Thermoelectric Performance in Triplet‐Ground‐State Polymer Intrinsically Boosted by Enhanced Proquinoidal Characteristic

Abstract Over the past decade, polymer thermoelectric materials featuring flexibility, lightness, and bio‐friendliness have been paid increasing attention as promising candidates for waste heat recovery and energy generation. For a long time, the dominant approach to optimizing the thermoelectric performance of most organic materials is chemical doping, which, however, is not always ideal for practical applications due to its tendency to involve intricate processing procedure and trigger material and device instability. Currently, the pursuit of single‐component neutral thermoelectric materials without exogenous doping presents a compelling alternative. In this work, we designed and synthesized a high‐spin polymer material, PBBT‐TT, by simultaneously employing thieno[3,4‐ b ]thiophene (T b T) and benzo[1,2‐ c : 4,5‐ c ′]bis[1,2,5]thiadiazole (BBT) units with pronounced proquinoidal characteristics, its analogue, PBBT‐T to demonstrate the effect of the T b T unit was also synthesized. The results indicate that because of the enhanced quinoidal resonance, increased spin density and strong intermolecular antiferromagnetic coupling, PBBT‐TT exhibits high intrinsic electrical conductivity and Seebeck coefficient, which showcases an outstanding power factor of 26.1 μW m −1 K −2 without doping. This achievement surpasses other neutral organic conjugated polymer and radical conductors, and is even comparable to some typical early‐stage doped polymers. Notably, PBBT‐TT exhibits remarkable ambient stability, retaining its initial thermoelectric performance over a 120‐day period. Our finding demonstrates that modulating the intermolecular spin interactions in open‐shell polymers through the introduction of strong proquinoidal units is an effective strategy for the development of doping‐free, intrinsically high‐performance polymer thermoelectric materials.