PhNHPh−Br, witha zerovalent nickel complex affords solublepoly(diphenylamine-4,4‘-diyl), P(DPA)(nBr−PhNHPh−Br +nNi(0)Lm → P(DPA)), withMn and Mw values of 6.4× 103 and 2.0 × 104 and an [η] value of0.66 dL g-1in high yield. P(DPA) has a well-regulated structure and beencharacterized by IR, NMR, and UV−visible spectroscopy, as well as by cyclic voltammetry. The polymershows a π−π* absorption band andphotoluminescence band at 379 and 417 nm, respectively, in NMP.P(DPA) shows two reversible andstable redox cycles at E° = 0.20 and 0.60 V vs Ag/Ag+. Dehalogenative copolymerization ofBr−PhNHPh−Br with 3,5-dibromotoluene, TolBr2, with the zerovalentnickel complex gives random copolymers, P(DPA-ran-Tol), and they behave analogously in the electrochemicalmeasurement. Films of P(DPA) and P(DPA-ran-Tol) exhibit electrochromism during their electrochemicaloxidation, and the P(DPA) film reversiblychanges its color stepwise from light brown to purple through red.P(DPA) shows electrical conductivityof 5 S cm-1 when treated withiodine.
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