<i>S</i>,<i>N</i>‑Heteroacene-Based Copolymers for Highly Efficient Organic Field Effect Transistors and Organic Solar Cells: Critical Impact of Aromatic Subunits in the Ladder π‑System

Three novel donor–acceptor alternating polymers containing ladder-type pentacyclic heteroacenes (<b>PBo</b>, <b>PBi</b>, and <b>PT</b>) are synthesized, characterized, and further applied to organic field effect transistors (OFETs) and polymer solar cells. Significant aspects of quinoidal characters, electrochemical properties, optical absorption, frontier orbitals, backbone coplanarity, molecular orientation, charge carrier mobilities, morphology discrepancies, and the corresponding device performances are notably different with various heteroarenes. <b>PT</b> exhibits a stronger quinoidal mesomeric structure, linear and coplanar conformation, smooth surface morphology, and better bimodal crystalline structures, which is beneficial to extend the π-conjugation and promotes charge transport via 3-D transport pathways and in consequence improves overall device performances. Organic photovoltaics based on the <b>PT</b> polymer achieve a power conversion efficiency of 6.04% along with a high short-circuit current density (<i>J</i>_SC) of 14.68 mA cm^–2, and a high hole mobility of 0.1 cm² V^–1 s^–1 is fulfilled in an OFET, which is superior to those of its counterparts, <b>PBi</b> and <b>PBo</b>