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Abstract Radical chemistries have attracted burgeoning attention due to their intriguing technological applications in organic electronics, optoelectronics, and magneto‐responsive systems. However, the potential of these magnetically active glassy polymers to transport spin‐selective currents has not been demonstrated. Here, the spin‐transport characteristics of the radical polymer poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl) (PTEO) allow for sustained spin‐selective currents when incorporated into typical device geometries with magnetically polarized electrodes. Annealing thin films of PTEO above its glass transition temperature results in a giant magnetoresistance effect (i.e., an MR of ≈80%) at 4 K. Additionally, ferromagnetic resonance spin‐pumping results in a relatively large effective spin‐mixing conductance of 1.18 × 10¹⁹m⁻²at the NiFe/PTEO interface. Due to the large spin‐density and radical‐radical exchange interactions, there is effective propagation of pure spin currents through PTEO in the NiFe/PTEO/Pd multilayer devices. This results in the transport of spin current over long distances with a spin diffusion length of 90.4 nm. The spin diffusion length and spin mixing conductance values surpass those reported in inorganic and metallic systems and are comparable to conventional doped conjugated polymers. This is the first example of spin transport in a nonconjugated radical polymer, and these findings underscore the promising spin‐transporting potential of radical polymers. 

Abstract Conductive polymers largely derive their electronic functionality from chemical doping, processes by which redox and charge‐transfer reactions form mobile carriers. While decades of research have demonstrated fundamentally new technologies that merge the unique functionality of these materials with the chemical versatility of macromolecules, doping and the resultant material properties are not ideal for many applications. Here, it is demonstrated that open‐shell conjugated polymers comprised of alternating cyclopentadithiophene and thiadiazoloquinoxaline units can achieve high electrical conductivities in their native “undoped” form. Spectroscopic, electrochemical, electron paramagnetic resonance, and magnetic susceptibility measurements demonstrate that this donor–acceptor architecture promotes very narrow bandgaps, strong electronic correlations, high‐spin ground states, and long‐range π‐delocalization. A comparative study of structural variants and processing methodologies demonstrates that the conductivity can be tuned up to 8.18 S cm⁻¹. This exceeds other neutral narrow bandgap conjugated polymers, many doped polymers, radical conductors, and is comparable to commercial grades of poly(styrene‐sulfonate)‐doped poly(3,4‐ethylenedioxythiophene). X‐ray and morphological studies trace the high conductivity to rigid backbone conformations emanating from strong π‐interactions and long‐range ordered structures formed through self‐organization that lead to a network of delocalized open‐shell sites in electronic communication. The results offer a new platform for the transport of charge in molecular systems.