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Three absorption systems starting at 624.1, 601.2, and 590.0 nm were detected in a 6 K neon matrix following deposition of mass selected  m / z  = 250 ions produced from corannulene vapour in a hot cathode ion source. The two latter systems were also observed after deposition of neutral corannulene in solid neon with concomitant bombardment of the matrix with argon ions. The features in the absorption spectrum are assigned to the 4 2 A′′  ←   X  2 A′′ transition of cylobutadieno-benzo[ghi]fluoranthene cation and to the 3 2 A′  ←   X  2 A′′ and 3 2 A′′  ←   X  2 A′ transitions of two Jahn-Teller structures of bowl-shaped corannulene cations, respectively. The assignment is based on excitation energies calculated with the SAC-CI and CASPT2 methods. The electronic absorption spectrum of protonated corannulene has onsets at 515.1 and 398.8 nm in a neon matrix, following deposition of a mass-selected beam produced by reactions of corannulene with EtOH 2  + . The absorptions are assigned, on the basis of theoretical predictions, to the 3,4 1 A  ←   X  1 A transitions. The electronic spectrum was also recorded in the gas phase using a resonant multiphoton fragmentation technique in an ion trap at vibrational and rotational temperatures of 15 K. The 3,4 1 A  ←   X  1 A transitions are observed with origin bands at 521 ± 1 nm and 396.4 ± 0.1 nm. The 3 1 A excited electronic state indicates fast internal conversion of ≈ 5 fs, while the 4 1 A state has a lifetime of ≈ 0.2 ps. A distinct vibrational pattern is discernible in the 4 1 A  ←   X  1 A transition.

Electronic Spectra of Corannulenic Cations and Neutrals in Neon Matrices and Protonated Corannulene in the Gas Phase at 15 K

Electronic Spectra of Corannulenic Cations and Neutrals in Neon Matrices and Protonated Corannulene in the Gas Phase at 15 K