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Please use this identifier to cite or link to this item: http://repository.iitr.ac.in/handle/123456789/19298
Title: Electrochemistry of Tri-substituted Porphyrins with β-Appended Ethyl Acetoacetate and Acetylacetone in Neutral and Basic Nonaqueous Solvents
Authors: Fang Y.
Yadav I.
Osterloh W.R.
Chaudhri N.
Sankar, Muniappan
Kadish K.M.
Published in: ChemElectroChem
Abstract: The electrochemistry of β-substituted tetraphenylporphyrins with a single ethyl acetoacetate (EAA), acetylacetone (acac), or ethyl acetate (EA) group and two antipodal H, Br or Ph groups was investigated in CH Cl containing 0.1 M tetrabutylammonium perchlorate (TBAP) before and after addition of base to solution in the form of tetrabutylammonium hydroxide (TBAOH). The tri-substituted porphyrins in their neutral form are represented as MTPP(EAA)X , MTPP(acac)X and MTPP(EA)X , where TPP is the dianion of tetraphenylporphyrin, M=H , Ni , Cu or Zn and X=H, Br or Ph. The singly reduced porphyrins are relatively stable on the cyclic voltammetry timescale, but this is not the case for the doubly reduced EAA and acac derivatives, which are highly reactive at room temperature, leading to a porphyrin product assigned as containing a deprotonated EAA or acac (enolate) substituent. Enolate-appended porphyrins were also generated in-situ by the addition of TBAOH, resulting in mono-anionic porphyrins that are harder to reduce by 110–160 mV as compared to the neutral compounds with the same β-substituents, suggesting a high degree of interaction between the deprotonated EAA or acac substituent and the porphyrin π-ring system. The chemically or electrochemically generated enolate-appended porphyrin could also be irreversibly oxidized by one electron at peak potentials between 0.10 and 0.30 V; the exact value depending upon solvent and type of β-diketo substituent.
Citation: ChemElectroChem(2020), 7(7): 1723-1732
URI: https://doi.org/10.1002/celc.202000191
http://repository.iitr.ac.in/handle/123456789/19298
Issue Date: 2020
Publisher: Wiley-VCH Verlag
Keywords: deprotonation
electrochemistry
enolate
porphyrinoids
β-diketo
Acetone
Cyclic voltammetry
Inorganic compounds
Olefins
Porphyrins
Solvents
Trichloroethylene
Degree of interaction
Dianion of tetraphenylporphyrin
Ethylacetoacetate
Neutral compounds
Non-aqueous solvents
Tetrabutylammonium hydroxid
ISSN: 21960216
Author Scopus IDs: 35215208100
57214584722
57200559482
56450499000
6701530390
7004463259
Author Affiliations: Fang, Y., School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, 212013, China, Department of Chemistry, University of Houston, Houston, TX 77204-5003, United States
Yadav, I., Department of Chemistry, Indian Institute of Technolo
Funding Details: E-680 Welch Foundation National Natural Science Foundation of China, NSFC: 21501070 Science and Engineering Research Board, SERB: SERB/EMR/2016/004016 China Postdoctoral Science Foundation: 2019M661735 Bangladesh Council of Scientific and Industr.We gratefully acknowledge support from the Natural Science Foundation of China (Grant No. 21501070), China Postdoctoral Science Foundation (Grant 2019M661735), Robert A. Welch Foundation (KMK, Grant E-680) and Science and Engineering Research Board (SERB/
Corresponding Author: Sankar, M.; Department of Chemistry, India; email: m.sankar@cy.iitr.ac.in
Appears in Collections:Journal Publications [CY]

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