McNicholas, Brendon J. and Blumenfeld, Carl and Kramer, Wesley W. and Grubbs, Robert H. and Winkler, Jay R. and Gray, Harry B. (2017) Electrochemistry in ionic liquids: Case study of a manganese corrole. Russian Journal of Electrochemistry, 53 (10). pp. 1189-1193. ISSN 1023-1935. doi:10.1134/S1023193517100068. https://resolver.caltech.edu/CaltechAUTHORS:20171020-140056026
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Abstract
Voltammetry of [5,10,15-tris(pentafluorophenylcorrole)]Mn(III) was investigated in four different ionic liquids (ILs): 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIm-TFSI); 1-ethyl-3-methylimidazolium ethylsulfate (EMIm-EtOSO_3); 1-ethyl-3-methylimidazolium triflate (EMIm-OTf); and 1-ethyl-3-methylimidazolium tetracyanoborate (EMIm-TCB). We found that Mn^(IV/III) E_(1/2) values depend on IL counter anion: OTf–< EtOSO_3− < TFSI− < TCB−. In EMIm-TCB and BMIm- TFSI, reversible, diffusion-controlled MnIV/III reactions occurred, as evidenced in each case by the ratio of anodic to cathodic diffusion coefficients over a range of scan rates. Axial coordination was evidenced by a cathodic to anodic diffusion coefficient ratio greater than one, an increasing cathodic to anodic peak current ratio with increasing scan rate, and a split Soret band in the UV-vis spectrum of the complex.
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| Additional Information: | © 2017 Pleiades Publishing, Ltd. Received January 6, 2017; in final form, February 3, 2017. First Online: 21 October 2017. This paper is the authors’ contribution to the special issue of Russian Journal of Electrochemistry dedicated to the 100th anniversary of the birth of the outstanding Soviet electrochemist Veniamin G. Levich. The article is published in the original. The authors thank Shabnam Hematian for helpful discussions. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) (H.B.G. and J. R. W.). Additional support was provided by King Fahd University of Petroleum and Minerals (R.H.G.). The authors declare no competing financial interest | ||||||||||
| Group: | CCI Solar Fuels | ||||||||||
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| Subject Keywords: | ionic liquids, electrochemistry, corroles, axial coordination, homogeneous voltammetry | ||||||||||
| Issue or Number: | 10 | ||||||||||
| DOI: | 10.1134/S1023193517100068 | ||||||||||
| Record Number: | CaltechAUTHORS:20171020-140056026 | ||||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20171020-140056026 | ||||||||||
| Official Citation: | McNicholas, B.J., Blumenfeld, C., Kramer, W.W. et al. Russ J Electrochem (2017) 53: 1189. https://doi.org/10.1134/S1023193517100068 | ||||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||
| ID Code: | 82541 | ||||||||||
| Collection: | CaltechAUTHORS | ||||||||||
| Deposited By: | Tony Diaz | ||||||||||
| Deposited On: | 20 Oct 2017 21:14 | ||||||||||
| Last Modified: | 15 Nov 2021 19:51 |
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