The photochemical and photophysical behavior of (dodecafluorosubphthalocyanaoto)boron(III) chloride was
examined in room-temperature solutions. The lowest energy absorption maximum of the complex is 570
nm, and the luminescence mirrors the absorption with a maximum at 586 nm (Stokes shift = 480 cm-1).
The emission is strong, with a quantum yield in deaerated acetonitrile of 0.66 and a lifetime of 2.6 ns. The
complex exhibits a reversible one-electron reduction in cyclic voltammetry (E° = −0.53 V vs SCE), and
this, combined with the relatively high singlet energy, indicates the emissive excited state is a strong oxidant.
Evaluation of the free energy dependence of the emission quenching with a series of substituted benzene
donors yields a value of 1.7 V vs SCE for the excited-state reduction potential, E(*/−). The excited complex
also reacts with tertiary amines. Photolysis in the presence of triphenylamine results in photoinduced electron
transfer and back reaction. Triethylamine, however, reacts efficiently with the excited subphthalocyanine to
yield a permanent photoproduct. The product has been characterized by FAB mass spectrometry as well as
1H and 19F NMR to be an adduct involving B−N bond formation.
Synthesis and Structural Characterization of Nonplanar Perfluoro Phthalonitriles. -The preparation and molecular level characterization of the first examples of substituted perfluorinated phthalonitriles are shown. -(GORUN, S. M.; BENCH, B. A.; CARPENTER, G.; BEGGS, M. W.; MAGUE, J. T.; ENSLEY, H. E.; J. Fluorine Chem. 91 (1998) 1, 37-40; Dep. Chem., Brown Univ., Providence, RI 02912, USA; EN)
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