The isomerization behaviors of 2-(phenylazo)imidazole (Pai-H) and 1-N-methyl-2-(phenylazo)imidazole (Pai-Me) have been investigated. The crystal structure of trans-Pai-Me was determined, revealing that key structures around the azo group are nearly identical among azobenzene, Pai-H, and Pai-Me. Pai-Me undergoes reversible cis/trans photoisomerization, whereas Pai-H responds poorly to irradiation. The quantum yields of trans-to-cis isomerization of Pai-Me on 454 and 355 nm excitation are 0.35 +/- 0.03 and 0.25 +/- 0.03, respectively, in toluene. The wavelength-dependent isomerization quantum yield is well-known for azobenzene, but these values are substantially higher than those of azobenzene. The activation energy of thermal cis-to-trans isomerization of Pai-Me in toluene is 79.0 +/- 3.5 kJ mol(-1), which is lower than that of azobenzene by 15 kJ mol(-1). The thermal cis-to-trans isomerization of Pai-H is even faster. Density functional theory calculations were performed, revealing that the energy gaps between the azo n-orbital and the highest pi-orbital of azoimidazoles are much narrower than that of azobenzene. Finally, a preliminary study suggested that metal ions can modulate the absorption spectrum of Pai-Me without a loss of the gross photochromic behavior.

Several 2- and 3-(phenylazo)pyridine derivatives were prepared. Most of their trans isomers have a large absorption band (∼2 × 104 M−1 cm−1 (1 M = 1 mol dm−3)) around 320 nm and a small absorption band (∼400 M−1 cm−1) around 450 nm. All of these compounds photoisomerize upon irradiation of the shorter (trans-to-cis) and longer (cis-to-trans) wavelength absorption bands. trans Isomers of 3-(phenylazo)pyridines axially coordinate more strongly to Zn–porphyrins than cis isomers, while the opposite is the case for 2-(phenylazo)pyridines, due to steric reasons. These phenylazopyridines quench the fluorescence of Zn–porphyrin upon coordination. These properties were exploited for the light-triggered fluorescence modulation of Zn–porphyrins. Light was irradiated to a mixed solution of phenylazopyridine and Zn–porphyrin to induce photoisomerization of the phenylazopyridine, which underwent association with, or dissociation from, the Zn–porphyrin, resulting in a decrease or increase of Zn–porphyrin fluorescence. For example, the fluorescence intensity of Zn–tetraphenylporphyrin reversibly changed by up to 50%, when 4-methoxy-2-(phenylazo)pyridine was employed.

Modulation of luminescence intensity triggered by light input is demonstrated. The system consists of a Zn–porphyrin and an azopyridine derivative, which axially coordinates to Zn–porphyrin and quenches its fluorescence more efficiently in the trans-form than in the cis-form. Thus, light-induced isomerization of the azopyridine results in the increase/decrease of the porphyrin fluorescence.