Solvent tuning of the excited-state properties of (2,2'-bipyridine)tetracyanoferrate(II): direct observation of a metal-to-ligand charge-transfer excited state of iron(II)

Journal Article · Wed May 27 00:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00245a053· OSTI ID:6365766

Winkler, J R; Creutz, C; Sutin, N

In contrast to Ru(bpy)/sub 3//sup 2 +/ and Os(bpy)/sub 3//sup 2 +/ (bpy = 2,2'-bipyridine) the lowest excited state of Fe(bpy)/sub 3//sup 2 +/ is LF (ligand field) rather than MLCT (metal-to-ligand charge transfer) in character. Replacement of a bpy by two stronger field CN/sup -/ ligands to give Fe(bpy)/sub 2/(CN)/sub 2/ does not alter this ordering. Here the authors report observations that show that in water this ordering is retained for Fe(bpy)(CN)/sub 4//sup 2 -/ even with its stronger ligand field but that the extraordinary solvent sensitivity of this complex can be used to access the MLCT state: the MLCT state is observed in the weak acceptor solvent acetone.

• Research Organization: Brookhaven National Lab., Upton, NY
• DOE Contract Number: AC02-76CH00016
• OSTI ID: 6365766
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 109:11
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACETONE
SOLVENT PROPERTIES
BIPYRIDINES
EXCITED STATES
FERRATES
WATER
EXPERIMENTAL DATA
LIGANDS
PHOTOCHEMISTRY
SOLVENTS
AZINES
CHEMISTRY
DATA
ENERGY LEVELS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
INFORMATION
IRON COMPOUNDS
KETONES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PYRIDINES
TRANSITION ELEMENT COMPOUNDS
400500* - Photochemistry
400201 - Chemical & Physicochemical Properties