Dioxadiazuliporphyrin: a near-IR redox switchable chromophore.
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.
Sprutta
Natasza
N
Department of Chemistry, University of Wrocław, 14 F. Joliot-Curie Street, Wrocław 50 383, Poland.
Siczek
Marta
M
Latos-Grazyński
Lechosław
L
Pawlicki
Miłosz
M
Szterenberg
Ludmiła
L
Lis
Tadeusz
T
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
D011165:Porphyrinogens; D011166:Porphyrins; C526479:dioxadiazuliporphyrin; C526480:dioxadiazuliporphyrinogen