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Isomerism in Complexes
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Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
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Mesofasas columnares sintonizables que utilizan complejos donante-aceptor aromáticos simétricos C2.

Joseph J Reczek1, Karen R Villazor, Vincent Lynch

  • 1Department of Chemistry and Biochemistry, The University of Texas at Austin, Texas 78712, USA.

Journal of the American Chemical Society
|June 15, 2006
PubMed
Resumen

Los investigadores crearon columnas moleculares de autoensamblaje utilizando derivados de naftaleno (Dan) rico en electrones y diimida (Ndi) con deficiencia de electrones. Estos materiales forman mesofasas estables, lo que permite un ajuste predecible de las temperaturas de transición de fase y exhiben cambios de color al cristalizarse.

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Área de la Ciencia:

  • Ciencia de los materiales Ciencia de los materiales.
  • Química supramolecular de las moléculas.
  • Electrónica orgánica y electrónica orgánica.

Sus antecedentes:

  • Los donantes de naftaleno (Dan) y los aceptores de naftalenetetracarboxílico diimida (Ndi) se utilizan en el autoensamblaje molecular.
  • Trabajos anteriores se centraron en el ensamblaje de la fase de solución de sistemas moleculares complejos.

Objetivo del estudio:

  • Para dirigir el ensamblaje de columnas extendidas con estructuras apiladas alternadas centradas en la cara en estado sólido utilizando derivados de Dan y Ndi.
  • Para investigar las propiedades térmicas y el comportamiento de fase de estos sistemas autoensamblados.
  • Para explorar la relación entre las propiedades de los componentes y el comportamiento de la mesofase.

Principales métodos:

  • Síntesis de 1,5-dialcoxinaftaleno (Dan) y derivados de 1,4,5,8-naftaleno y tetracarboxilo diimida (Ndi).
  • Formación y caracterización de mezclas 1:1 Dan:Ndi.
  • Análisis térmico (DSC, TGA) para determinar la estabilidad de la mesofase y las temperaturas de transición.
  • Análisis estructural de conjuntos de estado sólido.

Principales resultados:

  • 1:1 mezclas Dan:Ndi formaron mesofasas estables hasta 110°C.
  • Las mesofasas exhibieron fases de cristal blando/plástico y algunas propiedades cristalinas líquidas, con columnas donantes-aceptantes alternadas.
  • Se observó una correlación entre las temperaturas de transición de la mesofase y los puntos de fusión / despeje de los componentes individuales Dan y Ndi.
  • Los derivados estéricamente impedidos mostraron un cambio dramático de color de rojo a amarillo tras la cristalización debido a la separación de fase.

Conclusiones:

  • Los derivados de Dan y Ndi pueden dirigir eficazmente la formación de autoensamblajes columnares alternados en estado sólido.
  • Las temperaturas de transición de la mesofase son predeciblemente sintonizables mediante la selección de los componentes Dan y Ndi apropiados.
  • La separación de fases en sistemas estéricamente obstaculizados conduce a cambios significativos en las propiedades ópticas tras la cristalización.