Solvent and Structural Fluctuations Induced Symmetry-Breaking Charge Transfer in a Porphyrin Triad,The Journal of Physical Chemistry C

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Solvent and Structural Fluctuations Induced Symmetry-Breaking Charge Transfer in a Porphyrin Triad
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2018-08-22 , DOI: 10.1021/acs.jpcc.8b05363
Taeyeon Kim ₁ , Woojae Kim ₁ , Hirotaka Mori ₂ , Atsuhiro Osuka ₂ , Dongho Kim ₁

Affiliation

This study aims to show that the symmetry-breaking charge transfer (SBCT) in a donor–acceptor–donor (DAD) porphyrin triad occurs via solvent and structural fluctuations measured by using femtosecond broadband fluorescence upconversion spectroscopy, which can directly trace the origin of the emitting state by monitoring its emission dipole moment as a function of time. While the emission dipole moment of the triad in the excited state remains nearly unchanged in nonpolar solvents such as cyclohexane and toluene, it is significantly reduced in polar solvents such as benzonitrile due to a change in the emitting state from quadrupolar (the exciton coupled state) to dipolar symmetry (the relaxed S₁ state). The latter state is formed by the SBCT process of DAD via a combination of solvent and structural fluctuations.

中文翻译：

溶剂和结构波动诱导卟啉三联体的对称性突破性电荷转移

这项研究旨在表明，供体-受体-供体（DAD）卟啉三联体中的对称破缺电荷转移（SBCT）是通过使用飞秒宽带荧光上转换光谱法测量的溶剂和结构波动而发生的，该波动可直接追溯其起源。通过监视其发射偶极矩作为时间的函数来发射状态。在非极性溶剂（例如环己烷和甲苯）中，处于激发态的三重态的发射偶极矩几乎保持不变，但在极性溶剂（例如苯甲腈）中，由于四极态（激子耦合态）的发射态发生了变化，三态发射态的偶极矩几乎不变到偶极对称（松弛的S ₁状态）。后一种状态是由DAD的SBCT工艺通过溶剂和结构波动的组合而形成的。

更新日期：2018-08-22

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