<br>氮杂菲及其二聚体的电子结构,The Journal of Physical Chemistry A

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氮杂菲及其二聚体的电子结构
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2024-02-12 , DOI: 10.1021/acs.jpca.3c07740
F Sturm ₁ , L N Philipp ₁ , M Flock ₁ , I Fischer ₁ , R Mitric ₁

Affiliation

氮原子的插入通过在分子中引入 nπ* 态来改变多环芳烃的电子结构和光化学。为了更好地了解孤立的多环芳香族含氮烃（PANH）及其二聚体的电子结构以及分子中氮原子位置的影响，我们研究了三种不同的氮杂菲，苯并[ f ]喹啉，苯并[ h ]喹啉和菲啶，在联合实验和计算研究中。实验上，应用共振增强多光子电离（REMPI）光谱来表征激发电子态。氮杂菲单体的 REMPI 光谱具有相当相似的外观，1ππ* ← S ₀跃迁的起点在 3.645 和 3.670 eV 之间。与菲母体相反，2ππ* ← S ₀即使在能带原点也是宽且非结构化的。实验伴随着密度泛函理论计算，并使用与时间无关的方法模拟振动分辨光谱。菲和氮杂菲之间的差异归因于低位¹ (nπ*) 态引起的扰动，这会加速非辐射失活。对于二聚体，我们发现两个具有两个电子跃迁的 π 堆叠异构体各自对电子谱有贡献，导致难以分配的重叠谱带。

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The Electronic Structures of Azaphenanthrenes and Their Dimers

Insertion of a nitrogen atom modifies the electronic structures and photochemistry of polycyclic aromatic hydrocarbons by introducing nπ* states into the molecules. To better understand the electronic structures of isolated polycyclic aromatic nitrogen-containing hydrocarbons (PANHs) and their dimers as well as the influence of the position of the nitrogen atom in the molecule, we investigate three different azaphenanthrenes, benzo[f]quinoline, benzo[h]quinoline, and phenanthridine, in a joint experimental and computational study. Experimentally, resonance-enhanced multiphoton ionization (REMPI) spectroscopy is applied to characterize the excited electronic states. The REMPI spectra of the azaphenanthrene monomers have a rather similar appearance, with origins between 3.645 and 3.670 eV for the 1ππ* ← S₀ transition. In contrast to the phenanthrene parent, 2ππ* ← S₀ is broad and unstructured even at the band origin. The experiments are accompanied by density functional theory computation, and vibrationally resolved spectra are simulated using a time-independent approach. The differences between phenanthrene and the azaphenanthrenes are assigned to perturbations due to the low-lying ¹(nπ*) state, which accelerates nonradiative deactivation. For the dimers, it is found that two π-stacked isomers with two electronic transitions each contribute to the electronic spectrum, leading to overlapping bands that are difficult to assign.

更新日期：2024-02-12

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