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

RIS ID

131175

Publication Details

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.

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.

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Link to publisher version (DOI)

http://dx.doi.org/10.1016/j.saa.2018.10.022