Previously unknown alt-copoly(telluro-1,4-phenylene/azo-1,4-phenylene) and related polymers were synthesized by several different approaches, which include a) reductive polymerization of bis(4-nitrophenyl) tellurides with zinc; b) oxidative polymerization of bis(4-aminophenyl) telluride using a Cu'/Cu" redox system as catalyst under oxygen; c) electrochemical polymerization of bis(4-amino-3,5-dimethylphenyl) telluride; d) condensation polymerization of 1 ,I-dinitrosobenzene with bis(4-aminophenyl) telluride Te,Te-dichloride, and e) condensation polymerization of bis(4-nitrophenyl) telSince the last two decades, organotellurium compounds have been receiving increasing attention as special reagents, organic conductors, and new imaging systems [']. However, the literature contains comparatively few reports on tellurium-containing organic among which poly(ditelluromethy1ene) is of special interest, since it shows a noticeably high conductivity (0 i= S cm-lj upon bromine doping in spite of its non-conjugative aliphatic naturel51. Chemical doping presumably produces the positive holes on tellurium atoms, which are effectively transferred from chain to chain via telluride linkage.On the other hand, poly(azo-1,4-phenylene) and its analogs have been extensively studied and amply reported in the l i t e r a t~r e [~~-~~] .This may be attributed to the fact that these conjugated polymers are expected to display electrical conductivity due to their moderately low band energy gap and their stability towards p-type chemical Polymerization of aromatic diamines to the conductive azo polymer systems has usually been carried out by oxidative ways and the electrical conductivity of the azo polymers obtained reaches up to 0 = lop5 -S cm-I after chemical doping [15,18].With these findings in mind, the idea came to us that the combination of the n,n-conjugative azo, nconjugative 1,4-phenylene, and n-conjugative telluro functions in some alternate way may produce a novel polymer of higher electrical conductivity upon chemical doping because of the joint operation of the intrachain and interchain mechanisms of electrical conduction. However, a synthesis of such polymers has not been realized so far probably because of luride with bis(4-aminophenyl) telluride in the presence of sodium hydroxide. The polymers obtained were characterized by elemental analysis, 13C-CPMAS NMR, IR and UVvis spectroscopy, GPC, and inherent viscosity measurements, and their properties were examined, particularly their electrical conductivity. The electrical conductivities of the new polymers 9b, c and 10 were shown to increase from below lo-? up to S cm-' upon bromine doping in spite of their formally interrupted conjugation structure.the difficult access to appropriate starting materials. We have recently developed a convenient method for the preparation of bis(nitroary1) tellurides by using an in situ generated telluriudcopper couple as the tellurating agent [27]. By use of this new reagent system, a variety of bis(nitroary1) tellurides and hence bis(aminoar...
