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Crystallization-Induced Emission Enhancement or Quenching? Elucidating the Mechanism behind Using

Yutong Shang1, Yalei Ma1, Qiangbazhuoma1

  • 1Institute of New Concept Sensors and Molecular Materials, Key Laboratory of Applied Surface and Colloids Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, People's Republic of China.

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Summary

Predicting optical properties of fluorescent dyes in crystals is difficult. This study reveals how molecular conformation and packing influence fluorescence, enabling new applications in information encryption.

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Area of Science:

  • Materials Science
  • Photochemistry
  • Crystallography

Background:

  • Predicting optical properties of fluorescent dyes, particularly in crystalline states, remains a significant challenge due to complexities in molecular conformation, packing, and intermolecular coupling.
  • Understanding these factors is crucial for designing advanced luminescent materials with tailored optical characteristics.

Purpose of the Study:

  • To elucidate the critical roles of molecular conformation and packing in dictating the fluorescence emissions of crystalline materials.
  • To investigate the mechanisms behind crystallization-induced emission enhancement and quenching in homologous fluorophores.
  • To demonstrate the potential application of these crystalline materials in information encryption.

Main Methods:

  • Synthesis of two homologous fluorophores, Ph-MP and Ph-HP.
  • Experimental characterization of their optical properties in crystalline states.
  • Theoretical calculations to analyze molecular conformation, packing, and their influence on fluorescence.
  • Demonstration of information encryption using single-molecule-based versatile crystals.

Main Results:

  • Both synthesized fluorophores exhibited crystallization-induced emission enhancement and quenching.
  • The fluorescence behavior in the solid state was found to be dependent on distinct factors for each homologue.
  • Emission in Ph-MP crystals was governed by the twisted intramolecular charge transfer (TICT) effect.
  • Emission in Ph-HP crystals was primarily influenced by π-π stacking interactions.
  • Successful demonstration of information encryption utilizing the unique properties of these single-molecule-based crystals.

Conclusions:

  • Molecular conformation and packing are decisive factors controlling fluorescence emissions in crystalline materials.
  • The specific mechanisms (TICT vs. π-π stacking) governing fluorescence vary even between homologous compounds.
  • This understanding provides a pathway for developing high-performance luminescent materials.
  • The developed crystalline materials show promise for applications in advanced information encryption technologies.