Organometallic Photochemistry:: Basic Principles and Applications to Materials Chemistry

• David R. Tyler ^[1]
  1. [1] Department of Chemistry, University of Oregon
• Localización: Journal of chemical education, ISSN 0021-9584, Vol. 74, Nº 6 (June), 1997, págs. 668-672
• Idioma: inglés
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• Resumen

  • An overview is presented of organometallic photochemistry and its applications to materials chemistry. The excited states of typical organometallic complexes include ligand field excited states, metal-to-ligand charge-transfer excited states, ligand-to-metal charge-transfer excited states, Rydberg excited states, and excited states associated with metal-metal bonds. In general, each of these excited states leads to a particular type of photochemical reaction. Ligand field excited states typically lead to metal-ligand bond heterolysis, charge-transfer states to redox processes, and Rydberg states to homolytic metal-ligand bond dissociation. Excitations involving metal-metal bond states lead to metal-metal bond homolysis. Each of these photoprocesses has uses in materials chemistry. Metal-ligand bond dissociations are used to deposit thin films of metals or alloys. The thin films thus produced are used in the manufacture of semiconductors or microcircuitry. Likewise, metal-ligand bond dissociations are used to generate multiply coordinatively unsaturated catalysts for epoxide polymerization. Homolytic dissociations of metal-ligand bonds are used to initiate radical chain polymerization reactions. Irradiation of organometallic compounds on surfaces can be used to derivatize the metal surface. In these processes, a metal-ligand bond is dissociated and then replaced by a functionalized ligand bearing a redox active metal center. These derivatized surfaces are potentially useful in the fabrication of microfabricated circuits.