Symmetry-breaking charge transfer of visible light absorbing systems: Zinc dipyrrins

Cong Trinh; Kent Kirlikovali; Saptaparna Das; Maraia E. Ener; Harry B. Gray; Peter Djurovich; Stephen E. Bradforth; Mark E. Thompson

doi:10.1021/jp506855t

Symmetry-breaking charge transfer of visible light absorbing systems: Zinc dipyrrins

Cong Trinh, Kent Kirlikovali, Saptaparna Das, Maraia E. Ener, Harry B. Gray, Peter Djurovich, Stephen E. Bradforth, Mark E. Thompson^*

^*Corresponding author for this work

Chemistry

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

105 Scopus citations

Abstract

Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450-550 nm and exhibit high fluorescence quantum yields in nonpolar solvents (e.g., 0.16-0.66 in cyclohexane) and weak to nonexistent emission in polar solvents (i.e., <10^-3, in acetonitrile). The low quantum efficiencies in polar solvents are attributed to the formation of a nonemissive symmetry-breaking charge transfer (SBCT) state, which is not formed in nonpolar solvents. Analysis using ultrafast spectroscopy shows that in polar solvents the singlet excited state relaxes to the SBCT state in 1.0-5.5 ps and then decays via recombination to the triplet or ground states in 0.9-3.3 ns. In the weakly polar solvent toluene, the equilibrium between a localized excited state and the charge transfer state is established in 11-22 ps.

Original language	English (US)
Pages (from-to)	21834-21845
Number of pages	12
Journal	Journal of Physical Chemistry C
Volume	118
Issue number	38
DOIs	https://doi.org/10.1021/jp506855t
State	Published - Sep 25 2014

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Energy
Surfaces, Coatings and Films
Physical and Theoretical Chemistry

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title = "Symmetry-breaking charge transfer of visible light absorbing systems: Zinc dipyrrins",

abstract = "Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450-550 nm and exhibit high fluorescence quantum yields in nonpolar solvents (e.g., 0.16-0.66 in cyclohexane) and weak to nonexistent emission in polar solvents (i.e., <10-3, in acetonitrile). The low quantum efficiencies in polar solvents are attributed to the formation of a nonemissive symmetry-breaking charge transfer (SBCT) state, which is not formed in nonpolar solvents. Analysis using ultrafast spectroscopy shows that in polar solvents the singlet excited state relaxes to the SBCT state in 1.0-5.5 ps and then decays via recombination to the triplet or ground states in 0.9-3.3 ns. In the weakly polar solvent toluene, the equilibrium between a localized excited state and the charge transfer state is established in 11-22 ps.",

author = "Cong Trinh and Kent Kirlikovali and Saptaparna Das and Ener, {Maraia E.} and Gray, {Harry B.} and Peter Djurovich and Bradforth, {Stephen E.} and Thompson, {Mark E.}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

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doi = "10.1021/jp506855t",

language = "English (US)",

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TY - JOUR

T1 - Symmetry-breaking charge transfer of visible light absorbing systems

T2 - Zinc dipyrrins

AU - Trinh, Cong

AU - Kirlikovali, Kent

AU - Das, Saptaparna

AU - Ener, Maraia E.

AU - Gray, Harry B.

AU - Djurovich, Peter

AU - Bradforth, Stephen E.

AU - Thompson, Mark E.

PY - 2014/9/25

Y1 - 2014/9/25

N2 - Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450-550 nm and exhibit high fluorescence quantum yields in nonpolar solvents (e.g., 0.16-0.66 in cyclohexane) and weak to nonexistent emission in polar solvents (i.e., <10-3, in acetonitrile). The low quantum efficiencies in polar solvents are attributed to the formation of a nonemissive symmetry-breaking charge transfer (SBCT) state, which is not formed in nonpolar solvents. Analysis using ultrafast spectroscopy shows that in polar solvents the singlet excited state relaxes to the SBCT state in 1.0-5.5 ps and then decays via recombination to the triplet or ground states in 0.9-3.3 ns. In the weakly polar solvent toluene, the equilibrium between a localized excited state and the charge transfer state is established in 11-22 ps.

AB - Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450-550 nm and exhibit high fluorescence quantum yields in nonpolar solvents (e.g., 0.16-0.66 in cyclohexane) and weak to nonexistent emission in polar solvents (i.e., <10-3, in acetonitrile). The low quantum efficiencies in polar solvents are attributed to the formation of a nonemissive symmetry-breaking charge transfer (SBCT) state, which is not formed in nonpolar solvents. Analysis using ultrafast spectroscopy shows that in polar solvents the singlet excited state relaxes to the SBCT state in 1.0-5.5 ps and then decays via recombination to the triplet or ground states in 0.9-3.3 ns. In the weakly polar solvent toluene, the equilibrium between a localized excited state and the charge transfer state is established in 11-22 ps.

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JO - Journal of Physical Chemistry C

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ER -

Symmetry-breaking charge transfer of visible light absorbing systems: Zinc dipyrrins

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