title: Structural chemistry of polycyclic heteroaromatic compounds. Part XI. Photoelectron spectra and electronic structures of tetracyclic hetarenes of the triphenylene type.
abstract: The UV photoelectron spectra of several tetracyclic heteroaromatic compounds (2-9) which are pi-isoelectronic with triphenylene (1) have been recorded and analysed making use of semiempirical AM1 and PM3 as well as ab initio/DFT B3LYP calculations. In one series of compounds (2-7), the peripheral benzene rings of 1 are successively substituted by thiophene rings that are either [b]- or [c]-annellated with the central benzene unit. In 2-7 only marginal shifts are found for most of the IPs of electrons. In the benzotrithiophenes 5-7, a systematic variation is displayed by IP(pi7). Compared to 1, the pi electron system of benzo[c]trithiophene (7) is approximately two times as much destabilized as in the isomers 5 and 6 with [b]annellated thiophene rings. The IP[n(S)] values of the thiophene derivatives 2-7 indicate that these orbitals are clearly destabilized relative to thiophene. The same holds for the n(O) orbital of the furane derivative 9 in comparison with that of furane. In 9, only the higher pi MOs (pi7-pi9) are destabilized whereas the lower levels (pi1-pi4) are stabilized, and those in between (pi5-pi6) remain essentially unshifted. In the pyrrole derivative 8, all pi MOs are substantially destabilized by about 0.5-1.6 eV relative to 1.
authors.affiliation: Institut für Organische Chemie, Universität GH Essen, Germany. paul.rademacher@uni-essen.de
authors.forename: P
authors.initials: P
authors.lastname: Rademacher
authors.forename: C
authors.initials: C
authors.lastname: Heinemann
authors.forename: S
authors.initials: S
authors.lastname: Jänsch
authors.forename: K
authors.initials: K
authors.lastname: Kowski
authors.forename: M E
authors.initials: ME
authors.lastname: Weiss
mesh_terms: D002911:Chrysenes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008968:Molecular Conformation
chemical_list: D002911:Chrysenes; C009590:triphenylene