Conjugated
polyelectrolytes (CPEs) combine ionic, electronic, and
optical functionality with the mechanical and thermodynamic properties
of semiflexible, amphiphilic polyelectrolytes. Critical to CPE design
is the coupling between macromolecular conformations, ionic interactions,
and electronic transport, the combination of which spans electronic
to mesoscopic length scales, rendering coherent theoretical analysis
challenging. Here, we utilize a recently developed anisotropic coarse-grained
model in combination with a phenomenological tight-binding Hamiltonian
to explore the interplay of single-chain conformational and electronic
structure in CPEs. Accessible single-chain conformations are explored
as a function of solvent conditions and chain stiffness, reproducing
a rich landscape of rod-like, racquet, pearl necklace, and helical
conformations observed in previous works. The electronic structure
of each conformational archetype is further analyzed, incorporating
through-bond coupling, through-space coupling, and electrostatic contributions
to the Hamiltonian. Electrostatics is observed to influence electronic
structure primarily by modifying the accessible conformational space
and only minimally by direct modulation of on-site energies. Electron
transport in CPEs is most efficient in helical and racquet conformations,
which is attributed to the flattening of dihedrals and through-space
coupling within collapsed conformations. Relatedly, kink formation
within racquets does not significantly deteriorate electronic conjugation
within CPEsan insight critical to understanding transport
within locally ordered aggregates. These conclusions provide unprecedented
computational insight into structure function relationships defining
emerging classes of CPEs.