Caracterización fotofísica de complejos de carboxilatos de renio (I) tricarbonil diimina
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Fecha
2020
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Facultad/escuela
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es
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Universidad Andrés Bello
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Licencia CC
Licencia CC
Resumen
El renio (Re) es un metal de la tercera serie de transición, muy utilizado en joyería y se
obtiene a partir de la refinación del molibdeno (Mo). Dentro de los complejos de renio,
podemos destacar los complejos de haluro tricarbonil diimina de Renio (I), debido a sus
usos relevantes para la investigación, a sus propiedades fotofísicas, su síntesis,
estabilidad y a sus usos potenciales como la captura de luz para reacciones, la detección
de aniones, bioquímica y la foto-reducción de CO2.
Los complejos de tricarbonil de Renio (I) son interesantes para los investigadores y ha
impulsado a nuevos estudios, gracias a que sus propiedades fotofísicas pueden ser
modificadas cambiando la naturaleza de los ligandos a los cuales se coordina el centro
metálico.
En el presente trabajo, se realizó un estudio de la caracterización fotofísica de los
complejos de ReI
, [(bppdz)Re(CO)3Br], [(bppdz)Re(CO)3(OOCCH3)], [(phen)Re(CO)3Br]
y [(phen)Re(CO)3(OOCCH3)], previamente sintetizados en el Laboratorio de Síntesis
Inorgánica. Para el estudio fotofísico de los complejos, se realizaron mediciones de los
espectros de absorción y emisión en distintos solventes tales como diclorometano (DCM),
etanol/metanol (EtOH/MeOH), acetonitrilo (ACN) y dimetilformamida (DMF), se
determinaron los rendimientos cuánticos de emisión y de generación de oxígeno
molecular singlete y las mediciones de los tiempos de vida de luminiscencia.
Gracias a estos estudios se determinaron los efectos de la polaridad del solvente dentro
de los espectros de absorción y emisión de los compuestos y como afecta al
desplazamiento de la banda la sustitución del haluro (Br-) por un carboxilato (CH3COO-).
Rhenium (Re) is a metal of the third transition series, widely used in jewelry and is obtained from the refining of molybdenum (Mo). Within the Rhenium complexes, we can highlight the Rhenium (I) tricarbonyl diimine halide complexes, due to their relevant uses for research, their photophysical properties, their synthesis, stability and their potential uses such as capturing light for reactions, the detection of anions, biochemistry and the photo-reduction of CO2. Rhenium (I) tricarbonyl complexes are interesting for researchers and has prompted new studies, thanks to the fact that their photophysical properties can be modified by changing the nature of the ligands to which the metal center coordinates. In the present work, a study of the photophysical characterization of the ReI complexes, [(bppdz)Re(CO)3Br], [(bppdz)Re(CO)3(OOCCH3)], [(phen)Re(CO)3Br] and [(phen)Re(CO)3(OOCCH3)], previously synthesized in the Inorganic Synthesis Laboratory. For the photophysical study of the complexes, measurements of the absorption and emission spectra were carried out in different solvents such as dichloromethane (DCM), ethanol/methanol (EtOH/MeOH), acetonitrile (ACN) and dimethylformamide (DMF), the quantum emission and generation yields of singlet molecular oxygen and measurements of luminescence lifetimes. Thanks to these studies, the effects of solvent polarity were determined within the absorption and emission spectra of the compounds and how the replacement of the halide (Br- ) by a carboxylate (-OOCCH3) affects the displacement of the band. As a result of these studies, the effects of solvent polarity over the absorption and emission spectra of the compounds were determined, specially the band shifting related to the substitution of the halide (Br-) by a carboxylate (CH3COO-).
Rhenium (Re) is a metal of the third transition series, widely used in jewelry and is obtained from the refining of molybdenum (Mo). Within the Rhenium complexes, we can highlight the Rhenium (I) tricarbonyl diimine halide complexes, due to their relevant uses for research, their photophysical properties, their synthesis, stability and their potential uses such as capturing light for reactions, the detection of anions, biochemistry and the photo-reduction of CO2. Rhenium (I) tricarbonyl complexes are interesting for researchers and has prompted new studies, thanks to the fact that their photophysical properties can be modified by changing the nature of the ligands to which the metal center coordinates. In the present work, a study of the photophysical characterization of the ReI complexes, [(bppdz)Re(CO)3Br], [(bppdz)Re(CO)3(OOCCH3)], [(phen)Re(CO)3Br] and [(phen)Re(CO)3(OOCCH3)], previously synthesized in the Inorganic Synthesis Laboratory. For the photophysical study of the complexes, measurements of the absorption and emission spectra were carried out in different solvents such as dichloromethane (DCM), ethanol/methanol (EtOH/MeOH), acetonitrile (ACN) and dimethylformamide (DMF), the quantum emission and generation yields of singlet molecular oxygen and measurements of luminescence lifetimes. Thanks to these studies, the effects of solvent polarity were determined within the absorption and emission spectra of the compounds and how the replacement of the halide (Br- ) by a carboxylate (-OOCCH3) affects the displacement of the band. As a result of these studies, the effects of solvent polarity over the absorption and emission spectra of the compounds were determined, specially the band shifting related to the substitution of the halide (Br-) by a carboxylate (CH3COO-).
Notas
Unidad de Investigación (Licenciado en Química)
Financiado por FONDECYT 1200418. Financiamiento Basal AFB 180001 (CEDENNA)
Financiado por FONDECYT 1200418. Financiamiento Basal AFB 180001 (CEDENNA)
Palabras clave
Renio, Propiedades Fotofísicas