Excited-State Symmetry-Breaking Charge Separation Dynamics in Multibranched Perylene Diimide Molecules

激发态 化学 光化学 二亚胺 化学物理 超快激光光谱学 有机太阳能电池 光激发 分子内力 四聚体 光诱导电荷分离 分子 光谱学 原子物理学 聚合物 立体化学 有机化学 量子力学 光催化 催化作用 物理 人工光合作用
作者
Jie Kong,Wei Zhang,Gang Li,Dayujia Huo,Yuanyuan Guo,Xinmiao Niu,Yan Wan,Bo Tang,Andong Xia
出处
期刊:Journal of Physical Chemistry Letters [American Chemical Society]
卷期号:11 (24): 10329-10339 被引量:54
标识
DOI:10.1021/acs.jpclett.0c03210
摘要

As one of the most promising nonfullerene acceptors for organic photovoltaics, perylene diimide (PDI)-based multibranched molecules with twisted or three-dimensional (3D) geometric structures have been developed, which effectively increase the power conversion efficiency (PCE) of organic solar cells. Understanding the structure–property relationships in multichromophoric molecular architectures at molecular and ultrafast time levels is a crucial step in establishing new design principles in organic electronic materials. For this, photodriven excited-state symmetry-breaking charge separation (SB-CS) of PDI-based multichromophoric acceptors has been proposed to improve the PCE by reducing the self-aggregation of the planar PDI monomer. Herein, we investigated the intramolecular excited-state SB-CS and charge recombination (CR) dynamics of two symmetric phenyl-methane-based PDI derivatives, a twist dimer PM-PDI2 (phenyl-methane-based PDI dimer) and a 3D configuration tetramer PM-PDI4 (phenyl-methane-based PDI tetramer), in different solvents using ultrafast femtosecond transient absorption (fs-TA) spectroscopy and quantum chemical calculations. The quantum chemical calculations and steady-state spectra show that the two PDI derivatives undergo conformational changes upon excitation, leading to their emission states that have the characteristics of partial charge-transfer (CT) exciton in all solvents. Based on the evolution of the fs-TA data, it is observed that the evolution from the CT state to SB-CS state is disfavored in a weak polar solvent, whereas clear SB-CS spectroscopic signatures of cationic and anionic PDI are observed in polar solvents. Faster CS and slower CR processes of PM-PDI4 are observed in comparison to those of PM-PDI2. The crowded space in the 3D structure shortens the distance between the branches, leading to a stronger electronic coupling at the lowest excited state and a larger negative Gibbs free energy change of PM-PDI4 relative to that of PM-PDI2, which benefits the charge separation among PDI units in PM-PDI4. Besides, the 3D structure of PM-PDI4 also restricts rotation to a surface crossing region between the excited state and ground state, thus inhibiting nonradiative CR process and increasing the CS state lifetime. Our results suggest that the kinetics of CS and CR processes are strongly related to the molecular geometric structure, and the excited-state symmetry breaking in the 3D structure acceptor has superior photogenerated charge and photovoltaic properties from the perspective of ultrafast dynamics.
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