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La conformación de Linker controla los potenciales de oxidación y el electrocromismo en marcos orgánicos metálicos
Leonid Shupletsov1, Sebahat Topal1, Alina Schieck1
1Chair of Inorganic Chemistry I, Technische Universität Dresden, 01069 Dresden, Germany.
Journal of the American Chemical Society
|September 3, 2024
Resumen
Los investigadores desarrollaron nuevos materiales electrocrómicos (EC) utilizando sistemas de tipo Piccard dentro de marcos metálico-orgánicos (MOF) basados en circonio. Estos nuevos materiales CE basados en MOF ofrecen un cambio rápido, un alto contraste y una excelente estabilidad, que coincide con los estándares inorgánicos.
Área de la Ciencia:
- Ciencias de los materiales
- La electroquímica
- Nanotecnología
Sus antecedentes:
- Los materiales electrocrómicos (EC) son cruciales para las ventanas y pantallas inteligentes.
- Los materiales CE actuales se basan a menudo en una gama limitada de bloques de construcción.
- Las estructuras metálicas orgánicas (MOF) ofrecen propiedades sintonizables pero tienen aplicaciones CE limitadas.
Objetivo del estudio:
- Introducir nuevos materiales electrocrómicos basados en sistemas tipo Piccard integrados en MOF basados en zirconio (Zr-MOF).
- Investigar el rendimiento electrocrómico y la estabilidad de estos nuevos materiales.
- Explorar el control de las características redox a través de la topología de marco.
Principales métodos:
- Síntesis de Zr-MOFs que incorporan un ligando del tipo Piccard (N,N,N',N'-benzidina y tetrabenzoato).
- Caracterización de los materiales MOF electrocrómicos resultantes (DUT-65 y DUT-66).
- Pruebas electroquímicas para evaluar las velocidades de conmutación, la relación de contraste, la estabilidad y la reversibilidad.
Principales resultados:
- Los nuevos materiales Zr-MOF exhiben velocidades de conmutación rápidas y altas relaciones de contraste (> 53% de transmitancia en estado blanqueado, ~ 3% en estado coloreado).
- Los materiales demuestran una estabilidad de larga vida, comparable a los materiales inorgánicos CE, con un 90% de coloración alcanzado en 12,5 segundos para una película de 5 μm.
- La topología del marco bloquea la conformación del ligando, permitiendo características redox distintas y control sobre las vías de oxidación.
Conclusiones:
- La integración de sistemas del tipo Piccard en Zr-MOF produce materiales electrocrómicos de alto rendimiento.
- Estos materiales CE basados en MOF ofrecen una alternativa prometedora a los materiales CE inorgánicos tradicionales.
- El diseño del marco proporciona un método para ajustar y controlar el comportamiento electroquímico de los enlaces redox-activos.
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