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Small angle X-ray scattering (SAXS) studies inpoly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) withvarying conjugation, and polyethylene dioxythiophene complexed with polystyrenesulfonate (PEDOT-PSS) in different solvents have shown the important role ofpi-electron conjugation and solvent-chain interactions in controlling the chainconformation and assembly. In MEH-PPV, by increasing the extent of conjugationfrom 30 to 100 %, the persistence length (l_p) increases from 20 to 66Angstrom. Moreover, a pronounced second peak in the pair distribution functionhas been observed in fully conjugated chain, at larger length scales. Thisfeature indicates that the chain segments tend to self-assemble as theconjugation along the chain increases. In case of PEDOT-PSS, the chains undergosolvent induced expansion and enhanced chain organization. The clusters formedby chains are better correlated in dimethyl sulfoxide (DMSO) solution thanwater, as observed in the scattered intensity profiles. The values of radius ofgyration and the exponent (water: 2.6, DMSO: 2.31) of power-law decay, obtainedfrom the unified scattering function (Beaucage) analysis, give evidence forchain expansion from compact (in water) to extended coil in DMSO solutions,which is consistent with the Kratky plot analysis. The mechanism of thistransition and the increase in dc conductivity of PEDOT-PSS in DMSO solutionare discussed. The onset frequency for the increase in ac conduction as well asits temperature dependence probes the extent of connectivity in PEDOT-PSSsystem. The enhanced charge transport in PEDOT-PSS in DMSO is attributed to theextended chain conformation as observed in SAXS results.

Modified conformation and physical properties in conducting polymers due to varying conjugation and solvent interactions