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Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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La ruta de la superbase hacia los grupos de calcogénidos supertetraédricos.

Tao Wu1, Xianhui Bu, Puhong Liao

  • 1Department of Chemistry, University of California, Riverside, California 92521, USA.

Journal of the American Chemical Society
|February 17, 2012
PubMed
Resumen

Los investigadores sintetizaron mayores grupos discretos de calcogénidos supertetraédricos, incluido el mayor grupo T5 hasta la fecha. Las superbases orgánicas (DBN y DBU) estabilizaron la creciente carga negativa, superando un gran desafío de síntesis.

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Área de la Ciencia:

  • Química Inorgánica La Química Inorgánica es la química inorgánica.
  • Ciencia de los materiales Ciencia de los materiales.
  • Nanotecnología La nanotecnología es la nanotecnología.

Sus antecedentes:

  • Los cúmulos Tn supertetraédricos son fragmentos de una red cúbica de ZnS.
  • La síntesis de cúmulos Tn discretos más grandes es un desafío debido al aumento de la carga negativa.

Objetivo del estudio:

  • Para sintetizar más grandes grupos discretos de calcogénidos supertetraédricos.
  • Para superar los desafíos en la síntesis de grandes grupos de Tn.

Principales métodos:

  • Se utilizaron superbasas orgánicas, 1,5-diazabiciclo[4.3.0]non-5-eno (DBN) y 1,8-diazabiciclo[5.4.0]undec-7-eno (DBU), para estabilizar las cargas negativas.
  • Los racimos sintetizados van desde T3 hasta T5.

Principales resultados:

  • Se han sintetizado con éxito grupos discretos de calogenuros supertetraédricos desde T3 (10 sitios metálicos) hasta T5 (35 sitios metálicos).
  • El cúmulo T5 es el cúmulo Tn supertetraédrico molecular más grande reportado hasta la fecha.
  • Las superbases orgánicas estabilizaron efectivamente la carga negativa creciente en los cúmulos más grandes.

Conclusiones:

  • El uso de superbases orgánicas es una estrategia viable para sintetizar grandes y discretos cúmulos supertetraédricos.
  • Este trabajo amplía el rango de tamaño de los accesibles cúmulos moleculares supertetraédricos.
  • El cúmulo T5 representa un avance significativo en el campo de la síntesis de cúmulos supertetraédricos.