Radiative decay channel assessment to understand the sensing mechanism of a fluorescent turn-on Al3+ chemosensor

Manuel A. Treto-Suárez, Yoan Hidalgo-Rosa, Eduardo Schott, Ximena Zarate, Dayan Páez-Hernández

Resultado de la investigación: Article

Resumen

The turn-on luminescent chemosensor [2-Hydroxy-1-naphthaldehyde-(2-pyridyl) hydrazone] (L), selective to Al3+ ions, was studied by means of density functional theory (DFT) and time-dependent-DFT quantum mechanics calculations. The UV-Vis absorption and the radiative channel from the adiabatic S1 excited state were assessed in order to elucidate the selective sensing mechanism of L to Al3+ ions. We found that twisted intramolecular charge transfer (TICT) and photoelectron transfer (PET), which alter the emissive state, are responsible for the luminescence quenching in L. After coordination with Al3+, the TICT is blocked, and PET is no longer possible. So, the emission of the coordination complex is activated, and a fluorescence effect enhanced by chelation is observed. For compounds with Zn2+ and Cd2+, the luminescence quenching is caused by PET, while for Ni2+, ligand to metal charge transfer is the prominent mechanism. To go into more detail, the metal-ligand interaction was analyzed via the Morokuma-Ziegler energy decomposition scheme and the natural orbital of chemical valence.

Idioma originalEnglish
Número de artículoe26083
PublicaciónInternational Journal of Quantum Chemistry
DOI
EstadoAccepted/In press - 1 ene 2019

Huella dactilar

Photoelectrons
Charge transfer
photoelectrons
charge transfer
Density functional theory
Luminescence
Quenching
decay
Metals
quenching
Ions
luminescence
density functional theory
Ligands
Hydrazones
hydrazones
ligands
chelation
Quantum theory
Coordination Complexes

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Citar esto

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title = "Radiative decay channel assessment to understand the sensing mechanism of a fluorescent turn-on Al3+ chemosensor",
abstract = "The turn-on luminescent chemosensor [2-Hydroxy-1-naphthaldehyde-(2-pyridyl) hydrazone] (L), selective to Al3+ ions, was studied by means of density functional theory (DFT) and time-dependent-DFT quantum mechanics calculations. The UV-Vis absorption and the radiative channel from the adiabatic S1 excited state were assessed in order to elucidate the selective sensing mechanism of L to Al3+ ions. We found that twisted intramolecular charge transfer (TICT) and photoelectron transfer (PET), which alter the emissive state, are responsible for the luminescence quenching in L. After coordination with Al3+, the TICT is blocked, and PET is no longer possible. So, the emission of the coordination complex is activated, and a fluorescence effect enhanced by chelation is observed. For compounds with Zn2+ and Cd2+, the luminescence quenching is caused by PET, while for Ni2+, ligand to metal charge transfer is the prominent mechanism. To go into more detail, the metal-ligand interaction was analyzed via the Morokuma-Ziegler energy decomposition scheme and the natural orbital of chemical valence.",
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author = "Treto-Su{\'a}rez, {Manuel A.} and Yoan Hidalgo-Rosa and Eduardo Schott and Ximena Zarate and Dayan P{\'a}ez-Hern{\'a}ndez",
year = "2019",
month = "1",
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doi = "10.1002/qua.26083",
language = "English",
journal = "International Journal of Quantum Chemistry",
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publisher = "John Wiley and Sons Inc.",

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Radiative decay channel assessment to understand the sensing mechanism of a fluorescent turn-on Al3+ chemosensor. / Treto-Suárez, Manuel A.; Hidalgo-Rosa, Yoan; Schott, Eduardo; Zarate, Ximena; Páez-Hernández, Dayan.

En: International Journal of Quantum Chemistry, 01.01.2019.

Resultado de la investigación: Article

TY - JOUR

T1 - Radiative decay channel assessment to understand the sensing mechanism of a fluorescent turn-on Al3+ chemosensor

AU - Treto-Suárez, Manuel A.

AU - Hidalgo-Rosa, Yoan

AU - Schott, Eduardo

AU - Zarate, Ximena

AU - Páez-Hernández, Dayan

PY - 2019/1/1

Y1 - 2019/1/1

N2 - The turn-on luminescent chemosensor [2-Hydroxy-1-naphthaldehyde-(2-pyridyl) hydrazone] (L), selective to Al3+ ions, was studied by means of density functional theory (DFT) and time-dependent-DFT quantum mechanics calculations. The UV-Vis absorption and the radiative channel from the adiabatic S1 excited state were assessed in order to elucidate the selective sensing mechanism of L to Al3+ ions. We found that twisted intramolecular charge transfer (TICT) and photoelectron transfer (PET), which alter the emissive state, are responsible for the luminescence quenching in L. After coordination with Al3+, the TICT is blocked, and PET is no longer possible. So, the emission of the coordination complex is activated, and a fluorescence effect enhanced by chelation is observed. For compounds with Zn2+ and Cd2+, the luminescence quenching is caused by PET, while for Ni2+, ligand to metal charge transfer is the prominent mechanism. To go into more detail, the metal-ligand interaction was analyzed via the Morokuma-Ziegler energy decomposition scheme and the natural orbital of chemical valence.

AB - The turn-on luminescent chemosensor [2-Hydroxy-1-naphthaldehyde-(2-pyridyl) hydrazone] (L), selective to Al3+ ions, was studied by means of density functional theory (DFT) and time-dependent-DFT quantum mechanics calculations. The UV-Vis absorption and the radiative channel from the adiabatic S1 excited state were assessed in order to elucidate the selective sensing mechanism of L to Al3+ ions. We found that twisted intramolecular charge transfer (TICT) and photoelectron transfer (PET), which alter the emissive state, are responsible for the luminescence quenching in L. After coordination with Al3+, the TICT is blocked, and PET is no longer possible. So, the emission of the coordination complex is activated, and a fluorescence effect enhanced by chelation is observed. For compounds with Zn2+ and Cd2+, the luminescence quenching is caused by PET, while for Ni2+, ligand to metal charge transfer is the prominent mechanism. To go into more detail, the metal-ligand interaction was analyzed via the Morokuma-Ziegler energy decomposition scheme and the natural orbital of chemical valence.

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