Quenching of triplet states of organic compounds by copper(II) and nickel(II) 1,3-diketonates in acetonitrile solution. Energy and/or electron transfer

Journal Article · Thu Aug 04 04:00:00 EDT 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100082a022· OSTI ID:6914763

Hug, G L ^[1]; Marciniak, B ^[2]

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1. Univ. of Notre Dame, IN (United States)
2. Univ. of Notre Dame, IN (United States) A. Mickiewicz Univ., Poznan (Poland)

Rate constants for quenching of the triplet states of 15 organic compounds by copper(II) bis(2,4-pentanedionate), Cu(acac)[sub 2], copper(II) bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate), Cu(hfac)[sub 2], Ni(II) bis(2,4-pentanedionate), Ni(acac)[sub 2], and Ni(II) bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate), Ni(hfac)[sub 2], in acetonitrile solution have been measured using the nanosecond laser flash photolysis technique. The quenching data were interpreted in terms of energy or electron transfer alone or in terms of both as competitive processes. With a classical framework for energy and electron transfer, the correlations of the quenching rate constants with the standard free energy changes for energy and electron transfer were used to evaluate appropriate intrinsic barriers and transmission coefficients for both processes. In acetonitrile, quenching by Cu(acac)[sub 2] was suggested to occur mainly by electron transfer, whereas quenching by Cu(hfac)[sub 2] was shown to involve energy transfer to the ligand-localized triplet in combination with electron transfer. 58 refs., 4 figs., 5 tabs.

• OSTI ID: 6914763
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:31; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
99 GENERAL AND MISCELLANEOUS
990200 -- Mathematics & Computers
ACETONITRILE
AROMATICS
BENZENE
CHEMICAL REACTIONS
COMPILED DATA
COPPER COMPOUNDS
DATA
DECOMPOSITION
DIFFUSION
DISPERSIONS
ELECTRON TRANSFER
ENERGY
ENERGY LEVELS
ENERGY TRANSFER
EXCITED STATES
FREE ENERGY
HYDROCARBONS
INFORMATION
INFRARED SPECTRA
LASERS
MATHEMATICAL MODELS
MECHANICS
MIXTURES
MULTIPLETS
NICKEL COMPOUNDS
NITRILES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PHYSICAL PROPERTIES
QUANTUM MECHANICS
QUENCHING
SOLUTIONS
SPECTRA
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPOUNDS
TRIPLETS
VOLTAMETRY