Visible and infrared spectroelectrochemistry of zinc and manganese porphinones: Metal vs. porphyrin reduction

Tutunea, Florentina; Atifi, Abderrahman

doi:10.1016/j.jelechem.2015.02.024

Cited by 7 publications

(18 citation statements)

References 25 publications

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“…A scale factor of 0.94 was used for the m06 calculation of IR spectra, based on the empirical fit for a series of metalloporphinones. 29 …”

Section: Methodsmentioning

confidence: 99%

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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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“…A scale factor of 0.94 was used for the m06 calculation of IR spectra, based on the empirical fit for a series of metalloporphinones. 29 …”

Section: Methodsmentioning

confidence: 99%

“…The ligand, H2OEPone, was synthesized by literature procedures. 29 Anhydrous tetrahydrofuran (THF) was purchased from Sigma-Aldrich Chemical Co. and refluxed in the presence of sodium and benzophenone under nitrogen until the solution was a deep blue. Activated alumina was obtained from EMD (chromatographic grade, 80-200 mesh).…”

Section: Chemicalsmentioning

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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“…[24][25][26] Only the m06 functional was used for the NMR calculations. The Wachters basis set was used for iron.…”

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confidence: 99%

“…In calculating the infrared spectra by DFT, it was found from previous studies on related complexes 25 that a scale factor of 0.94 was appropriate for the m06 functional and 1.0 for the bp86 and mpwvwn functionals, though the bp86 functional tended to underestimate the vibrational energies. The results are shown in Table 2.…”

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confidence: 99%

X-ray Structure and Properties of the Ferrous Octaethylporphyrin Nitroxyl Complex

et al. 2016

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Synopsis:The X-ray crystal structure of [Fe(OEP) (NO)]− is reported, along with infrared and NMR spectra. The Fe−N−O bond angle decreased upon reduction and was consistent with those in other {FeNO} 8 complexes. The 1 H NMR spectrum was reported, which was different from those for other S = 0 metalloporphyrin complexes due to the displacement of the Fe atom from the porphyrin plane. This spectrum was consistent with DFT calculations.NOT THE PUBLISHED VERSION; this is the author's final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page.Inorganic Chemistry, Vol 55, No. 5 (2016): pg. 2070-2075. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society. 2 AbstractThe preparation and characterization of the iron octaethylporphyrin nitroxyl ion, [Fe(OEP), is reported. The complex was synthesized by the oneelectron reduction of Fe(OEP)(NO) using anthracenide as the reducing agent. The compound was isolated as the potassium (2.2.2)cryptand salt. The anion was characterized using X-ray analysis with visible and infrared spectroscopy. The spectral features of the iron nitroxyl complex were consistent with previous literature reports. The important structural changes upon reduction were a significant decrease in the Fe-N-O bond angle from 142° to 127° and an increase in the N-O bond length from that in the starting nitrosyl moiety. The porphyrin ring became significantly less planar upon reduction, but the displacement of the iron atom from the 24-atom plane was essentially unchanged. In spite of the attempt to encapsulate the potassium ion with the (2.2.2)cryptand, significant interaction between K + and the oxygen of the nitroxyl were observed, indicating a contact ion pair in the crystal structure. Comparison between the experimental structure and the DFT-calculated parameters were reported. The results are consistent with the Fe-N-O moiety being the site of the reduction, with little evidence for the reduction of the iron itself or the porphyrin ring. The proton NMR spectrum was also obtained, NOT THE PUBLISHED VERSION; this is the author's final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page.Inorganic Chemistry, Vol 55, No. 5 (2016): pg. 2070-2075. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society.3 and the chemical shifts were significantly different from other S = 0 metalloporphyrin complexes. These shifts, though, were consistent wit...

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“…The electrochemical cell in transmission IR-SEC most frequently uses a mesh electrode configuration. 11,15,[28][29][30][31] This configuration was first reported by Murray et al 32 for the use in UV/Vis-SEC and later adapted by Moss et al 11 for the use in IR-SEC.…”

Section: Transmission Ir-secmentioning

confidence: 99%

Spectroelectrochemistry, the future of visualizing electrode processes by hyphenating electrochemistry with spectroscopic techniques

Lozeman

Führer

Olthuis

et al. 2020

Analyst

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The combination of electrochemistry and spectroscopy, known as spectroelectrochemistry (SEC), is an already established approach. By combining these two techniques, the relevance of the data obtained is greater than what it would be when using them independently. A number of review papers have been published on this subject, mostly written for experts in the field and focused on recent advances. In this review, written for both the novice in the field and the more experienced reader, the focus is not on the past but on the future. The scope is narrowed down to four techniques the authors claim to have the most potential for the future, namely: infrared spectroelectrochemistry (IR-SEC), Raman spectroelectrochemistry (Raman-SEC), nuclear magnetic resonance spectroelectrochemistry (NMR-SEC) and, perhaps slightly more controversial but certainly promising, electrochemistry mass-spectrometry (EC-MS).

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Visible and infrared spectroelectrochemistry of zinc and manganese porphinones: Metal vs. porphyrin reduction

Cited by 7 publications

References 25 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

X-ray Structure and Properties of the Ferrous Octaethylporphyrin Nitroxyl Complex

Spectroelectrochemistry, the future of visualizing electrode processes by hyphenating electrochemistry with spectroscopic techniques

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