Reactions of the excited state of polypyridyl chromium(III) ion
There has been much recent interest in the photochemistry and photophysics of transition metal polypyridine complexes due to the possibility of their use in solar energy conversion systems. The excited state of these compounds are known to undergo useful electron transfer and energy transfer reactions. This work attempts to elucidate the mechanism of the quenching of *CrL{sub 3}{sup 3+} (where L = 2,2{prime}-bipyridine, 4,4{prime}-dimethyl-2,2{prime}-bipyridine, 1,10-phenanthroline, 5-chloro-1,10-phenanthroline, 5-methyl-1,10-phenanthroline) by oxalate ions in neutral pH. Evidence suggests an ion-pairing pre-equilibrium followed by rate limiting electron transfer to produce CrL{sub 3}{sup 2+} and CO{sub 2}{sup {minus}} can then react with ground state chromium(III) species to produce another mole of the reduced product or it can produce a secondary transient as in the case of phenanthroline and substituted phenanthroline complexes. The secondary transient reacts to produce CrL{sub 3}{sup 2+} in a subsequent reaction. 85 refs., 24 figs., 7 tabs.
- Research Organization:
- Ames Lab., IA (USA)
- Sponsoring Organization:
- DOE/ER
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 6764870
- Report Number(s):
- IS-T-1442; ON: DE91000741
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
AROMATICS
AZAARENES
AZINES
BIPYRIDINES
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CARBOXYLIC ACID SALTS
CHALCOGENIDES
CHROMIUM COMPLEXES
CHROMIUM COMPOUNDS
COMPLEXES
ELECTRON TRANSFER
ENERGY LEVELS
EXCITED STATES
HETEROCYCLIC COMPOUNDS
ION PAIRS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXALATES
OXIDES
OXYGEN COMPOUNDS
PHENANTHROLINES
PYRIDINES
QUENCHING
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS