Ananda M. Sarker

Polymerization of 1,4-bis(tetrahydrothiopheniomethyl)-2-cyano-5-methoxybenzene dibromide: synthesis of electronically ‘push-pull’ substituted poly(p-phenylene vinylene)s

Abstract The base-induced polymerization of 1,4-bis(tetrahydrothiopheniomethyl)-2-cyano-5-methoxybenzene dibromide in aqueous acetonitrile yields a soluble polyelectrolyte which may be thermally eliminated to give the electronically ‘push-pull’ substituted poly(2-cyano-5-methoxy-1,4-phenylene vinylene). Ultraviolet-visible and infra-red spectral studies showed production of the conjugated polymer, with a band gap of ca. 2.6–3.0eV (410–480 nm) that varied somewhat as a function of elimination conditions. Elemental analysis indicates some retention of tetrahydrothiophenium side groups in the polyelectrolyte polymer, despite the use of a variety of elimination conditions. The retention of side chains in this synthesis is possibly due to a significant degree of irregularity in the positions of the cyano and methoxy substitutents in the eliminated polymer, resulting from non-regioselectivity in this polymerization. This reaction demonstrates the potential in the Wessling process for polymerization of p-xylylenes that have electronically very asymmetric (‘push-pull’) substitution patterns.

Light emitting poly(para-phenylenevinylene-alt-3-tert butyl-meta-phenylenevinylenes

Abstract Poly(para-phenylenevinylene-alt-3-tert-butyl-meta-phenylenevinylene) was synthesized by Wittig condensation with varying ratio of cis and trans olefin bonds. The luminescent properties of the unisomerized and trans-isomerized polymers (1 and 2, respectively) were compared. Nearly identical emission spectra were observed for both polymers in dilute solutions, but the emission intensity of 1 is lower. This is attributed to the cis vinylic moieties in 1, which favor nonradiative excited state decay processes by limiting formation of a planar excited state. Double layer LEDs with the configuration ITO/PPV/(1 or 2)/Ca–Al were fabricated. Substantially better efficiencies and luminances were observed for devices made with polymer 2 as the emissive layer, by comparison to 1. The results show that the elimination of cis olefin defects in these polymers is important for the optimization of LEDs.