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Redes de polímeros con Pd (II) y Pt (II) cúbicos M6 L12 Junciones de jaulas orgánicas y metálicas: síntesis y
Julia Zhao1, Eduard O Bobylev1, David J Lundberg2
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Journal of the American Chemical Society
|September 29, 2023
Resumen
En este estudio se introducen geles poliméricos metálicos orgánicos (polyMOC) que utilizan iones de paladio (II) y platino (II). Estos nuevos poliMOC demuestran propiedades de disipación de energía sintonizables mediante el control de la dinámica de intercambio metal-ligando.
Área de la Ciencia:
- Ciencias de los materiales
- Química de los polímeros
- Química supramolecular
Sus antecedentes:
- Las jaulas/poliedros metal-orgánicos (MOC) son los bloques de construcción clave para las redes de polímeros avanzados.
- Las investigaciones anteriores no han explorado los poliMOC de los MOC estables basados en Pt (II) o los sistemas mixtos Pd (II) / Pt (II).
- El impacto de la dinámica de intercambio metal-ligando en la disipación de energía de los poliMOC sigue sin investigarse en gran medida.
Objetivo del estudio:
- Introducir una nueva arquitectura de jaula orgánica-metálica de polímeros (polyMOC).
- Para demostrar la síntesis de poliMOC utilizando mezclas de iones de paladio (II) y platino (II).
- Investigar la relación entre la dinámica de intercambio metal-ligando y la disipación de energía de los poliMOC.
Principales métodos:
- Geles de poliMOC sintetizados mediante hebras de polietilenglicol (PEG) entrelazadas por cubos M6L12 (M=Pd(II), Pt(II) o mezclas.
- Varió el contenido de Pd (II) dentro de las estructuras de la red polyMOC.
- Se analizaron las tasas de relajación de tensión y la dinámica de intercambio metal-ligando a nivel de la unión M6L12.
Principales resultados:
- Desarrolló una nueva clase de geles polyMOC con estructuras de red ajustables.
- Las tasas de relajación de tensión ajustables alcanzadas abarcan tres órdenes de magnitud por el contenido variable de Pd{\displaystyle Pd{\mathrm {II}}} y Pt{\displaystyle Pt{\mathrm {II}}} .
- Se han observado comportamientos únicos de relajación en los poliMOC de metales mixtos, lo que indica interacciones cooperativas intraconjuntivas.
Conclusiones:
- Se introdujo una nueva arquitectura MOC para el diseño y la síntesis de polyMOC.
- Se han obtenido con éxito poliMOC a partir de mezclas de iones metálicos Pd (II) /Pt (II).
- Se demostró que los poliMOC exhiben un comportamiento de relajación único debido a las uniones multivalentes, lo que permite un control independiente de las propiedades del material.
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