Azarias Cloé, Pawelek Mylène, Jacquemin Denis
CEISAM, UMR CNRS 6230, BP 92208, Universite de Nantes , 2, Rue de la Houssiniere, 44322 Nantes, Cedex 3, France.
Institut Universitaire de France , 1, rue Descartes, F-75231 Paris Cedex 05, France.
J Phys Chem A. 2017 Jun 8;121(22):4306-4317. doi: 10.1021/acs.jpca.7b03644. Epub 2017 May 26.
Using ab initio approaches accounting for environmental effects, we investigate the ground- and excited-state properties of four subporphyrinoids: subporphyrin, subporphyrazine, tribenzosubporphyrin, and subphthalocyanine. We first show that the selected level of theory, that is DFT(PBE0), is able to reproduce the structure and NMR spectra of all compounds. The aromaticity of these four macrocyclic entities are next quantified and it is showed that these bowl-shape induced molecules present very strong aromatic characters. Next we analyze the spectral signatures of all four compounds using an approach going beyond the vertical approximation. The 0-0 energies are reproduced with a mean absolute deviation smaller than 0.1 eV, and the very good agreement obtained between experimental and theoretical band shapes allows us to unravel the vibronic contributions responsible to the specific band shapes of these subporphyrinoids. Finally, we investigate a large series of substituted subporphyrins, demonstrate the quality of the trends that are obtained with theory and design new compounds presenting red-shifted optical bands.
使用考虑环境效应的从头算方法，我们研究了四种亚卟啉类化合物的基态和激发态性质：亚卟啉、亚卟嗪、三苯并亚卟啉和亚酞菁。我们首先表明，所选的理论水平，即密度泛函理论（PBE0），能够重现所有化合物的结构和核磁共振谱。接下来对这四个大环实体的芳香性进行了量化，结果表明这些碗状诱导分子具有很强的芳香特征。接下来，我们使用一种超越垂直近似的方法分析了所有四种化合物的光谱特征。0-0能量的重现平均绝对偏差小于0.1 eV，实验和理论能带形状之间取得的良好一致性使我们能够揭示导致这些亚卟啉类化合物特定能带形状的振动电子贡献。最后，我们研究了一系列取代亚卟啉，证明了理论得到的趋势的质量，并设计了具有红移光学带的新化合物。
