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Complejos trinucleares de bis-ferrocenil-piridinediimina con acoplamiento electrónico dependiente de la unión al
Cole Carter1, Yosi Kratish1, Titel Jurca1
1Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, United States.
Journal of the American Chemical Society
|October 16, 2020
Resumen
Este estudio sintetizó complejos de dicloruro de metal con ligandos bis-ferrocenilo, revelando el acoplamiento electrónico entre las unidades de ferroceno al unirse al metal. Este acoplamiento influye en las transiciones electrónicas y permite una comunicación de súper intercambio, con implicaciones para la catálisis.
Área de la Ciencia:
- Química organometálica
- Química de coordinación
- Ciencias de los materiales
Sus antecedentes:
- Los derivados del ferroceno son bloques de construcción versátiles en la química de coordinación.
- La comprensión de la comunicación electrónica en complejos metálicos es crucial para el diseño de materiales funcionales.
- Los ligandos de piridinediimina (PDI) ofrecen propiedades electrónicas sintonizables.
Objetivo del estudio:
- Sintetizar y caracterizar una serie de complejos de dicloruro metálico con un ligando de piridinediimina sustituido por bis-ferrocenilo.
- Para investigar el acoplamiento electrónico entre las unidades de ferroceno en coordinación con un centro metálico.
- Explorar las implicaciones de esta comunicación electrónica para la catálisis y las propiedades de los materiales.
Principales métodos:
- Síntesis sistemática de los complejos (Fc2PDI) MCl2 (M = Mg, Zn, Fe y Co).
- Caracterización mediante cristalografía, espectroscopia (UV-vis, cerca de IR), electroquímica (voltametría cíclica) y métodos computacionales (DFT).
- Análisis de las transiciones electrónicas y las interacciones orbitales.
Principales resultados:
- El acoplamiento electrónico entre las unidades de ferroceno se activa al unirse fragmentos de MCl2, evidenciado por la oxidación secuencial y las bandas de transferencia de carga entre valencias (IVCT).
- Los espectros UV-vis muestran mezcla orbital entre el ferroceno y el ligando PDI, con mayores intensidades de transición y desplazamientos al rojo.
- Los cálculos de DFT sugieren un acoplamiento de súper intercambio a través del LUMO, mediado por la coincidencia de energía entre los orbitales de ferroceno y PDI.
Conclusiones:
- La coordinación a los fragmentos de MCl2 induce una comunicación electrónica significativa entre las unidades de ferroceno en los ligandos Fc2PDI.
- Las distorsiones estructurales durante la oxidación del ferroceno introducen orbitales d vacíos en la esfera de coordinación secundaria, lo que influye en las propiedades electrónicas.
- Los hallazgos tienen implicaciones para el diseño de nuevos catalizadores y materiales electrónicamente activos basados en complejos ferroceno-metálicos.
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