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A non-photochromic diarylethene 2o with an N-phenylaza-15-crown-5 was synthesized. When the nitrogen atom in the aza-crown ring was protonated, it became photochromic due to the prevention of a twisted intramolecular charge transfer (TICT). Although addition of a monovalent metal cation (Li+, Na+, K+, Rb+, Cs+, Cu+, Ag+) in acetonitrile could not stop the TICT so that it was not photochromic, the addition of a multivalent metal cation (Mg2+, Ca2+, Sr2+, Ba2+, Fe2+, Ni2+, Al3+, Sb5+) changed 2o to be photochromic due to the strong attraction of the lone pair on the nitrogen atom. In the presence of excess Cu2+, 2o was oxidized to be EPR-detectable 2o·+, which was thermally unstable as well as inert towards visible-light irradiation. However, 2o·+ was further oxidized to be fairly stable 2o2+ by the irradiation of 365-nm light in the presence of Cu2+. ESI–MS measurements strongly suggested the generation of 2o·+ by mixing 2o with Cu(ClO4)2 in acetonitrile, and the transformation of 2o·+ to 2o2+ by successive 365-nm light irradiation. Fe3+ similarly worked as the oxidant, but the two-step oxidation of 2o to 2o2+ occurred more easily. [ABSTRACT FROM AUTHOR]