Spectroscopic and electrochemical characterization of nickel .beta.-oxoporphyrins: identification of nickel(III) oxidation products

Connick, Patricia A.; Macor, Kathleen A.

doi:10.1021/ic00024a038

Cited by 69 publications

(21 citation statements)

References 7 publications

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“…This compares with a 20 and 30 mV shift of the E° in acetonitrile and methylene chloride, respectively, and a 60 (acetonitrile) and 100 mV (methylene chloride) shift of the E2° value. 18 The third reduction of Ni(OEPone) has not been previously reported. With the addition of AmNTf2, the reduction peaks shifted to more positive potentials whereas the oxidation peaks shifted to less positive potentials (Figure 4).…”

Section: Cyclic Voltammetry and Spectroelectrochemistry Of Nickel Octmentioning

confidence: 89%

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Spectroscopic Evidence of Nanodomains in THF/RTIL Mixtures: Spectroelectrochemical and Voltammetric Study of Nickel Porphyrins

Atifi

2015

Anal. Chem.

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The presence and effect of RTIL nanodomains in molecular solvent/RTIL mixture were investigated by studying the spectroelectrochemistry and voltammetry of nickel octaethylporphyrin (Ni(OEP)) and nickel octaethylporphinone (Ni(OEPone)). Two oxidation and 2−3 reduction redox couples were observed, and the UV−visible spectra of all stable products in THF and RTIL mixtures were obtained. The E°values for the reduction couples that were studied were linearly correlated with the Gutmann acceptor number, as well as the difference in the E°values between the first two waves (ΔE 12 °= |E 1 °− E 2 °|). The ΔE 12 °for the reduction was much more sensitive to the %RTIL in the mixture than the oxidation, indicating a strong interaction between the RTIL and the anion or dianion. The shifts in the E°values were significantly different between Ni(OEP) and Ni(OEPone). For Ni(OEP), the E 1 °values were less sensitive to the %RTIL than were observed for Ni(OEPone). Variations in the diffusion coefficients of Ni(OEP) and Ni(OEPone) as a function of %RTIL were also investigated, and the results were interpreted in terms of RTIL nanodomains. To observe the effect of solvation on the metalloporphyrin, Ni(OEPone) was chosen because it contains a carbonyl group that can be easily observed in infrared spectroelectrochemistry. It was found that the ν CO band was very sensitive to the solvent environment, and two carbonyl bands were observed for Ni(OEPone) − in mixed THF/RTIL solutions. The higher energy band was attributed to the reduced product in THF, and the lower energy band attributed to the reduced product in the RTIL nanophase. The second band could be observed with as little as 5% of the RTIL. No partitioning of Ni(OEPone) + into the RTIL nanodomain was observed. DFT calculations were carried out to characterize the product of the first reduction. These results provide strong direct evidence of the presence of nanodomains in molecular solvent/RTIL mixtures.

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Section: Cyclic Voltammetry and Spectroelectrochemistry Of Nickel Octmentioning

confidence: 89%

“…The voltammetry of both complexes exhibited at least two reversible one-electron reduction and three one-electron oxidation redox couples. [14][15][16][17][18] Lexa et al. 16 formulated the first reduction product to be Ni I (OEP) − using UVvisible and EPR spectroscopies.…”

mentioning

confidence: 99%

Spectroscopic Evidence of Nanodomains in THF/RTIL Mixtures: Spectroelectrochemical and Voltammetric Study of Nickel Porphyrins

Atifi

2015

Anal. Chem.

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“…Different factors are effecting of the electrochemical properties and the redox behavior of the transition metal complexes such as axial ligation degree, charge type, coordination number, division of unsaturation, substitution manner and size of the chelate ring. 49,50,51,52,53,54 In our study to promote an understanding of the redox behavior of nine six-coordinate, three each of Cobalt(II), Copper(II) and Nickel(II) complexes of ligands A, D and E, cyclic voltammetric measurements of the complexes were recorded in ethanolic solution in range from +2.0 to -2.0 V using 0.1 Molar [Bu4N][BF4] at sweep rate of 0.1 V. Sec -1 . Same cell setup was used in all CV measurements and the ferrocene/ ferrocenium couple (Fc/Fc + ), E 1/2 = 0.505 V, ∆Ep= 130 mV) was employed as a criterion.…”

Section: Electrochemical Studiesmentioning

confidence: 99%

Novel Nickel (II), Copper (II) and Cobalt (II) Complexes of Schiff Bases A, D and E: Preparation, Identification, Analytical and Electrochemical Survey

2018

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A novel set of Cobalt(II), Copper(II) and Nickel(II) complexes of ligands, (E)-2-(((2,5-difluorophenyl)imino) methyl)phenol (A), (E)-2,4-dibromo-1-((2-hydroxybenzylidene) amino)anthracene-9,10-dione (D) & (Z)-1-((1-([1,1'-biphenyl]-4-yl)-2-bromoethylidene) amino)-2,4-dibromo anthracene-9,10-dione (E) were synthesized and characterized. Their structures were investigated on the basis of CHN, conductance measurements and spectral studies (H1-NMR & C13-NMR,FT-infrared and Electronic spectroscopies), cyclic voltammetry. It has observed from spectral and analytical studies that metal complexes have the composition of (ML2.X2) and one mole of ligand behaves as bidentate chelating agents around the corresponding metal ion. From solubility test, we obtained that metal complexes of ligands A, D and E had no ionic properties and dissolve partially in polar and slightly in nonpolar solvents. These results confirmed the behavior of metal complexes as weak electrolyte from their low value of molar conductivity. Conductance data and solubility test of the complexes enhanced them to be (1:2 M:L ratio). All data confirmed an octahedral geometry of these complexes and their structures as {[M (A, D or E)2(CH3COO)2], when M= Co or Ni} and {[Cu (A, D or E)2 Cl2]}. Cyclic voltammetry measurements were accomplished of Cobalt(II), Copper(II) and Nickel(II) complexes using Pt wire as counter electrode and Ag/AgNO3 as reference electrode and (Bu4N+PF6+) as supporting electrolyte. The result exhibit the irreversible process showing single one electron transfer process of Cobalt(II) and Nickel(II) complexes and unique quasi-reversible redox couple is attributed to Cu(II) complexes.

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“…Generally the redox behavior of the complexes depends on some factors such as: the chelate ring size, axial ligation, degree and distribution of unsaturation and substitution pattern in the chelate ring [42][43][44][45]. In the present study, we attempted to use cyclic voltammeteric measurements for understanding redox behavior of Yb(QS) 3 .…”

Section: Study Of Electrochemical Behavior Of Yb(qs)mentioning

confidence: 99%

Electrochemical spectroscopic investigations on the interaction of an ytterbium complex with DNA and their analytical applications such as biosensor

Ilkhani¹,

Arvand²,

Hejazi³

et al. 2011

International Journal of Biological Macromolecules

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Spectroscopic and electrochemical characterization of nickel .beta.-oxoporphyrins: identification of nickel(III) oxidation products

Cited by 69 publications

References 7 publications

Spectroscopic Evidence of Nanodomains in THF/RTIL Mixtures: Spectroelectrochemical and Voltammetric Study of Nickel Porphyrins

Spectroscopic Evidence of Nanodomains in THF/RTIL Mixtures: Spectroelectrochemical and Voltammetric Study of Nickel Porphyrins

Novel Nickel (II), Copper (II) and Cobalt (II) Complexes of Schiff Bases A, D and E: Preparation, Identification, Analytical and Electrochemical Survey

Electrochemical spectroscopic investigations on the interaction of an ytterbium complex with DNA and their analytical applications such as biosensor

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