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Cristales moleculares porosos por las supramoleculas de coordinación macrocíclica
Irene Bassanetti1, Angiolina Comotti, Piero Sozzani
1Dipartimento di Chimica, Università degli Studi di Parma , viale delle Scienze 17/a, 43124 Parma, Italy.
Journal of the American Chemical Society
|September 25, 2014
Resumen
Este estudio demuestra cómo la coordinación de iones de plata con ligandos y contra-aniones específicos crea estructuras cúbicas porosas. Estos materiales adsorben selectivamente los gases CO2 y N2O, con una porosidad ajustable mediante la modificación del ligando.
Área de la Ciencia:
- Química supramolecular de las moléculas.
- Coordinación Química de la Coordinación
- Ciencia de los materiales Ciencia de los materiales.
Sus antecedentes:
- El diseño de materiales porosos funcionales es crucial para aplicaciones como el almacenamiento y separación de gases.
- El autoensamblaje supramolecular ofrece una ruta versátil para construir arquitecturas complejas con propiedades sintonizables.
Objetivo del estudio:
- Investigar la formación de distintos isómeros supramoleculares (polímeros de coordinación y macrociclos) utilizando iones de plata, ligandos funcionalizados y contra-aniones específicos.
- Caracterizar las estructuras cúbicas resultantes y evaluar su microporosidad permanente y su selectividad de adsorción de gases.
Principales métodos:
- Síntesis de cinco ligandos de bis ((pirazolyl) metano) funcionalizados con tioéter.
- Coordinación de los ligandos con iones de plata (Ag(+)) y contra-aniones (triflato, CF3SO3(-), y hexafluorofosfato, PF6(-)).
- Caracterización estructural utilizando isotermas de difracción de rayos X y adsorción de gas.
- Espectroscopia de RMN de estado sólido para estudiar la difusión de moléculas invitadas.
Principales resultados:
- Se formaron dos isómeros supramoleculares distintos: cadenas poliméricas de coordinación helicoidal con CF3SO3(-) y macrociclos hexaméricos con PF6(-).
- Los macrociclos Hexameric se autoensamblan en estructuras cúbicas con microporosidad permanente, exhibiendo adsorción selectiva de CO2 y N2O sobre CH4 y N2.
- La funcionalización de ligandos moduló la microporosidad, y la RMN de estado sólido confirmó la accesibilidad de los huéspedes a las cavidades.
Conclusiones:
- La elección juiciosa de iones metálicos, ligandos y contra-aniones permite el diseño racional de complejas arquitecturas supramoleculares.
- Los materiales cúbicos sintetizados demuestran potencial para aplicaciones de separación selectiva de gases.
- La modificación de ligandos proporciona una estrategia para ajustar el tamaño de los poros y las propiedades de adsorción de estos materiales de coordinación porosos.
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