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<p>Excited-state intramolecular proton transfer (ESIPT) plays a critical role in many chemical processes, and it is essential to develop diverse regulating mechanisms of ESIPT molecules. Herein we report control of ESIPT luminogens with the combination of competing dynamic covalent bonds and non-covalent hydrogen bonds. The incorporation of amino-containing ESIPT fluorophores into 2-formylbenzenesulfonamide offers a versatile platform for dictating reactivity and fluorescence. The competition between intramolecular hydrogen bonding of sulfonamide NH and dynamic ring-fusion of NH with nearby aldehyde site in ring-chain tautomers enables diverse emission of cyclic hemiaminal, ketoimine upon ESIPT, and anionic intramolecular charge transfer (ICT) band in solution. Dynamic covalent reactions with amines give luminogen-dependent ketoimine or ICT emission, with hydrogen bonding from imine nitrogen affecting proton transfer of sulfonamide. In the solid state of one luminogen the engagement of adjacent aldehyde for intramolecular hydrogen bonding affords ICT emission while higher energy excitation induced ketoimine emission. Mechanical grinding and acid fuming treatment allows structural conversion and cyclic hemiaminal/ketoimine emission, further achieving switch of multistate emission colors. Finally, dynamic covalent reactions with amino acids provide a facile way for tuning distinct emission in the solution and solid state. The results should find broad utility in molecular switches, chemical sensing, and intelligent materials.</p>

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Excited-state intramolecular proton transfer luminogens regulated by competing dynamic covalent bonds and hydrogen bonds

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月25日

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  • Fa Zhong,
  • Hebo Ye,
  • Hanxun Zou,
  • Jieyun Huang,
  • Lei You

摘要

Excited-state intramolecular proton transfer (ESIPT) plays a critical role in many chemical processes, and it is essential to develop diverse regulating mechanisms of ESIPT molecules. Herein we report control of ESIPT luminogens with the combination of competing dynamic covalent bonds and non-covalent hydrogen bonds. The incorporation of amino-containing ESIPT fluorophores into 2-formylbenzenesulfonamide offers a versatile platform for dictating reactivity and fluorescence. The competition between intramolecular hydrogen bonding of sulfonamide NH and dynamic ring-fusion of NH with nearby aldehyde site in ring-chain tautomers enables diverse emission of cyclic hemiaminal, ketoimine upon ESIPT, and anionic intramolecular charge transfer (ICT) band in solution. Dynamic covalent reactions with amines give luminogen-dependent ketoimine or ICT emission, with hydrogen bonding from imine nitrogen affecting proton transfer of sulfonamide. In the solid state of one luminogen the engagement of adjacent aldehyde for intramolecular hydrogen bonding affords ICT emission while higher energy excitation induced ketoimine emission. Mechanical grinding and acid fuming treatment allows structural conversion and cyclic hemiaminal/ketoimine emission, further achieving switch of multistate emission colors. Finally, dynamic covalent reactions with amino acids provide a facile way for tuning distinct emission in the solution and solid state. The results should find broad utility in molecular switches, chemical sensing, and intelligent materials.