Ligand control of the mechanism of photosensitization by copper(I) compounds

Journal Article · Mon Feb 01 04:00:00 EST 1982 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00132a015· OSTI ID:5807246

Borsub, N; Chang, S C; Kutal, C

Formation of a ground-state complex between CuBr(py)(PPh/sub 3/) (py is pyridine) and norbornadiene (NBD) occurs upon mixing the compounds in benzene. Irradiation of the complex with 313-nm light generates the valence isomer quadricyclene (Q) with moderate observed quantum efficiency. This efficiency varies with the nature and concentration of excess ligands present in solution. Spectral studies reveal that this behavior arises fom the creation of new Cu(I) species whose sensitization properties differ from those of CuBr(py)(PPh/sub 3/). Thus a sufficient excess of triphenylphosphine converts the parent compound to CuBr(PPh/sub 3/)/sub 3/. The latter species functions as an effective sensitizer for Q production but by a pathway involving bimolecular interaction of photoexcited CuBr(PPh/sub 3/)/sub 3/ with ground-state NBD. These results demonstrate that the mechanism of sensitization by Cu(I) can be controlled by the judicious addition of ligands to the system.

• Research Organization: Univ. of Georgia, Athens
• DOE Contract Number: FG02-79ER10540
• OSTI ID: 5807246
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 21:2; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ABSORPTION SPECTRA
ALKENES
AROMATICS
AZINES
BENZENE
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMATOGRAPHY
COMPLEXES
COPPER COMPLEXES
CYCLOALKENES
DATA
EFFICIENCY
ELECTRON SPECTRA
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
GAS CHROMATOGRAPHY
GROUND STATES
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
ISOMERIZATION
KINETICS
LIGANDS
NORBORNADIENE
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
PHOTOCHEMICAL REACTIONS
PYRIDINES
QUADRICYCLENE
QUANTUM EFFICIENCY
REACTION KINETICS
SEPARATION PROCESSES
SPECTRA
SPECTROPHOTOMETRY
TRANSITION ELEMENT COMPLEXES