Cd(II) enhanced fluorescence and Zn(II) quenched fluorescence with phenylenevinylene terpyridine: A theoretical investigation
2019
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 S 1 excited state. When mepvpt chelates Cd(II), the molecular structure becomes more planar and S 3,4 → S 0 radiation rates become higher than that of mepvpt, which results in CHEF. When mepvpt chelates Zn(II), a new S 4 → S 0 emission with low oscillator strength occurs and high S 4 → T n 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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