The generation of the first persistent radical cation of naphthalenediimide with Cu(2+)/Fe(3+) under ambient conditions is reported. An alternate anionic trigger generates a persistent radical anion within the same motif. Steric protection and H-bonding enhances the half-life of radical cation by 290-fold. The radical anion and cation have orthogonal spin density, panchromatic and NIR optical bands, which can be applied as attractive multichannel probes.