Symmetry-Breaking Charge Transfer of Visible Light Absorbing Systems: Zinc Dipyrrins

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• 作者：Cong Trinh ; Kent Kirlikovali ; Saptaparna Das ; Maraia E. Ener ; Harry B. Gray ; Peter Djurovich ; Stephen E. Bradforth ; Mark E. Thompson
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：September 25, 2014
• 年：2014
• 卷：118
• 期：38
• 页码：21834-21845
• 全文大小：652K
• ISSN：1932-7455

文摘

Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450鈥?50 nm and exhibit high fluorescence quantum yields in nonpolar solvents (e.g., 0.16鈥?.66 in cyclohexane) and weak to nonexistent emission in polar solvents (i.e., <10^鈥?, 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鈥?.5 ps and then decays via recombination to the triplet or ground states in 0.9鈥?.3 ns. In the weakly polar solvent toluene, the equilibrium between a localized excited state and the charge transfer state is established in 11鈥?2 ps.