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Photophysics and photochemistry of 2,2'-bipyridine and 1,10-phenanthroline complexes of vanadium(II)

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00231a031· OSTI ID:5454830
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The lifetimes of the lowest energy excited states of V(bpy)/sub 3//sup 2 +/ (bpy = 2,2'-bipyridine) and V(phen)/sub 3//sup 2 +/ (phen = 1,10-phenanthroline) are 500 ps and 1.8 ns, respectively, in ethanol at room temperature. These lifetimes are much shorter than those for the isoelectronic chromium(III) complexes. The lowest energy excited states in the vanadium systems are probably either /sup 2/E//sup 2/T/sub 1/ or quartet MLCT states. Electrode potentials for the V(NN)/sub 3//sup 3+/2+/ couples are approximately 0.09 (NN = bpy) and 0.13 V (NN = phen) in CH/sub 3/CN vs. Fc/Fc/sup +/ (Fc = ferrocene), based on cyclic voltammetry data. Irradiation of V(phen)/sub 3//sup 2 +/ in its lowest energy electronic absorption band (lambda/sub max/ = 640 nm) in the presence of various electron acceptors results in one-electron oxidation and ultimate formation of (phen)/sub 2/V(..mu..-OH)/sub 2/V(phen)/sub 2//sup 4 +/. Similar photoredox processes are observed for V(bpy)/sub 3//sup 2 +/. The photooxidation mechanism involves oxidative quenching of the V(NN)/sub 3//sup 2 +/ excited state, followed by hydrolysis and dimerization of V(NN)/sub 3//sup 2 +/.

Research Organization:
Washington Univ., St. Louis, MO
OSTI ID:
5454830
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:11; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ABSORPTION SPECTRA
ABSORPTION SPECTROSCOPY
ALCOHOLS
AROMATICS
AZAARENES
AZINES
BIPYRIDINES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
ELECTRON TRANSFER
ENERGY LEVELS
ETHANOL
EXCITED STATES
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
LIFETIME
MEDIUM TEMPERATURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHENANTHROLINES
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PYRIDINES
REDOX REACTIONS
SPECTRA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
VANADIUM COMPLEXES
VOLTAMETRY