TY - JOUR
T1 - Synthesis, cyclic voltammetric studies, and electrogenerated chemiluminescence of a new phenylquinoline-biphenothiazine donor-acceptor molecule
AU - Lai, Rebecca Y.
AU - Kong, Xiangxing
AU - Jenekhe, Samson A.
AU - Bard, Allen J.
PY - 2003/10/15
Y1 - 2003/10/15
N2 - We report the synthesis, electrochemistry, and luminescence of a novel ECL emitting compound containing two electron-accepting hexyl-phenylquinoline groups covalently attached to the 3,3′-positions of the electron-donating 10,10′-dimethylbiphenothiazine group. The optimized geometry as determined from semiempirical MNDO calculations shows that the two quinoline groups are twisted 82.5° from the two phenothiazine rings, indicating a lack of electron delocalization among these groups. This unique geometry allows generation of localized radical cations and radical anions capable of generating ECL upon annihilation. However, the phenothiazine rings are twisted 46.5° relative to each other, suggesting possible interactions between the two moieties. This is evident in the electrochemical behavior in which two closely spaced one-electron oxidations, rather than a single two-electron oxidation wave, were observed. The photophysical properties of BHQ-BPZ show strong resemblances to the parent compound, BPQ-PTZ, which contains a single phenothiazine moiety. In addition, the ECL spectrum produced via radical ion annihilation shows good agreement with the fluorescence emission of the compound.
AB - We report the synthesis, electrochemistry, and luminescence of a novel ECL emitting compound containing two electron-accepting hexyl-phenylquinoline groups covalently attached to the 3,3′-positions of the electron-donating 10,10′-dimethylbiphenothiazine group. The optimized geometry as determined from semiempirical MNDO calculations shows that the two quinoline groups are twisted 82.5° from the two phenothiazine rings, indicating a lack of electron delocalization among these groups. This unique geometry allows generation of localized radical cations and radical anions capable of generating ECL upon annihilation. However, the phenothiazine rings are twisted 46.5° relative to each other, suggesting possible interactions between the two moieties. This is evident in the electrochemical behavior in which two closely spaced one-electron oxidations, rather than a single two-electron oxidation wave, were observed. The photophysical properties of BHQ-BPZ show strong resemblances to the parent compound, BPQ-PTZ, which contains a single phenothiazine moiety. In addition, the ECL spectrum produced via radical ion annihilation shows good agreement with the fluorescence emission of the compound.
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U2 - 10.1021/ja036600q
DO - 10.1021/ja036600q
M3 - Article
C2 - 14531707
AN - SCOPUS:0141885393
SN - 0002-7863
VL - 125
SP - 12631
EP - 12639
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 41
ER -