Department of Chemistry and Biotechnology, School of Science, Tallinn University of Technology Address, Akadeemia tee 15, 12618, Tallinn, Estonia.
ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France.
Chemphyschem. 2021 Sep 3;22(17):1817-1833. doi: 10.1002/cphc.202100345. Epub 2021 Jul 12.
In the present work, sixteen different zinc porphyrins (possessing different meso substituents) with and without a chiral guest were modelled using DFT and TD-DFT approaches in order to understand the influence of various controlling factors on electronic circular dichroism (ECD) spectra. Two major aspects are influenced by these factors: excitation energy of the electronic transitions and their intensity. In the case of excitation energy, the influence increases in the following order: orientation of the peripheral substituents<substituent's nature<axial ligation. However, the deformation of the porphyrin plane does not affect the excitation energies. In the case of intensity, the influence increases as follows: substituent's nature<conrotatory orientation of the peripheral substituents<deformation of the porphyrin plane<disrotatory orientation of the peripheral substituents<axial ligation.
在本工作中，使用 DFT 和 TD-DFT 方法对十六种不同的锌卟啉（具有不同的中位取代基）及其带有手性客体和不带手性客体的模型进行了模拟，以了解各种控制因素对电子圆二色性（ECD）光谱的影响。这两个主要方面受到以下因素的影响：电子跃迁的激发能量及其强度。在激发能量方面，影响的顺序为：外围取代基的取向<取代基的性质<轴向配位。然而，卟啉平面的变形不会影响激发能量。在强度方面，影响的顺序为：取代基的性质<外围取代基的协同旋转取向<卟啉平面的变形<外围取代基的对映旋转取向<轴向配位。
