Aryloxo Derivatives of Phosphorus(V) Porphyrins. Synthesis, Spectroscopy, Electrochemistry, and Singlet State Properties

Inorganic Chemistry

Volumn 35, Issue 17, 1996, Pages 4829-4836

  Anita Rao, T ^a   Maiya, Bhaskar G ^a  

^a UNIVERSITY OF HYDERABAD   (India)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 2542600905     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic9513200     Document Type: Article

References (49)

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34. While the singlet state energy of the "porphyrin part" of each aryloxo P(V) porphyrin is 2.008 ± 0.008 V, that of the aromatic axial ligands is expected to be ca. >3.0 V in each case (see, Murov, S. L. Handbook of Photochemistry; Marcel Dekker, Inc.: New York: 1973. Turro, N. J. Modern molecular photochemistry; Benjamin/Cummings: Menlo Park. CA, 1978.)
35. While the singlet state energy of the "porphyrin part" of each aryloxo P(V) porphyrin is 2.008 ± 0.008 V, that of the aromatic axial ligands is expected to be ca. >3.0 V in each case (see, Murov, S. L. Handbook of Photochemistry; Marcel Dekker, Inc.: New York: 1973. Turro, N. J. Modern molecular photochemistry; Benjamin/Cummings: Menlo Park. CA, 1978.)
36. + possesses a "neutral" porphyrin radical species and a cation radical of the aryloxo ligand.
37. +/P(V) values are more positive by at least 1.8 V. It should be noted here that the energies of the charge transfer states estimated here are only "apparent" values. This is because we have employed oxidation potentials of the precursor "free" phenols and not those of the bound aryloxo ligands in the calculation and, in addition, the exact oxidation potentials of the P(V) porphyrins are not known with certainty.
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