Chirogenesis in Zinc Porphyrins: Theoretical Evaluation of Electronic Transitions, Controlling Structural Factors and Axial Ligation,ChemPhysChem

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Chirogenesis in Zinc Porphyrins: Theoretical Evaluation of Electronic Transitions, Controlling Structural Factors and Axial Ligation
ChemPhysChem ( IF 2.3 ) Pub Date : 2021-07-02 , DOI: 10.1002/cphc.202100345
Irina Osadchuk _{1,

2} , Riina Aav ₁ , Victor Borovkov ₁ , Eric Clot ₂

Affiliation

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.

中文翻译：

锌卟啉的手性作用：电子跃迁、控制结构因素和轴向连接的理论评估

在目前的工作中，使用 DFT 和 TD-DFT 方法对具有和不具有手性客体的 16 种不同的锌卟啉（具有不同的内消旋 取代基）进行建模，以了解各种控制因素对电子圆二色性（ECD）光谱的影响。这些因素影响两个主要方面：电子跃迁的激发能及其强度。在激发能的情况下，影响按以下顺序增加：外围取代基的取向<取代基的性质<轴向连接。然而，卟啉平面的变形并不影响激发能。在强度的情况下，影响如下增加：取代基的性质<外围取代基的顺旋取向<卟啉平面的变形<外围取代基的反旋取向<轴向连接。

更新日期：2021-09-03

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