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Photoredox and Sensitization Processes Involving Transition Metal Polypyridine Complexes

  • K. Kalyanasundaram
Chapter
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Part of the Catalysis by Metal Complexes book series (CMCO, volume 14)

Abstract

2,2’-bipyridine, 1,10-phenanthroline and related polypyridine ligands are unique in their ability to complex to a large number of transition metal ions across the periodic table. The complexation equilibria and redox reactivity of these complexes have been the focus of experimental investigations for many years [1–3]. Complexes of ions with d6 electronic configuration are attractive from photophysical and photochemical properties point of view. Systematic studies started with the first reports of room-temperature luminescence from Ru(bpy)3 2+ in 1959 by Paris and Brandt[4]. This was followed by key observations by Adamson et al. in the early seventies [5,6] that Ru(bpy)3 2+ could photosensitize aquation of Pt(II)-cyano complexes (eq.1) and redox decomposition of Co(III)-ammine complexes (eq.2):
$$PtC{I_4}^{{2_ - }} + {H_2}O\xrightarrow[{hv}]{{Ru(bpy){3^{2 + }}}}PtC{I_3}{({H_2}O)^ - } + C{I^ - }$$
(1)
$$Co{(N{H_3})_5}B{r^{2 + }}\xrightarrow[{hv}]{{Ru(bpy){3^{2 + }}}}C{o_{aq}}^{3 + } + 5N{H_3} + B{r^ - }$$
(2)
Around this time Fujita and Kobayashi [7] reported detection of phosphorescence of Cr(III) upon excitation of the Ru(bpy)3 2+ band in the double salts composed of CrL6 3− and Ru(bpy)3 2+ (L = CN, ox/2,…)
$$Ru(bhy){3^{2 + *}} \ldots CrL{6^{3 - }} \to Ru{(bhy)_3}^{2 + } \ldots CrL{6^{3 - *}}$$
(3)
Possible intermolecular energy / electron transfer processes were invoked to explain the sensitization. The mechanistic propositions were soon verified by additional luminescence quenching, flash photolysis and sensitization studies.

Keywords

Excited State Mixed Ligand Complex Lower Excited State Quench Rate Constant Sensitization Process 
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Copyright information

© Springer Science+Business Media Dordrecht 1993

Authors and Affiliations

  • K. Kalyanasundaram
    • 1
  1. 1.Institut de Chimie PhysiqueEcole Polytechnique Fédérale de LausanneLausanneSwitzerland

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