Time-resolved emission at the glass-to-fluid transition. Localization or delocalization in polypyridyl-based metal-to-ligand charge-transfer excited states of ruthenium and osmium

Journal Article · Thu Mar 12 00:00:00 EST 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100290a008· OSTI ID:6772978

Danielson, E; Lumpkin, R S; Meyer, T J

The time dependence of MLCT excited-state emission for (Os(phen)(das)/sub 2/)/sup 2 +/ in the glass-to-fluid transition region in 4:1 ethanol-methanol is analogous to that observed earlier for (Ru(bpy)/sub 3/)/sup 2 +/. This observation calls into question the earlier suggestion that the origin of the time dependence in the emission spectrum of Ru(bpy)/sub 3//sup 2 +/ is a delocalized, (Ru(bpy/sup -1//3)/sub 3/)/sup 2 +/*, to localized, ((bpy)/sub 2/Ru(bpy/sup -/))/sup 2 +/I, transition. In the osmium complex the time-dependent shifts to lower energy are proposed to arise from a dynamic solvent effect involving solvent dipole reorientations.

• Research Organization: Univ. of North Carolina, Chapel Hill
• DOE Contract Number: AS05-78ER06034
• OSTI ID: 6772978
• Journal Information: J. Phys. Chem.; (United States), Vol. 91:6
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
OSMIUM COMPLEXES
ELECTRONIC STRUCTURE
EXCITED STATES
PHASE TRANSFORMATIONS
RADIATIONLESS DECAY
PYRIDINES
EMISSION SPECTROSCOPY
EXPERIMENTAL DATA
FLUIDS
GLASS
LIFETIME
LIGANDS
METALS
SOLVENTS
TEMPERATURE DEPENDENCE
TIME DEPENDENCE
AZINES
COMPLEXES
DATA
DE-EXCITATION
ELEMENTS
ENERGY LEVELS
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties