20 research outputs found
Zur Kenntnis der Azulene, XIV. Darstellung substituierter Glutacondialdehyd-Derivate und ihre Überführung in Azulene
Die drei Picoline sowie 3-Chlor-pyridin reagieren mit Bromcyan in Gegenwart aromatischer Amine unter Ringaufspaltung. 3-Methyl- und 3-Chlor-pyridin liefern dabei mit N-Methyl-anilin offenkettige Cyanamid-Derivate. Einige in 4- bzw. in 2- und 4-Stellung substituierte Pyrylium-Salze lassen sich mit aromatischen Aminen ebenfalls in Glutacondialdehyd-Derivate überführen. Ferner wird die Darstellung von ω-Amino-pentadienalen aus dem Vilsmeier-Komplex und α.β-ungesättigten Carbonylverbindungen beschrieben. Die Kondensation der neuen substituierten Glutacondialdehyd-Derivate mit Cyclopentadien führt zu im 7-Ring substituierten Azulenen
Excited states and electron transfer reactions of C<sub>60</sub>(OH)<sub>18</sub> in aqueous solution
Dynamic light scattering of fullerenol solutions [C60(OH)18] reveals evidence for the formation of fullerene aggregates at high solute concentration (up to 3.85×10-2 mol dm-3). This hydrophilic fullerene derivative emits very weak fluorescence regardless of its concentration. Photolysis (35 ps; λex=355 nm) of C60(OH)18 in aqueous solution yields the immediate formation of a transient singlet excited state with broad absorption in the 550–800 nm region with ε670nm=2130 d mol-1 cm-1. The energetically higher-lying singlet excited state transforms via intersystem crossing (i.e., with τ1/2=500 ps) to the also broadly absorbing (550-800 nm), triplet excited state. In contrast, at low solute concentration, the features of the (∗T1→∗Tn) absorption differ significantly exhibiting an absorption maximum at 650 nm concomitant to a shoulder at 570 nm. The π-radical anion of fullerenol, [C60(OH)18]·−, generated by electron transfer from hydrated electrons and (CH3)2C(OH) radicals, absorbs with λmax at 870, 980 and 1050 nm. Based on electron transfer studies with suitable electron donor/acceptor substrates, the reduction potential of the C60(OH)18/[C60(OH)18]·− couple was estimated to be in the range between -0.358 and -0.465 V vs. NHE