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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Electronic Structure and Absorption Properties of Strongly Coupled Porphyrin-Perylene Arrays
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Electronic Structure and Absorption Properties of Strongly Coupled Porphyrin-Perylene Arrays

机译：强耦合卟啉-Per阵列的电子结构和吸收性能

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Porphyrin-perylene arrays are ideal candidates for light-harvesting systems capable of panchromatic absorption. In this work, we employ density functional theory (DFT) and time-dependent DFT to investigate the unique UV-vis absorption properties exhibited by a series of ethynyl-linked porphyrin-perylene arrays that were previously synthesized and characterized spectroscopically [Chem. Commun. 2014 , 50 , 14512 - 5 ]. We find that the ethynyl linker is responsible for strong electronic coupling of porphyrin and perylene subunits in these systems. Additionally, these arrays exhibit a low barrier to rotation around the ethynyl linker (<1.4 kcal/mol per one perylene substituent), which results in a wide range of molecular conformations characterized by different porphyrin-perylene dihedral angles being accessible at room temperature. The best match between the calculated and experimental UV-vis spectra is obtained by averaging the calculated UV-vis spectra over the range of conformations defined by the porphyrin-perylene dihedral angles. Finally, our calculations suggest that the transitions in the lower energy region (550-750 nm) can be assigned to the excitations originating from the porphyrin subunit; the mid-energy region transitions (450-550 nm) are assigned to the perylene-centered excitations, while the high-energy transitions (350-450 nm) involve contributions from both porphyrin and perylene subunits.
机译：卟啉-per阵列是能够全色吸收的光收集系统的理想候选者。在这项工作中，我们采用密度泛函理论（DFT）和随时间变化的DFT来研究由一系列乙炔基连接的卟啉-per阵列显示的独特的UV-vis吸收特性，这些阵列先前是通过光谱合成和表征的。公社2014，50，14512-5]。我们发现乙炔基接头负责这些系统中卟啉和per亚基的强电子偶联。此外，这些阵列显示出较低的绕乙炔基连接的旋转障碍（每一个per取代基<1.4 kcal / mol），这导致了宽范围的分子构象，其特征是在室温下可获得不同的卟啉-per二面角。通过对由卟啉-per二面角定义的构象范围内的计算得出的UV-vis光谱求平均值，可以得到计算得出的UV-vis光谱与实验UV-vis光谱之间的最佳匹配。最后，我们的计算表明，在较低能量区域（550-750 nm）的跃迁可以归因于卟啉亚基的激发。中能区跃迁（450-550 nm）分配给以ylene为中心的激发，而高能跃迁（350-450 nm）涉及卟啉和per亚基的贡献。

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