Artículo
Photolysis of an asymmetrically substituted diazene in solution and in the crystalline state
Hoijemberg, Pablo Ariel
; Karlen, Steven D.; Sanramé, Carlos Norberto; Aramendia, Pedro Francisco
; García Garibay, Miguel Angel
Fecha de publicación:
03/2009
Editorial:
Royal Society of Chemistry
Revista:
Photochemical and Photobiological Sciences
ISSN:
1474-905X
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
In this work we study the product distribution in the steady state photolysis of a diazene, (1-biphenyl-4-yl-1-methyl-ethyl)-tert-butyl diazene, and a ketone, 2,4-bis(biphenyl-4-yl)-2,4-dimethyl-pentan-3-one, in the solid state and in solution. The two compounds yield 1-biphenyl-4-yl-1-methyl-ethyl (BME) radicals upon photolysis. The ketone yields two units of this radical, whereas the diazene yields one BME and one tert-butyl radical. Product analysis of the two compounds in solution makes it possible to differentiate their origin from their corresponding geminate cages, and from the different encounter pairs in the case of the asymmetrically substituted diazene photolysis. In this way we obtain a complete reaction scenery for the diazene, a compound with interesting features as a radical photoinitiator and as a cage effect probe in fluid media. The reaction in cages containing two BME radicals shows a decrease by a factor of 4 in the ratio of combination to disproportionation products upon going from the solid to the liquid phase. On the contrary, the reaction in cages containing a BME and a tert-butyl radical shows a 30-fold increase in combination to disproportionation ratio in liquid compared to the crystal. We analyze the reasons for these differences considering the differences in the reactivity of the radicals and in cage rigidity.
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Articulos(INQUIMAE)
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Citación
Hoijemberg, Pablo Ariel; Karlen, Steven D.; Sanramé, Carlos Norberto; Aramendia, Pedro Francisco; García Garibay, Miguel Angel; Photolysis of an asymmetrically substituted diazene in solution and in the crystalline state; Royal Society of Chemistry; Photochemical and Photobiological Sciences; 8; 7; 3-2009; 961-969
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