π-conjugated polymers prepared by organometallic polycondensation and metal complexes of the polymers

Organometallic dehalogenative polycondensation of dihaloaromatic compounds produces various pi -conjugated polymers. pi -Conjugated polynzers with nitrogen in the aromatic ring form metal complexes, and regioregular pi -conjugated polymers such as head-to-tail poly(3-hexylthiophene-2,5-diyl) (HT-P3HexTh), form a stacked structure. New examples are given in this paper. Poly(1,5-naphthyridine-2,6-diyl) (P(2,6-Nap)) formed a complex with Ru(bpy)(2)(2+) (bpy = 2,2'-bipyridine). The molar ratio between the monomeric unit and Ru(bpy)(2)(2+) in the formed complex was about 1:1, and the complex showed overlapped absorption bands in the region 370-460 nm. Dehalogenative polycondensation of a porphyrinatozinc(II complex having two 5-bromo-2-thienyl units at the 5,15-positions gave a two porphyrinatozinc(II) polymer. The polymer exhibited a strong B absorption band at 416 nm and two weak Q bands at 546 and 584 nm. The polymer emitted light at the onset position of the Q bands (591 nm) when irradiated with 424 nm UV light this result indicated occurrence of a transfer of energy absorbed at the B band to an excited state concerned with the Q bands. A cast polymer film was electrochemically active both in the oxidation and reduction regions. Electrochemically p-doped and HT-P3HexTh formed a stacked stacked structure, similar to neutral HT-P3HexTh. The p-doped HT-P3HexTh (dopant BF4- showed mt electrical conductivity of 7.3 x 10(-3) S cm(-1) at room temperature. Copyright (C) 2000 John Wiley & Sons, Ltd.