title: Dioxadiazuliporphyrin: a near-IR redox switchable chromophore.
abstract: The synthesis of dioxadiazuliporphyrinogen 7 and its oxidized forms: dioxadiazuliporphyrin 8 and dication 8(2+), is reported. These compounds were characterized in solution using UV-vis and 1H and 13C NMR spectroscopic means and in the solid state via single-crystal X-ray diffraction analysis. Dioxadiazuliporphyrin is a nonaromatic porphyrinoid, readily and reversibly oxidizable to its cation radical and to the aromatic carbaporphyrinoid dication, which can be viewed as a 21,23-dicarba-22,24-dioxaporphyrin with two fused tropylium rings. Further insight into the geometric and magnetic manifestations of aromaticity and antiaromaticity in the case of the redox couple 8, 8(2+) is obtained using density functional calculations and nucleus-independent chemical shifts.
authors.affiliation: Department of Chemistry, University of Wrocław, 14 F. Joliot-Curie Street, Wrocław 50 383, Poland.
authors.forename: Natasza
authors.initials: N
authors.lastname: Sprutta
authors.forename: Marta
authors.initials: M
authors.lastname: Siczek
authors.forename: Lechosław
authors.initials: L
authors.lastname: Latos-Grazyński
authors.forename: Miłosz
authors.initials: M
authors.lastname: Pawlicki
authors.forename: Ludmiła
authors.initials: L
authors.lastname: Szterenberg
authors.forename: Tadeusz
authors.initials: T
authors.lastname: Lis
mesh_terms: D018360:Crystallography, X-Ray; D007259:Infrared Rays; D009682:Magnetic Resonance Spectroscopy / Q000379:methods / Q000592:standards; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011165:Porphyrinogens / Q000138:chemical synthesis / Q000737:chemistry / Q000528:radiation effects; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry / Q000528:radiation effects*; D012015:Reference Standards; D013237:Stereoisomerism
chemical_list: D011165:Porphyrinogens; D011166:Porphyrins; C526479:dioxadiazuliporphyrin; C526480:dioxadiazuliporphyrinogen