Symmetry-Breaking Charge Transfer of Visible Light Absorbing Systems: Zinc Dipyrrins
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 efficienc...
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| Published in | Journal of physical chemistry. C Vol. 118; no. 38; pp. 21834 - 21845 |
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| Main Authors | , , , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
United States
American Chemical Society
25.09.2014
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| Online Access | Get full text |
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| 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. |
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| AbstractList | 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. 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. 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 , 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 | Djurovich, Peter Bradforth, Stephen E Das, Saptaparna Kirlikovali, Kent Gray, Harry B Trinh, Cong Ener, Maraia E Thompson, Mark E |
| AuthorAffiliation | Department of Chemistry California Institute of Technology University of Southern California |
| AuthorAffiliation_xml | – name: University of Southern California – name: California Institute of Technology – name: Department of Chemistry |
| Author_xml | – sequence: 1 givenname: Cong surname: Trinh fullname: Trinh, Cong – sequence: 2 givenname: Kent surname: Kirlikovali fullname: Kirlikovali, Kent – sequence: 3 givenname: Saptaparna surname: Das fullname: Das, Saptaparna – sequence: 4 givenname: Maraia E surname: Ener fullname: Ener, Maraia E – sequence: 5 givenname: Harry B surname: Gray fullname: Gray, Harry B – sequence: 6 givenname: Peter surname: Djurovich fullname: Djurovich, Peter – sequence: 7 givenname: Stephen E surname: Bradforth fullname: Bradforth, Stephen E – sequence: 8 givenname: Mark E surname: Thompson fullname: Thompson, Mark E email: met@usc.edu |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/25270268$$D View this record in MEDLINE/PubMed https://www.osti.gov/biblio/1159174$$D View this record in Osti.gov |
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| Snippet | Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450–550 nm and exhibit high fluorescence quantum yields in nonpolar solvents... Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450-550 nm and exhibit high fluorescence quantum yields in nonpolar solvents... Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450–550 nm and exhibit high fluorescence quantum yields in nonpolar solvents... |
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| SubjectTerms | Absorption Charge transfer Decay Excitation spectra Ground state Nanomaterials Solvents Zinc |
| Title | Symmetry-Breaking Charge Transfer of Visible Light Absorbing Systems: Zinc Dipyrrins |
| URI | http://dx.doi.org/10.1021/jp506855t https://www.ncbi.nlm.nih.gov/pubmed/25270268 https://search.proquest.com/docview/1762068563 https://search.proquest.com/docview/1826615338 https://www.osti.gov/biblio/1159174 https://pubmed.ncbi.nlm.nih.gov/PMC4174994 |
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