Polychromatic femtosecond fluorescence studies of metal-polypyridine complexes in solution

Olivier Bräm; Fabrizio Messina; Ahmed M. El-Zohry; Andrea Cannizzo; Majed Chergui

doi:10.1016/j.chemphys.2011.11.022

Polychromatic femtosecond fluorescence studies of metal-polypyridine complexes in solution

Olivier Bräm
, Fabrizio Messina
, Ahmed M. El-Zohry
, Andrea Cannizzo
, Majed Chergui^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

82 Scopus citations

Abstract

Femtosecond-resolved broadband fluorescence studies are reported for[M(bpy) ₃] ²⁺ (M = Fe, Ru), RuN3 and RuN719 complexes in solution. We investigated the pump wavelength dependence of the fluorescence of aqueous [Fe(bpy) ₃] ²⁺ and the solvent and ligand dependence of the fluorescence of Ru-complexes excited at 400 nm. For all complexes, the ¹MLCT fluorescence appears at zero time delay with a mirror-like image with respect to the absorption. It decays in ≤30-45 fs due to intersystem crossing to the ³MLCT states, but a longer lived component of ∼190 fs additionally shows up in RuN719 and RuN3. No solvent effects are detected. The very early dynamics are characterized by internal conversion (IC) and intramolecular vibrational redistribution (IVR) processes on a time scale which we estimate to ≤10 fs using the ¹MLCT lifetime as an internal clock.

Original language	English
Pages (from-to)	51-57
Number of pages	7
Journal	Chemical Physics
Volume	393
Issue number	1
DOIs	https://doi.org/10.1016/j.chemphys.2011.11.022
State	Published - 17 Jan 2012
Externally published	Yes

Bibliographical note

Funding Information:
We thank Dr M.K. Nazeeruddin for providing us with RuN3 and RuN719 samples and for useful discussions. This work was supported by the Swiss NSF via Grants 200021-107956 and 200021-105239 .

Keywords

Fluorescence up-conversion
IVR
Internal conversion
Intersystem crossing
Metal-polypyridine complexes
Ultrafast

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1016/j.chemphys.2011.11.022

Cite this

@article{175670ca68bd4e8db9751b827fbb1a56,

title = "Polychromatic femtosecond fluorescence studies of metal-polypyridine complexes in solution",

abstract = "Femtosecond-resolved broadband fluorescence studies are reported for[M(bpy) 3] 2+ (M = Fe, Ru), RuN3 and RuN719 complexes in solution. We investigated the pump wavelength dependence of the fluorescence of aqueous [Fe(bpy) 3] 2+ and the solvent and ligand dependence of the fluorescence of Ru-complexes excited at 400 nm. For all complexes, the 1MLCT fluorescence appears at zero time delay with a mirror-like image with respect to the absorption. It decays in ≤30-45 fs due to intersystem crossing to the 3MLCT states, but a longer lived component of ∼190 fs additionally shows up in RuN719 and RuN3. No solvent effects are detected. The very early dynamics are characterized by internal conversion (IC) and intramolecular vibrational redistribution (IVR) processes on a time scale which we estimate to ≤10 fs using the 1MLCT lifetime as an internal clock.",

keywords = "Fluorescence up-conversion, IVR, Internal conversion, Intersystem crossing, Metal-polypyridine complexes, Ultrafast",

author = "Olivier Br{\"a}m and Fabrizio Messina and El-Zohry, \{Ahmed M.\} and Andrea Cannizzo and Majed Chergui",

note = "Funding Information: We thank Dr M.K. Nazeeruddin for providing us with RuN3 and RuN719 samples and for useful discussions. This work was supported by the Swiss NSF via Grants 200021-107956 and 200021-105239 .",

year = "2012",

month = jan,

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doi = "10.1016/j.chemphys.2011.11.022",

language = "English",

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T1 - Polychromatic femtosecond fluorescence studies of metal-polypyridine complexes in solution

AU - Bräm, Olivier

AU - Messina, Fabrizio

AU - El-Zohry, Ahmed M.

AU - Cannizzo, Andrea

AU - Chergui, Majed

N1 - Funding Information: We thank Dr M.K. Nazeeruddin for providing us with RuN3 and RuN719 samples and for useful discussions. This work was supported by the Swiss NSF via Grants 200021-107956 and 200021-105239 .

PY - 2012/1/17

Y1 - 2012/1/17

N2 - Femtosecond-resolved broadband fluorescence studies are reported for[M(bpy) 3] 2+ (M = Fe, Ru), RuN3 and RuN719 complexes in solution. We investigated the pump wavelength dependence of the fluorescence of aqueous [Fe(bpy) 3] 2+ and the solvent and ligand dependence of the fluorescence of Ru-complexes excited at 400 nm. For all complexes, the 1MLCT fluorescence appears at zero time delay with a mirror-like image with respect to the absorption. It decays in ≤30-45 fs due to intersystem crossing to the 3MLCT states, but a longer lived component of ∼190 fs additionally shows up in RuN719 and RuN3. No solvent effects are detected. The very early dynamics are characterized by internal conversion (IC) and intramolecular vibrational redistribution (IVR) processes on a time scale which we estimate to ≤10 fs using the 1MLCT lifetime as an internal clock.

AB - Femtosecond-resolved broadband fluorescence studies are reported for[M(bpy) 3] 2+ (M = Fe, Ru), RuN3 and RuN719 complexes in solution. We investigated the pump wavelength dependence of the fluorescence of aqueous [Fe(bpy) 3] 2+ and the solvent and ligand dependence of the fluorescence of Ru-complexes excited at 400 nm. For all complexes, the 1MLCT fluorescence appears at zero time delay with a mirror-like image with respect to the absorption. It decays in ≤30-45 fs due to intersystem crossing to the 3MLCT states, but a longer lived component of ∼190 fs additionally shows up in RuN719 and RuN3. No solvent effects are detected. The very early dynamics are characterized by internal conversion (IC) and intramolecular vibrational redistribution (IVR) processes on a time scale which we estimate to ≤10 fs using the 1MLCT lifetime as an internal clock.

KW - Fluorescence up-conversion

KW - IVR

KW - Internal conversion

KW - Intersystem crossing

KW - Metal-polypyridine complexes

KW - Ultrafast

UR - https://www.scopus.com/pages/publications/84855567552

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DO - 10.1016/j.chemphys.2011.11.022

M3 - Article

AN - SCOPUS:84855567552

SN - 0301-0104

VL - 393

SP - 51

EP - 57

JO - Chemical Physics

JF - Chemical Physics

IS - 1

ER -

Polychromatic femtosecond fluorescence studies of metal-polypyridine complexes in solution

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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