Molecular Dioxygen‐Mediated Passivation of Electron Traps in n‐Type Organic Charge‐Transfer Complexes

The inherent susceptibility of n‐type organic semiconductors to molecular dioxygen (O 2 ) results in electron trapping or in unintended p‐doping, which in turn diminishes their electron mobility. This concept is challenged in the present study by exploring O 2 interactions with organic charge‐transfer complexes (CTCs), where electron donor–acceptor interactions generate partially delocalized electronic states. Using a CTC comprising a phenazine electron donor and a 7,7,8,8‐tetracyanoquinodimethane (TCNQ) electron acceptor, we demonstrate that its exposure to O 2 does not lead to electron extraction but instead enhances the charge‐transfer activity. The increased electron density at the TCNQ acceptor upon CTC exposure to O 2 is attributed to electron trap‐states passivation by O 2 , without evidence of chemisorption. This passivation mitigates recombination losses, resulting in a threefold photoluminescence quantum yield increase, enhanced electrical conductivity, and improved charge‐transfer state efficiency. Similar O 2 ‐mediated conductivity enhancements are observed across additional donor–acceptor pairs, proving the broader applicability of this effect, and paving the way for designing O 2 ‐enhanced advanced organic electronic materials.