AbstractThe photophysical properties of near-infrared (NIR) emissive aza-boron-dipyrromethene (aza-BDP) dyes incorporating nitrofluorene and alkoxy decorations were intensively investigated. Their highly reversible one-electron reduction process showed characteristic electrofluorochromic (EF) properties in the NIR range, depending on the substituents. The nitrofluorene ethynyl-substituted (Type I) dyes showed smaller EF effects than the alkoxy-containing (Type II) dyes because of the difference in their intrinsic fluorescence contrast between the neutral and reduced states (radical anion). In addition, the Type II chromophores showed a larger diffusion coefficient for ion transport, which enhanced the EF contrast and the response time for the fluorescence change at a given step potential. With an optimized condition, the NIR EF ON/OFF ratio reached a value of 6.1 and a long cyclability over 1000 EF cycles between −0.4 V and +0.4 V switching potentials, with approximately 20% loss of the initial ON/OFF switching ratio. The NIR EF switching was visually observed through a visible light cut-off filter, featuring high fluorescence contrast.