Photoelectron spectroscopy and photochemistry of tetracyanoethylene radical anion in the gas phase

► Adiabatic electron affinity of C2(CN)4 (TCNE) is 3.16 ± 0.02 eV. ► First direct spectroscopic determination of electron affinity of TCNE. ► Photodissociation of TCNE yields CN, C2(CN)2- and C2(CN)3-.