title: Electron transfer reaction of porphyrin and porphycene complexes of Cu(II) and Zn(II) in acetonitrile.
abstract: The outer-sphere one-electron oxidation reaction of the Cu(II) and Zn(II) complexes of nonplanar 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin and planar porphycenes as well as those of 2,3,7,8,12,13,17,18-octaethylporphyrin and 5,10,15,20-tetraphenylporphyrin by Cu(2+) giving corresponding pi-cation radicals was investigated spectrophotometrically in acetonitrile. The electron self-exchange rate constants between the parent porphyrin and porphycene complexes and their pi-cation radicals were determined using the Marcus cross relation for the electron transfer reaction. The obtained rate constants are in the order of 10(9) to 10(11) M(-1) s(-1) for the planar porphyrin and porphycene complexes and 10(4) to 10(6) M(-1) s(-1) for the nonplanar OETPP complexes at T = 25.0 degrees C. The relatively slow self-exchange reaction of the distorted porphyrin complexes, as compared with those for the planar porphyrin and porphycene complexes, was ascribed to the significant deformation of the complex associated with the oxidation reaction from the parent complex to the corresponding pi-cation radical.
authors.affiliation: Department of Chemistry, Aichi University of Education, Kariya, 448-8542, Japan.
authors.forename: Kaori
authors.initials: K
authors.lastname: Aoki
authors.forename: Toshimitsu
authors.initials: T
authors.lastname: Goshima
authors.forename: Yohei
authors.initials: Y
authors.lastname: Kozuka
authors.forename: Yukiko
authors.initials: Y
authors.lastname: Kawamori
authors.forename: Noboru
authors.initials: N
authors.lastname: Ono
authors.forename: Yoshio
authors.initials: Y
authors.lastname: Hisaeda
authors.forename: Hideo D
authors.initials: HD
authors.lastname: Takagi
authors.forename: Masahiko
authors.initials: M
authors.lastname: Inamo
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D004583:Electrons; D007700:Kinetics; D010084:Oxidation-Reduction; D011166:Porphyrins / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D015032:Zinc / Q000737:chemistry*
chemical_list: D000097:Acetonitriles; D011166:Porphyrins; C051407:porphycene; D003300:Copper; D015032:Zinc; C032159:acetonitrile