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Cd(II) enhanced fluorescence and Zn(II) quenched fluorescence with phenylenevinylene terpyridine: A theoretical investigation

Journal Article


Abstract


  • Phenylenevinylene terpyridine (mepvpt) shows chelation enhanced fluorescence (CHEF) with Cd(II) and chelation quenched fluorescence (CHQF) with Zn(II), respectively. To understand the behaviors, we studied their intrinsic optical properties using DFT/TDDFT methods. The results show that fluorescence quantum yields (FQY) of mepvpt, mepvpt-Cd and mepvpt-Zn are low due to high ISC rates from higher excited states rather than the S1 excited state. When mepvpt chelates Cd(II), the molecular structure becomes more planar and S3,4 → S0 radiation rates become higher than that of mepvpt, which results in CHEF. When mepvpt chelates Zn(II), a new S4 → S0 emission with low oscillator strength occurs and high S4 → Tn ISC rates appear, which leads to CHQF. This proposed mechanism of metal fluorescence enhancing/quenching suggests a design strategy for single-molecular multi-analyte sensors.

Authors


  •   Zhang, Zhiyong (external author)
  •   Wang, Chengjun (external author)
  •   Zhang, Zhongzhi (external author)
  •   Luo, Yijing (external author)
  •   Sun, Shanshan (external author)
  •   Zhang, Guangqing

Publication Date


  • 2019

Citation


  • Zhang, Z., Wang, C., Zhang, Z., Luo, Y., Sun, S. & Zhang, G. (2019). Cd(II) enhanced fluorescence and Zn(II) quenched fluorescence with phenylenevinylene terpyridine: A theoretical investigation. Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 209 40-48.

Scopus Eid


  • 2-s2.0-85055025852

Number Of Pages


  • 8

Start Page


  • 40

End Page


  • 48

Volume


  • 209

Place Of Publication


  • Netherlands

Abstract


  • Phenylenevinylene terpyridine (mepvpt) shows chelation enhanced fluorescence (CHEF) with Cd(II) and chelation quenched fluorescence (CHQF) with Zn(II), respectively. To understand the behaviors, we studied their intrinsic optical properties using DFT/TDDFT methods. The results show that fluorescence quantum yields (FQY) of mepvpt, mepvpt-Cd and mepvpt-Zn are low due to high ISC rates from higher excited states rather than the S1 excited state. When mepvpt chelates Cd(II), the molecular structure becomes more planar and S3,4 → S0 radiation rates become higher than that of mepvpt, which results in CHEF. When mepvpt chelates Zn(II), a new S4 → S0 emission with low oscillator strength occurs and high S4 → Tn ISC rates appear, which leads to CHQF. This proposed mechanism of metal fluorescence enhancing/quenching suggests a design strategy for single-molecular multi-analyte sensors.

Authors


  •   Zhang, Zhiyong (external author)
  •   Wang, Chengjun (external author)
  •   Zhang, Zhongzhi (external author)
  •   Luo, Yijing (external author)
  •   Sun, Shanshan (external author)
  •   Zhang, Guangqing

Publication Date


  • 2019

Citation


  • Zhang, Z., Wang, C., Zhang, Z., Luo, Y., Sun, S. & Zhang, G. (2019). Cd(II) enhanced fluorescence and Zn(II) quenched fluorescence with phenylenevinylene terpyridine: A theoretical investigation. Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 209 40-48.

Scopus Eid


  • 2-s2.0-85055025852

Number Of Pages


  • 8

Start Page


  • 40

End Page


  • 48

Volume


  • 209

Place Of Publication


  • Netherlands