Multi-stimuli responsive behavior of two Zn(ii) complexes based on a Schiff base with high contrast

Abstract

A novel fluorescent material that can change its emission properties in response to different external stimuli holds significant importance for the development of sensors, information storage, and encryption materials. In this work, we designed and synthesized two zinc(II) coordination compounds, [Zn(HL)I₂]·CH₃OH (1) and [Zn(HL)Br₂]·CH₃OH (2), which exhibit remarkable changes in their emission properties under three different external stimuli. The two compounds were prepared using a simple one-pot method by reacting zinc(II) salts with 4-(N,N-diphenylamino)benzaldehyde and 3-amino-2-pyridinone. Under the stimulation of NH₃ vapor, both compounds underwent decomposition, leading to a transformation of their fluorescence from yellow to blue, exhibiting a significant blue-shift of more than 170 nm. After exposure to HCl vapor, the fluorescence color of the two original compounds changed from yellow to red, and the color change could be easily distinguished by the naked eye under UV light irradiation. Then after fumigation with NH₃ vapor, the color of both samples changed from red to blue. Based on the high-contrast NH₃-responsive properties and HCl-responsive properties, we designed and developed test papers capable of detecting HCl vapor and NH₃ vapor. Furthermore, due to the transformation from the crystalline state to the amorphous state during grinding, the two compounds also demonstrated high-contrast mechanochromic luminescence properties. After grinding, the color of the two compounds changes significantly from yellow to orange.