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- W2043702973 abstract "Voltammetric measurements at a Pt-rdde, where vacuum deposited metal-N4 chelate (MeN4C) layers, namely CoTPP, CuTPP (TPP = tetraphenylporphyrine) and CoTAA (TAA = dibenzotetraazaannulene), with a thickness of about 0.35μm to be present at the disc, were performed in 0.1 M LiClO4 in acetonitrile. Any dissolved cationic species can be rereduced at the ring. Anodic dissolution was found to be the only process throughout. The cations dissolve layer by layer. From charge stoichiometry, dimeric and trimeric mono- or dications [(MeN4C)y]z+ were concluded, namely y = 2, z = 1 for CoTPP and y = 3, z = 2 for CuTPP and CoTAA. Cathodic redeposition at the ring cathode could not be observed in any case. Thus the absolute symmetry of the cathodic ring signal with respect to the anodic potentiodynamic dissolution is attributed to the formation of dissolved dimers and trimers. Steric hindrance of the bulky cations is regarded to be responsible for the hindered electrocrystallization. The peak potentials for the anodic dissolution of CoTPP, CuTPP and CoTAA are found to be 0.82, 1.28 and 0.47 V vs. she, respectively. They do not correspond to the redox potentials for dissolved species. This is discussed in great detail. The voltammetric measurements in LiClO4/MeCN are complemented by experiments in 0.01 M aqueous H2SO4." @default.
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- W2043702973 date "1993-05-01" @default.
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- W2043702973 title "Anodic oxidation of cobalt and copper-N4 chelates in the solid state" @default.
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- W2043702973 doi "https://doi.org/10.1016/0013-4686(93)87008-2" @default.
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