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 04:00:00 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), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:11; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

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