Clean Singlet Oxygen Production by a ReI Complex Embedded in a Flexible Self-Standing Polymeric Silsesquioxane FilmReport as inadecuate




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Rhenium complexes are versatile molecular building blocks whose tunable photophysical properties are useful in diverse opto-related applications. Herein we report the synthesis and characterization of a novel ReI tricarbonyldiimine complex, phenReCO3Br phen: 1,10-phenanthroline, which was found to be an efficient singlet oxygen O21Δg photosensitizer in homogeneous solution ΦO21Δg = 0.55 dichloromethane and 0.16 dimethylformamide. The photophysical properties of phenReCO3Br were thoroughly characterized in solution and modeled by means of density functional theory DFT and time-dependent TD-DFT quantum mechanical calculations. The Re complex was incorporated into a flexible polymeric silsesquioxane SSO film, which has excellent dopant compatibility, chemical resistance, and mechanical properties. When phenReCO3Br is embedded in the SSO film, it is found to retain most of the photophysical characteristics observed for the complex in solution. In particular, the phenReCO3Br-doped SSO films were able to photosensitize O21Δg when illuminated with blue light ∼405 nm. The O21Δg sensitization by films in acetonitrile was followed by the photooxidation of the well-known O21Δg chemical trap 9,10-dimethylanthracene DMA and confirmed by the direct observation of the O21Δg luminescence spectrum centered at 1270 nm and the measurement of its kinetic profile. These results highlight the potential application of this type of polymeric material in the production of biological- or microbial-photoinactivating flexible surfaces or in the implementation of interfacial solid-liquid strategies for the photoinduced oxidation of organic compounds in solution.Nota general

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Author: Spada, Ramiro M.; - Cepeda Plaza, Marjorie; - Gómez, María L.; - Günther Sapunar, Germán; - Jaque, Pablo; - Pizarro, Nancy;

Source: http://repositorio.uchile.cl/



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