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Mãrtire, D.O.; Jux, N.; Aramendía, P.F.; Martín Negri, R.; Lex, J.; Braslavsky, S.E.; Schaffner, K.; Vogel, E. "Photophysics and Photochemistry of 22π and 26π Acetylene-Cumulene Porphyrinoids" (1992) Journal of the American Chemical Society. 114(25):9969-9978
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Abstract:

The aromatic 26π acetylene-cumulene porphyrinoid 8 has been synthesized by a reaction sequence involving reductive carbonyl coupling of the dialdehyde 12 utilizing low-valent titanium in the crucial step. Like its lower 22π homologs 6 and 7, the new tetrapyrrolic macrocycle 8 is centrosymmetric in the crystal and has a practically planar ring framework. The photophysical and photochemical properties of 6-8 have been studied and compared to those of the related 8π porphycene 5. The absorption spectrum of 8 has the most red-shifted and intensified visible bands (εmax = 119600 at 889 nm in dichloromethane) of this particular series of (4 + 2)π porphyrinoids. None of the compounds exhibit any photoreactivity. The photophysical properties were determined by a combination of techniques, including steady-state thermal lensing, flash photolysis, laser-induced optoacoustic spectroscopy (LIOAS), and steady-state and time-resolved NIR spectroscopy. The 22π and 26π porphyrinoids do not phosphoresce. The triplet energy (ET) of 7 was therefore measured by way of reversible energy transfer to oxygen yielding singlet molecular oxygen, O2(1Δg), indirect detection by LIOAS of the increase in triplet yield induced by O2(3Σg-)-enhanced S ⟶T intersystem crossing afforded the ET of 6, and an upper limit of ET could be obtained by energy-transfer experiments from O2(1Δg) to 8. The quantum yields of fluorescence, triplet formation, and the ET values dropped significantly on going from 5 to 6-8 (all measurements at room temperature). The triplet energies of 6, 7, and 8 are all below the energy of O2(1Δg). Compound 7, with the highest ET of the three, produces O2(1Δg) with a quantum yield of ΦΔ= 0.06 through a reversible energy-transfer mechanism. Although this value is about six times smaller than ΦΔ of 5, the phototherapeutic activities of both 5 and 7 toward tumors in mice are comparable. The ΦΔ values for 6 and 8 are lower than 10-3; hence, these porphyrinoids do not function as photodynamic sensitizers. © 1992, American Chemical Society. All rights reserved.

Registro:

Documento: Artículo
Título:Photophysics and Photochemistry of 22π and 26π Acetylene-Cumulene Porphyrinoids
Autor:Mãrtire, D.O.; Jux, N.; Aramendía, P.F.; Martín Negri, R.; Lex, J.; Braslavsky, S.E.; Schaffner, K.; Vogel, E.
Filiación:Max-Planck-Institut für Strahlenchemie, D-4330 Mülheim an der Ruhr, Germany
Max-Planck-Institut für Strahlenchemie Institut für Organische Chemie, Universitat Köln, D-5000 Köln 41, Germany
Facultad de Ciencias Exactas y Naturales, Departamento de Quimica Inorgénica, Analitica y Quimica Fisica, Universidad de Buenos Aires, 1428 Buenos Aires, Argentina
Año:1992
Volumen:114
Número:25
Página de inicio:9969
Página de fin:9978
DOI: http://dx.doi.org/10.1021/ja00051a032
Título revista:Journal of the American Chemical Society
Título revista abreviado:J. Am. Chem. Soc.
ISSN:00027863
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v114_n25_p9969_Martire

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Citas:

---------- APA ----------
Mãrtire, D.O., Jux, N., Aramendía, P.F., Martín Negri, R., Lex, J., Braslavsky, S.E., Schaffner, K.,..., Vogel, E. (1992) . Photophysics and Photochemistry of 22π and 26π Acetylene-Cumulene Porphyrinoids. Journal of the American Chemical Society, 114(25), 9969-9978.
http://dx.doi.org/10.1021/ja00051a032
---------- CHICAGO ----------
Mãrtire, D.O., Jux, N., Aramendía, P.F., Martín Negri, R., Lex, J., Braslavsky, S.E., et al. "Photophysics and Photochemistry of 22π and 26π Acetylene-Cumulene Porphyrinoids" . Journal of the American Chemical Society 114, no. 25 (1992) : 9969-9978.
http://dx.doi.org/10.1021/ja00051a032
---------- MLA ----------
Mãrtire, D.O., Jux, N., Aramendía, P.F., Martín Negri, R., Lex, J., Braslavsky, S.E., et al. "Photophysics and Photochemistry of 22π and 26π Acetylene-Cumulene Porphyrinoids" . Journal of the American Chemical Society, vol. 114, no. 25, 1992, pp. 9969-9978.
http://dx.doi.org/10.1021/ja00051a032
---------- VANCOUVER ----------
Mãrtire, D.O., Jux, N., Aramendía, P.F., Martín Negri, R., Lex, J., Braslavsky, S.E., et al. Photophysics and Photochemistry of 22π and 26π Acetylene-Cumulene Porphyrinoids. J. Am. Chem. Soc. 1992;114(25):9969-9978.
http://dx.doi.org/10.1021/ja00051a032