title: Carbocations Confined in a Thiatriazuliporphyrin Frame.
abstract: In the search for tricarbaporphyrinoids, a three-component acid-catalyzed condensation of azulene, 2,5-bis[(p-tolyl)hydroxymethyl]thiophene, and an aryl aldehyde has been elaborated, affording the appropriate thiatriazuliporphyrinogens. The subsequent oxidation yielded a rare example of a macrocyclic organic tetracation, which can be readily and reversibly converted into macrocyclic tri- and dicarbocations by addition of one or two hydroxides bound at the meso position(s). Further insight into the influence of carbocation formation on the geometry, electronic structure, and magnetic manifestation in (1) H NMR spectroscopy has been obtained by using density functional theory calculations. The charge distribution was evaluated by mapping electron density surfaces with electrostatic potential (ESP).
authors.affiliation: Wydział Chemii, Uniwersytet Wrocławski, ul. F. Joliot-Curie 14, 50-383, Wrocław, Poland. natasza.sprutta@chem.uni.wroc.pl.
authors.forename: Natasza
authors.initials: N
authors.lastname: Sprutta
authors.affiliation: Wydział Chemii, Uniwersytet Wrocławski, ul. F. Joliot-Curie 14, 50-383, Wrocław, Poland.
authors.forename: Monika
authors.initials: M
authors.lastname: Wełnic
authors.affiliation: Wydział Chemii, Uniwersytet Wrocławski, ul. F. Joliot-Curie 14, 50-383, Wrocław, Poland.
authors.forename: Michał J
authors.initials: MJ
authors.lastname: Białek
authors.affiliation: Wydział Chemii, Uniwersytet Wrocławski, ul. F. Joliot-Curie 14, 50-383, Wrocław, Poland.
authors.forename: Tadeusz
authors.initials: T
authors.lastname: Lis
authors.affiliation: Wydział Chemii, Uniwersytet Wrocławski, ul. F. Joliot-Curie 14, 50-383, Wrocław, Poland.
authors.forename: Ludmiła
authors.initials: L
authors.lastname: Szterenberg
authors.affiliation: Wydział Chemii, Uniwersytet Wrocławski, ul. F. Joliot-Curie 14, 50-383, Wrocław, Poland. lechoslaw.latos-grazynski@chem.uni.wroc.pl.
authors.forename: Lechosław
authors.initials: L
authors.lastname: Latos-Grażyński
keywords: annulene; azulene; carbaporphyrinoids; carbocations; macrocycles