Harmonizing Energies: The Interplay Between a Nonplanar SalEn‐Type Molecule and a TEMPO Moiety in a New Hybrid Energy‐Storing Redox‐Conducting Polymer.

Redox‐conducting polymers based on SalEn‐type complexes have attracted considerable attention due to their potential applications in electrochemical devices. However, their charge transfer mechanisms, physical and electrochemical properties remain unclear, hindering their rational design and optimization. This study aims to establish the influence of monomer geometry on the polymer's properties by investigating the properties of novel nonplanar SalEn‐type complexes, poly[N,N'‐bis(salicylidene)propylene‐2‐(hydroxy)diaminonickel(II)], and its analog with 2,2,6,6‐tetramethylpiperidinyl‐N‐oxyl (TEMPO)‐substituted bridge (MTS). To elucidate the charge transfer mechanism, operando UV–Vis spectroelectrochemical analysis, electrochemical impedance spectroscopy, and electron paramagnetic resonance are employed. Introducing TEMPO into the bridge moiety enhanced the specific capacity of the poly(MTS) material to 95 mA h g−1, attributed to TEMPO's and conductive backbone's charge storage capabilities. Replacement of the ethylenediimino‐bridge with a 1,3‐propylenediimino‐ bridge induced significant changes in the complex geometry and material's morphology, electrochemical, and spectral properties. At nearly the same potential, polaron and bipolaron particles emerged, suggesting intriguing features at the overlap point of the electroactivity potentials ranges of polaron–bipolaron and TEMPO, such as a disruption in the connection between TEMPO and the conjugation chain or intramolecular charge transfer. These results offer valuable insights for optimizing strategies to create organic materials with tailored properties for use in catalysis and battery applications. [ABSTRACT FROM AUTHOR]