Infrared spectra of isoquinolinium (iso-C9H7NH+) and isoquinolinyl radicals (iso-C9H7NH and 1-, 3-, 4-, 5-, 6-, 7- and 8-iso-HC9H7N) isolated in solid para-hydrogen

Abstract

Protonated polycyclic aromatic nitrogen heterocycles (H⁺PANH) are prospective candidates that may contribute to interstellar unidentified infrared (UIR) emission bands because protonation enhances the relative intensities of the bands near 6.2, 7.7 and 8.6 μm, and the presence of the N atom induces a blue shift of the ring-stretching modes so that the spectra of H⁺PANH match better with the 6.2 μm feature in class-A UIR spectra. We report the infrared (IR) spectra of protonated isoquinoline (the 2-isoquinolinium cation, iso-C₉H₇NH⁺), its neutral counterpart (the 2-isoquinolinyl radical, iso-C₉H₇NH), and another mono-hydrogenated product (the 6-isoquinolinyl radical, 6-iso-HC₉H₇N), produced on the electron-bombardment of a mixture of isoquinoline (iso-C₉H₇N) with excess para-hydrogen (p-H₂) during matrix deposition at 3.2 K. To generate additional isomers of hydrogenated isoquinoline, we irradiated iso-C₉H₇N/Cl₂/p-H₂ matrices at 365 nm to generate Cl atoms, followed by IR irradiation to generate H atoms via Cl + H₂ (v = 1) → HCl + H; the H atoms thus generated reacted with iso-C₉H₇N. In addition to iso-C₉H₇NH and 6-iso-HC₉H₇N observed in the electron-bombardment experiments, we identified six additional hydrogenated isoquinoline species, 1-, 3-, 4-, 5-, 7- and 8-iso-HC₉H₇N, via their IR spectra; hydrogenation on the N atom and all available carbon atoms except for the two sharing carbon atoms on the fused ring was observed. Spectral groupings were achieved according to their behaviors after maintenance of the matrix in darkness and on secondary photolysis at various wavelengths. The assignments were supported via comparison of the experimental results with the vibrational wavenumbers and IR intensities of possible isomers predicted using the B3LYP/6-311++G(d,p) method. The implications in the identification of the UIR band are discussed.