Photophysical and Photochemical Investigation of a Dodecafluorosubphthalocyanine Derivative

Abstract

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.

cis andtrans Forms of a Binuclear Subphthalocyanine

“…We have replaced the 4-tert-butylphthalonitrile with tetrafluorophthalonitrile to prevent the formation of positional isomers that the 4-tert-butyl substituent engenders, and to reduce the number of benzo units that can undergo halogenation, an unavoidable side reaction when BBr 3 or BCl 3 is used in SubPc syntheses. [5] We also report the X-ray crystal structure analysis of the perfluorinated monomer, [6] derived from the cyclotrimerization of tetrafluorophthalonitrile, which is unavoidably the major product of the reaction. [7] [5] a) N. Kobayashi, T. Fukuda, D. Lelievre, Inorg.…”

“…Chem. 2000, 39, 3632 ± 3637; [8] These low-field proton signals at d % 10.5 ppm were not reported in reference [6]. [9] Few examples have been described of intramolecular interactions between phthalocyanine subunits in related binuclear phthalocyanine systems in which the two Pc moieties are connected through benzene rings.…”

Comparative electronic structures and UV–vis spectra of tribenzosubporphyrin, tribenzomonoazasubporphyrin, tribenzodiazasubporphyrin, and subphthalocyanine: Insight from DFT and TDDFT calculations

“…The smallest phthalocyanine analogue is the subphthalocyanine macrocycle, which consists of only three isoindole fragments and three meso-nitrogen atoms [2]. Although subphthalocyanine was reported by Meller and Ossko in 1972 [3], its chemistry, redox and photophysical properties of its substituted analogues were only scarcely explored until 1990s [4][5][6][7][8][9][10][11][12][13], when several research groups became interested in their unique characteristics. Subphthalocyanines have nonplanar, bowl-like structures along with a 14 -electron aromatic core with a trigonal-pyramidal boron atom as the central atom.…”

Optical Recording Properties of a Novel Subphthalocyanine Thin Film

“…Subphthalocyanine (SubPc) is a new kind of Pc-related compounds [6][7][8][9][10][11][12][13]. It shares many of the excellent properties of Pcs such as thermal and chemical stability.…”

“…However, there are few reports published hitherto about its optical recording performance. Most of the researches on this kind of compounds have been restricted to nonlinear optical applications [6][7][8][9][10][11][12]. In this paper, we studied the optical and recording properties of a novel trinitro-substituted SubPc thin film.…”