The design, synthesis, and electropolymn. of sterically hindered pyrrole derivs. are described. Endo and exo adducts of cyclopentadiene and N-phenylmaleimide were converted to give bicyclo[2.2.1]heptane-fused pyrrole monomers, in which a Ph group is rigidly placed proximate the pyrrole fragment. Oxidative polymn. of these monomers affords highly conductive polypyrroles. The rigid mol. scaffold of the pyrrole monomers limits cross-communication between adjacent conducting strands and produces a defined narrow potential window of high cond. dominated by intrachain polaronic charge carriers. The resultant loosely packed polymer chains allow for superior sensory properties. Notably, the elec. cond. of oxidatively doped poly(7) could be reversibly modulated in aq. electrolytes at pH 3-9. [on SciFinder(R)]