Institut de Química Computacional and Departament de Química, Universitat de Girona, C/ Maria Aurèlia Capmany 69, 17003 Girona, Catalonia, Spain.
Phys Chem Chem Phys. 2019 Dec 7;21(45):25098-25107. doi: 10.1039/c9cp04104d. Epub 2019 Nov 6.
Molecular arrays containing donor-acceptor sites and antenna molecules are promising candidates for organic photovoltaic devices. Photoinduced electron transfer (PET) in multi-chromophore systems is controlled by a subtle interplay of donor and acceptor properties and solvent effects. In the present study, we explore how PET of fullerene [C]-Zn-porphyrin-BODIPY triads can be modulated by passing from non-polar to polar media. To this end we perform a computational study of this complex using the DFT/TDDFT method. We find that the stabilization energy of charge transfer states by a polar medium depends significantly on whether the BODIPY moiety acts as an electron donor or an electron acceptor. To understand this effect of the environment, a detailed analysis of the initial and final states of the ET reactions is performed. We show that additional deactivation channels of the porphyrin excited state may come into play as solvent polarity increases.
含有给体-受体位点和天线分子的分子阵列是有机光伏器件有前途的候选者。多色团体系中的光诱导电子转移 (PET) 受供体和受体性质以及溶剂效应的微妙相互作用控制。在本研究中，我们探索了富勒烯 [C]-Zn-卟啉-BODIPY 三联体的 PET 如何通过从非极性到极性介质来调节。为此，我们使用 DFT/TDDFT 方法对该复合物进行了计算研究。我们发现，通过极性介质稳定电荷转移态的能量取决于 BODIPY 部分是作为电子给体还是电子受体。为了理解环境的这种影响，对 ET 反应的初始和最终状态进行了详细分析。我们表明，随着溶剂极性的增加，卟啉激发态的额外去激活通道可能会起作用。
