Effect of Gd3+ ions on the luminescence of opa-Gly

Wierzchaczewski, M.; Sidorowicz, A.; Łukowiak, E.; Stręk, W.; Gawryszewska, Paula

doi:10.1007/bf02606670

Cited by 3 publications

(2 citation statements)

References 5 publications

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“…For this reason, it makes a big difference if the paramagnetic effect is involved or not in calculations. Clearly, this finding suggests that the fluorescence quenching mechanism is not solely dependent on the enhancement of the rate of ISC ( k ISC ) in the paramagnetic metal complexes as reported previously ,− but also on the decrement of the fluorescence emission rate constant k f induced by the paramagnetic effect.…”

Section: Resultssupporting

confidence: 78%

“…Actually, there are a limited number of studies on this topic, and most of them have just ascribed the fluorescence quenching mechanism for the Gd(III) complexes to the significant enhancement of the ISC (S 1 → T 1 ) rate. Nevertheless, the reported reasons of the ISC rate increase for these Gd(III) complexes in the literature are quite confusing and sometimes controversial since the ISC rate enhancement can be caused by anyone of the paramagnetic effect − and the heavy-atom effect − alone or their combination . In other words, a certain conclusion could be drawn that the paramagnetic effect can modify the emission properties of the Gd(III) metal complexes and is different from the heavy-atom effect.…”

Section: Introductionmentioning

confidence: 99%

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Effect of Paramagnetic Open-Shell Gadolinium(III) Texaphyrin on Its Kinetics and Electronic Structures in Fluorescence and Phosphorescence Emission States

Huang

2019

J. Phys. Chem. C

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The paramagnetic effect, which was often found to quench the fluorescence and decrease the phosphorescence radiative lifetime, has not been quantitatively studied for gadolinium(III) complexes that do not have low-lying 4f orbitals. Meanwhile, much attention also needs to be paid to distinguish the paramagnetic effect with the heavy-atom effect, both of which are believed to display a very similar influence on the kinetics of fluorescence and phosphorescence. In this work, a detailed theoretical investigation of the paramagnetic effect observed in earlier experiments for the open-shell gadolinium(III) texaphyrin (Gd-Tex) is given by the time-dependent density functional theory with the 4f-in-valence lanthanide pseudopotential. The results show that the paramagnetic effect is realized by the interaction between Gd(III) 4f and ligand σ excited electrons bridged by the Gd(III) 6s orbital, and the electronic structure of the ligand-centered fluorescence emission state is mixed with the metal-centered ones, which significantly affects the fluorescence quenching mechanism. No such hybrid state is observed in the Gd-Tex phosphorescence spectrum, indicating that the heavy-atom effect should be to blame for the much shorter radiative lifetime of phosphorescence in the paramagnet. The findings in this work help to rationalize the existing experimental data and to promote the potential therapeutic usage of texaphyrins as photosensitizers in the photodynamic therapy.

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Section: Resultssupporting

confidence: 78%

Section: Introductionmentioning

confidence: 99%

Effect of Paramagnetic Open-Shell Gadolinium(III) Texaphyrin on Its Kinetics and Electronic Structures in Fluorescence and Phosphorescence Emission States

Huang

2019

J. Phys. Chem. C

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Spin Exchange Processes Involving Exited Triplet States

Likhtenshtein

2016

Electron Spin Interactions in Chemistry and Biology

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Induced Intersystem Crossing at the Fluorescence Quenching of Laser Dye 7-Amino-1,3-Naphthalenedisulfonic Acid by Paramagnetic Metal Ions

2009

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The fluorescence and triplet state quenching of 7-amino-1,3-naphthalenesulfonic acid by paramagnetic metal ions have been investigated in an aqueous medium. The basic mechanism of the fluorescence quenching involves the static and dynamic electron transfer to the paramagnetic cation. The induced S(1)-->T(1) intersystem crossing at fluorescence quenching of the fluorophore by Cu2+ cation has been found. There is a correlation between triplet state quenching rate constants and values of the efficient paramagnetic susceptibility and spin of the cations. The rate constants for the quenching pathways have been calculated.

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Effect of Gd3+ ions on the luminescence of opa-Gly

Cited by 3 publications

References 5 publications

Effect of Paramagnetic Open-Shell Gadolinium(III) Texaphyrin on Its Kinetics and Electronic Structures in Fluorescence and Phosphorescence Emission States

Effect of Paramagnetic Open-Shell Gadolinium(III) Texaphyrin on Its Kinetics and Electronic Structures in Fluorescence and Phosphorescence Emission States

Spin Exchange Processes Involving Exited Triplet States

Induced Intersystem Crossing at the Fluorescence Quenching of Laser Dye 7-Amino-1,3-Naphthalenedisulfonic Acid by Paramagnetic Metal Ions

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