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<p>Dynamic luminescent materials display adaptable emission characteristics when subjected to diverse stimuli, substantially facilitating anti-counterfeiting and encryption applications. However, achieving multi-level information storage and encoding remains a formidable challenge. Herein, two supramolecular isomeric copper-cluster-based metal-organic frameworks (MOFs), {[(Cu<sub>4</sub>I<sub>4</sub>)<sub>3</sub>(TPSA)<sub>4</sub>]·12DMAc}<sub><i>n</i></sub> (<b>1</b>) and {[(Cu<sub>4</sub>I<sub>4</sub>)(TPSA)(CH<sub>3</sub>CN)]·3DEF}<sub><i>n</i></sub> (<b>2</b>), have been successfully synthesized by precisely tuning coordination environments and connection modes of metal clusters. The isomers, constructed by the same building blocks, display different spatial structures, leading to similar steady-state luminescence but distinct stimuli-responsive behaviors. Either thermal or DMSO stimulus induces red-shifted luminescence of complex <b>1</b>, accompanied by a color change from yellow to orange. In contrast, the luminescence of <b>2</b> remains essentially unchanged upon these stimuli. Experimental analyses reveal that the large deformation of the four-connected [Cu<sub>4</sub>I<sub>4</sub>] units in <b>1</b>, including the contraction of Cu–Cu distance and [Cu<sub>4</sub>] core, may be the possible mechanism for the observed redshift in emission. Upon sequential stimulation by light, DMSO, and temperature, smart inks of two MOFs can be effectively implemented in multi-level anti-counterfeiting and logic gates.</p>

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Dynamic luminescence modulation in copper-cluster-based MOFs for advanced anti-counterfeiting applications

  • 期刊论文

  • 发表日期：

    2026年1月27日

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  • Yunfang Zhao,
  • Zhiyuan Wu,
  • Zhijia Li,
  • Jieping Zhang,
  • Hang Lei,
  • Xue Gao,
  • Yongsheng Liu,
  • Feilong Jiang,
  • Lian Chen,
  • Maochun Hong

摘要

Dynamic luminescent materials display adaptable emission characteristics when subjected to diverse stimuli, substantially facilitating anti-counterfeiting and encryption applications. However, achieving multi-level information storage and encoding remains a formidable challenge. Herein, two supramolecular isomeric copper-cluster-based metal-organic frameworks (MOFs), {[(Cu4I4)3(TPSA)4]·12DMAc}n (1) and {[(Cu4I4)(TPSA)(CH3CN)]·3DEF}n (2), have been successfully synthesized by precisely tuning coordination environments and connection modes of metal clusters. The isomers, constructed by the same building blocks, display different spatial structures, leading to similar steady-state luminescence but distinct stimuli-responsive behaviors. Either thermal or DMSO stimulus induces red-shifted luminescence of complex 1, accompanied by a color change from yellow to orange. In contrast, the luminescence of 2 remains essentially unchanged upon these stimuli. Experimental analyses reveal that the large deformation of the four-connected [Cu4I4] units in 1, including the contraction of Cu–Cu distance and [Cu4] core, may be the possible mechanism for the observed redshift in emission. Upon sequential stimulation by light, DMSO, and temperature, smart inks of two MOFs can be effectively implemented in multi-level anti-counterfeiting and logic gates.