Relationship between the emission spectra and resonance Raman excitation profiles of W(CO)/sub 4/(. cap alpha. -diimine) complexes

Journal Article · Wed Dec 18 04:00:00 EST 1985 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00220a015· OSTI ID:5973533

Servaas, P C; van Dijk, H K; Snoeck, T L; Stufkens, D J; Oskam, A

The photophysical properties of several W(CO)/sub 4/(..cap alpha..-diimine) complexes at 293 and 80 K are reported. For complexes of the type W(CO)/sub 4/L (L = substituted 1,10-phenanthroline or 2,2'-bipyridine) three emissions are found while the lowest energy emission is not observed at room temperature for complexes of the type W(CO)/sub 4/L (L = substituted 1,4-diaza-1,3-butadiene or pyridine-2-carbaldehyde imine). The highest energy emission in all these complexes is assigned to be LF in character; the other ones appear to have MLCT character. The occurrence of the lowest energy emission, which is related to the z-polarized b/sub 2/..-->..b/sub 2//sup */ transition, depends on the MLCT character of this transition. This relationship is deduced from the resonance Raman excitation profiles and the luminescence excitation spectra of these complexes. Complexes with strong MLCT character for the z-polarized b/sub 2/ ..-->.. b/sub 2//sup */ transition show a low-energy emission, while this is not the case for complexes with much less MLCT character for this transition. These results are explained by the efficiency of the radiationless processes, which is large when metal-ligand stretching modes act as promoting modes. 20 references, 6 figures, 2 tables.

• Research Organization: Univ. of Amsterdam, Netherlands
• OSTI ID: 5973533
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:26; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
CHEMISTRY
COMPLEXES
DATA
DE-EXCITATION
EMISSION SPECTRA
EMISSION SPECTROSCOPY
ENERGY LEVELS
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EXPERIMENTAL DATA
IMINES
INELASTIC SCATTERING
INFORMATION
LASER SPECTROSCOPY
LIGANDS
LOW TEMPERATURE
LUMINESCENCE
MEDIUM TEMPERATURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMISTRY
PHYSICAL PROPERTIES
RADIATIONLESS DECAY
RAMAN SPECTROSCOPY
RESONANCE SCATTERING
SCATTERING
SPECTRA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES