Two-photon isomerization triggers two-photon-excited fluorescence of an azobenzene derivative.

Photoisomerization provides a general means for photo-controlling molecular structure and function, and two-photon induced isomerization has some advantages over one-photon processes. Here, we report the two-photon absorption (TPA) induced optical properties and characteristics of an azobenzene derivative, namely N-(3,4,5-octanoxyphenyl)-N'-4-[(4-hydroxyphenyl)azophenyl]1,3,4-oxadiazole (AOB-t8). With the activation of red light, the photoproduct of cis-AOB-t8 isomers has been unambiguously identified, and the two-photon induced isomerization process of AOB-t8 in THF is characterized with the relevant rate constants of forward and backward reactions. The TPA coefficients and cross-sections of AOB-t8 at different wavelengths, and nonlinear optical refractive index are determined from femtosecond nonlinear optical measurements. Particularly, the results indicate that the two-photon excited emission can be effectively triggered by the two-photon-induced isomerization from trans- to cis-AOB-t8, demonstrating an on-switch from non-fluorescence to visible blue emission. Consistent with the observations from one-photon excitation, we suggest that the enhanced two-photon excited fluorescence of AOB-t8 solution originates from the combined contribution of cis-AOB-t8 monomer and its aggregates, i.e., the conformation transition from trans- to cis-AOB-t8 opens the emission channel and the self-assembly aggregation of cis-AOB-t8 isomers further enhances the fluorescence upon red light excitation.