Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

PHOTOREDUCTION OF ZINC PORPHIN BY ASCORBIC ACID*

Abstract— Zinc porphin is photoreduced to zinc chlorin through an intermediate dihydroporphin (PH₂) by ascorbic acid in ethanol containing 1% to 10% (v/v) piperidine. Under the same conditions zinc chlorin is more slowly photoreduced to zinc tetrahydroporphin. The reactions leading to chlorin are photosensitized by the product chlorin and so are autocatalytic in red light. Quantum yields for these reactions range up to 0.05.Other aliphatic amines catalyze these reactions, but at rates peculiar to the amine. The immediate product of reduction of zinc porphin, PH₂, is distinguished by an intense band at 437 nm; it reverts to porphin in the dark in the presence of oxygen or dehydroascorbic acid. Its conversion to chlorin is effected by light absorbed by porphin or chlorin, but not by light absorbed by PH₂ itself. A suggested structure for PH₂, compatible with the observed reactions, has added hydrogens on one bridge carbon and one β-pyrrole carbon. The possibility of an analogy between these reactions and the biochemical conversion of protochlorophyll to chlorophyll is discussed.     

DODECYLPYRIDINIUM ALKANOATES STABILIZE DISPERSED CHLOROPHYLL

In the presence of a surfactant that does not ligate Mg, chlorophyll is adsorbed to polyethylene particles swollen with tetradecane principally as the infrared-absorbing, highly polymeric species Chl 740. Examples of such surfactants are quaternary ammonium salts and soaps. However, when surfactants of opposite charge are present together, in this case dodecylpyridinium iodide and Na butyrate or myristate, chlorophyll may exist entirely in a dispersed form absorbing around 666 nm. Absorption and fluorescence spectral data show that much of the dispersed pigment is still associated, but as dimeric and perhaps short oligomeric species. It is concluded from fluorescence lifetime analysis that most of the observed fluorescence comes from a small population of chlorophyll that is probably monomeric and isolated; fluorescence of more highly associated species decays with a wide range of lifetimes. The capacity for photochemical sensitization of these particles with dispersed chlorophyll is similar to that of particles with ligating surfactants examined earlier. Structures are suggested for chlorophyll association in which Mg is ligated by water hydrogen-bonded to a carboxylate group, while the dodecylpyridinium counterion lies near the chlorophyll ring. The effect of the two surfactants is synergistic. Overall, spectra of dispersed chlorophyll adsorbates resemble most closely those of colloidal chlorophyll suspensions prepared by dilution of solutions in polar organic solvents with water.