Fluorescence Toggling Mechanism of Photochromic Phenylhydrazones: N–N Single Bond Rotation-Assisting E/Z Photoisomerization Differs from Imine

Abstract

Photochromic phenylhydrazones are one of the most promising candidates for a photoswitchable fluorescent probe with potential applications in various fields, but mechanistic understanding of the origin of this unique behavior is limited. In this work, we explored the emission nature and switching mechanism of a model phenylhydrazone-based fluorescent photoswitch, DMA-PHA, by means of TD-DFT and CASPT2 calculations. The fluorescence-emitting Z configuration of DMA-PHA does not involve an excited-state intramolecular proton transfer process since the resonance effect between the DMA group and the rest part of the molecule in the excited state strengthens the hydrogen bond and thus stabilizes the emissive state. The light-induced fluorescence toggling results from E↔Z interconversion driven by an out-of-plane C═N bond torsion and assisted by a N-N single bond rotation, which in total lead to a charge separation process losing the fluorescence activity. The N-N bond rotation in phenylhydrazone further enhances the competitive nonradiative decay and reduces the photoisomerization yields. The theoretical results will provide the guidance for the rational design of novel and improved photoswitchable fluorescent probes with desired performances.