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<p>Dynamic phosphorescence holds significant potential for practical applications. However, achieving precise regulation of dynamic luminescence (enhancement or quenching) presents considerable challenges. Herein, a terpyridine-modified bifunctional alkynyl ligand (EPTpy) stabilized copper cluster [Cu<sub>3</sub>(dppm)<sub>3</sub>(EPTpy)<sub>2</sub>]PF<sub>6</sub> (<b>Cu</b><sub><b>3</b></sub>) was synthesized. The <b>Cu</b><sub><b>3</b></sub> cluster, characterized by its terminal coordination sites, facilitates further chelation with Zn<sup>2+</sup> to form a <b>Cu</b><sub><b>3</b></sub><b>-Zn</b> cluster, resulting in a significant red-shift in emission from 535 to 620 nm. It is worth noting that their film quantum yields can be increased over 14-fold compared to crystals, reaching 47.33% (<b>Cu</b><sub><b>3</b></sub>) and 68.63% (<b>Cu</b><sub><b>3</b></sub><b>-Zn</b>), respectively. Both clusters exhibit dynamic phosphorescence behavior, including phosphorescence quenching and enhancement. Specifically, the dynamic phosphorescence quenching originates from the strategically designed EPTpy ligand, triggered by radicals induced photochromism. On the other hand, dynamic photoactivated phosphorescence enhancement is achieved through rapid O<sub>2</sub> consumption via energy transfer between triplet states and molecular oxygen in PMMA thin films, facilitated by the bright emission, large <i>k</i><sub>ISC</sub>, and long intrinsic lifetime. Leveraging this tunable dynamic phosphorescence, a series of patterns was designed for applications in information encryption and storage. This work offers feasible approaches for regulating luminescence and advancing the understanding of the intriguing photophysical properties of clusters.</p>

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Dual-mode dynamic phosphorescence modulation in bifunctional ligand-stabilized copper clusters for information encryption

  • 期刊论文

  • 发表日期：

    2026年3月4日

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  • Fei Xu,
  • Xiang-Ming Zeng,
  • Liao-Yuan Yao,
  • Guo-Yu Yang

摘要

Dynamic phosphorescence holds significant potential for practical applications. However, achieving precise regulation of dynamic luminescence (enhancement or quenching) presents considerable challenges. Herein, a terpyridine-modified bifunctional alkynyl ligand (EPTpy) stabilized copper cluster [Cu3(dppm)3(EPTpy)2]PF6 (Cu3) was synthesized. The Cu3 cluster, characterized by its terminal coordination sites, facilitates further chelation with Zn2+ to form a Cu3-Zn cluster, resulting in a significant red-shift in emission from 535 to 620 nm. It is worth noting that their film quantum yields can be increased over 14-fold compared to crystals, reaching 47.33% (Cu3) and 68.63% (Cu3-Zn), respectively. Both clusters exhibit dynamic phosphorescence behavior, including phosphorescence quenching and enhancement. Specifically, the dynamic phosphorescence quenching originates from the strategically designed EPTpy ligand, triggered by radicals induced photochromism. On the other hand, dynamic photoactivated phosphorescence enhancement is achieved through rapid O2 consumption via energy transfer between triplet states and molecular oxygen in PMMA thin films, facilitated by the bright emission, large kISC, and long intrinsic lifetime. Leveraging this tunable dynamic phosphorescence, a series of patterns was designed for applications in information encryption and storage. This work offers feasible approaches for regulating luminescence and advancing the understanding of the intriguing photophysical properties of clusters.