The Electronic Structures of Azaphenanthrenes and Their Dimers

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2024-02, Vol.128 (7), p.1250-1259
• Main Authors: Sturm, F., Philipp, L. N., Flock, M., Fischer, I., Mitric, R.
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.3c07740

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.