Strong and Atmospherically Stable Dicationic Oxidative Dopant

Increasing the doping level of semiconducting polymer using strong dopants is essential for achieving good electrical conductivity. As for p‐dopant, raising the electron affinity of a neutral compound through the dense introduction of electron‐withdrawing group has always been the predominant strategy to achieve strong dopant. However, this simple and intuitive strategy faces extendibility, accessibility, and stability issues for further development. Herein, the use of dicationic state of tetraaryl benzidine (TAB(2+)) in conjunction with bis(trifluoromethylsulfonyl)imide anion (TFSI(−)) as a strong and atmospherically stable p‐dopant (TAB–2TFSI), for which the concept is hinted from a rapid and spontaneous dimerization of radical cation dopant, is demonstrated. TAB–2TFSI possesses a large redox potential such that it would have deteriorated when in contact with H(2)O. However, no trace of degradation after 1 year of storage under atmospheric conditions is observed. When doping the state‐of‐the‐art semiconducting polymer with TAB–2TFSI, a high doping level together with significantly enhanced crystallinity is achieved which led to an electrical conductivity as high as 656 S cm(−1). The concept of utilizing charged molecule as a dopant is highly versatile and will potentially accelerate the development of a strong yet stable dopant.