Metal-to-ligand charge-transfer (MLCT) photochemistry. Experimental evidence for the participation of a higher lying MLCT state in polypyridyl complexes of ruthenium(II) and osmium(II)

Journal Article · Thu Jan 11 04:00:00 EST 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100364a039· OSTI ID:6713368

Lumpkin, R S; Worl, L A; Murtaza, Z; Meyer, T J ^[1]; Kober, E M ^[2]

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1. Univ. of North Carolina, Chapel Hill (USA)
2. Los Alamos National Laboratory, NM (USA)

Evidence is presented which supports the existence of a thermally accessible, higher lying metal-to-ligand charge-transfer (MLCT) excited state for polypyridyl complexes of Ru(II) and Os(II). This state is shown to exist for complexes both in solution and in the solid state. It is typically found to occur at 300-800 cm{sup {minus}1} above the lowest lying MLCT state and to have a decay rate constant of 10{sup 6}-10{sup 8} s{sup {minus}1}. This decay rate constant is about 10 times faster than the decay rate constant for the next lower lying MLCT state. The decay process appears to be almost completely nonradiative with the radiative decay rate constant estimated to be 10{sup 6} s{sup {minus}1} or slower. The higher lying MLCT states can make a significant contribution to nonradiative decay at room temperature.

• OSTI ID: 6713368
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:1; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400101* -- Activation
Nuclear Reaction
Radiometric & Radiochemical Procedures
400500 -- Photochemistry
CHARGE TRANSPORT
CHEMISTRY
COMPLEXES
DATA
DATA ANALYSIS
ELEMENTS
EXPERIMENTAL DATA
INFORMATION
LIGANDS
MEASURING INSTRUMENTS
MEASURING METHODS
METALS
NUMERICAL DATA
OSMIUM COMPLEXES
PHOTOCHEMISTRY
PYRIDYL RADICALS
RADICALS
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES