One-electron oxidation of metalloporphycenes as studied by radiolytic methods

Journal Article · Thu Aug 01 04:00:00 EDT 1996 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/jp960942j· OSTI ID:380907

Guldi, D M; Field, J ^[1]; Grodkowski, J; Neta, P ^[2]; Vogel, E ^[3]

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1. Univ. of Notre Dame, IN (United States)
2. National Inst. of Standards and Technology, Gaithersburg, MD (United States)
3. Universitaet zu Koeln (Germany)

One-electron and two-electron oxidations of 2,7,12,17-tetrapropylporphycene (H{sub 2}TPrPc) and its Fe, Co, Ni, Cu, and Sn complexes in CH{sub 2}Cl{sub 2}, CCl{sub 4}, and 2-PrOH solutions have been studied by radiolytic techniques. Formation and decay of intermediates formed upon one-electron oxidation have been followed by kinetic spectrophotometric pulse radiolysis, and the absorption spectra of stable oxidation products have been recorded following {gamma}-radiolysis. H{sub 2}TPrPc is oxidized to the {pi}-radical cation and then to the dication, which is stable in aprotic solvents but is transformed to a different product in 2-PrOH. Similar oxidation to the {pi}-radical cation and then to the dication was observed for the Cu{sup II}, Sn{sup IV}, Co{sup III}, and Fe{sup III} porphycenes. Co{sup II} and Ni{sup II} porphycenes underwent radiolytic oxidation to form stable Co{sup III} and Ni{sup III} products. The stability of the latter is in contrast with previous electrochemical observations, and the difference is ascribed to the effect of the axial ligand. 18 refs., 7 figs., 1 tab.

• OSTI ID: 380907
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 32 Vol. 100; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
CATIONS
CHEMICAL REACTION KINETICS
COBALT COMPLEXES
COPPER COMPLEXES
IRON COMPLEXES
NICKEL COMPLEXES
ORGANOMETALLIC COMPOUNDS
OXIDATION
RADICALS
RADIOLYSIS
REACTION INTERMEDIATES
SYNTHESIS
TIN COMPLEXES