Manipulating the properties of MLCT excited states

Anderson, Peter A., Keene, F. Richard, Meyer, Thomas J., Moss, John A., Strouse, Geoffrey F., and Treadway, Joseph A. (2002) Manipulating the properties of MLCT excited states. Dalton Transactions, 2002 (20). pp. 3820-3831.

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Systematic variation of the ligand environment has allowed design of the absorbance characteristics of polypyridyl complexes of ruthenium(II) to produce “black absorbers” which absorb throughout the visible region. The presence of acceptor ligands with low-lying Π* levels red shift the energies of the lowest energy MLCT bands, while MLCT and Π→Π* bands originating on other ligands can be used to fill in the higher-energy regions of the spectrum. Incorporation of anionic ligands or other electron-donating ligands causes a red shift in MLCT band energies compared to bpy by manipulation of dΠ energy levels. Attention to these design principles has led to the synthesis of complexes which absorb appreciably in the near IR, and are free from complications caused by thermally accessible dd states. Although their emission energies (and energy gaps) are at low energy in the near IR, the use of lowest lying, delocalised acceptor ligands provides lifetime enhancements (compared to bpy) that can be dramatic.

Item ID: 240
Item Type: Article (Research - C1)
ISSN: 1477-9234
Keywords: black absorber, photosensitizer, MLCT, solar energy conversion
Date Deposited: 03 May 2007
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 51%
03 CHEMICAL SCIENCES > 0306 Physical Chemistry (incl Structural) > 030606 Structural Chemistry and Spectroscopy @ 49%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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