Isomerisation of an intramolecular hydrogen-bonded photoswitch: Protonated azobis(2-imidazole)

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Abstract

Photoisomerisation of protonated azobis(2-imidazole), an intramolecular hydrogen-bonded azoheteroarene photoswitch molecule, is investigated in the gas phase using tandem ion mobility mass spectrometry. The E and Z isomers exhibit distinct spectral responses, with E-Z photoisomerisation occurring over the 360-520 nm range (peak at 460 nm), and Z-E photoisomerisation taking place over the 320-420 nm range (peak at 390 nm). A minor photodissociation channel involving loss of N2 is observed for the E-isomer with a maximum efficiency at 390 nm, blue-shifted by ≈70 nm relative to the wavelength for maximum photoisomerisation response. Loss of N2 is also the predominant collision-induced dissociation channel. Electronic structure calculations suggest that E-isomer photoisomerisation involves S1(ππ∗) excitation, whereas the Z-isomer photoisomerisation involves S2(ππ∗) excitation. Conversion between the E and Z isomers through collisional excitation, which is calculated to occur through both inversion and torsion pathways, is investigated experimentally by colliding the molecular ions with nitrogen buffer gas over a range of electric fields. This study demonstrates the versatility of tandem ion mobility mass spectrometry for exploring the isomerisation of molecular photoswitches initiated by either light or collisions.

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Bull, J. N., Scholz, M. S., Coughlan, N. J. A., & Bieske, E. J. (2017). Isomerisation of an intramolecular hydrogen-bonded photoswitch: Protonated azobis(2-imidazole). Physical Chemistry Chemical Physics, 19(20), 12776–12783. https://doi.org/10.1039/c7cp01733b

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