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Title: Effect of fused indanedione (IND) groups and antipodal β-substituents on electrochemical properties of unsymmetrical metalloporphyrins
Authors: Osterloh W.R.
Fang Y.
Chaudhri N.
Cong L.
Sankar, Muniappan
Kadish K.M.
Published in: Journal of Porphyrins and Phthalocyanines
Abstract: The interacting effect of fused indanedione (IND) groups and antipodal Br β-substituents on the electroreduction of free-base and transition metal tetraphenylporphyrins (TPPs) are elucidated through the use of cyclic voltammetry. A systematic study of the reduction potentials for mono-and di-fused derivatives of MTPP(IND)(R)2 and MTPP(IND)2(R)2 where R = Br or H and M = CuII, NiII, ZnII or H2 is carried out in pyridine containing 0.1 M tetrabutylammonium perchlorate (TBAP) as supporting electrolyte and demonstrates how the overall electrochemical properties of these compounds can be tuned by systematic changes in the number of meso-βfused IND groups on the molecule and the presence or absence of electron-withdrawing Br β-substituents. Under these solution conditions, two reversible one-electron reductions are seen for H2TPP, while three reversible reductions are obtained for H2TPP (IND) or H2TPP (IND)Br2 and four for H2TPP (IND)2Br2. Multiple reductions also occur for the other investigated mono-and di-fused metalloporphyrins. Plots of measured E1/2 values for the two ring-centered reductions of compounds in a given series vs.The number of fused IND groups are linear and with slopes varying in magnitude between 15 and 230 mV/IND depending upon the product of the electron transfer (anion radical or dianion), the specific central metal ion and the presence or absence of Br substituents on the pyrrole ring opposite the fused IND group(s). It is anticipated that the information from this study can be used for predicting the reduction potentials for yet to be synthesized compounds where a specific redox reactivity is desired.
Citation: Journal of Porphyrins and Phthalocyanines(2020), 24(10): 1155-1165
Issue Date: 2020
Publisher: World Scientific
Keywords: cyclic voltammetry
fused porphyrins
ISSN: 10884246
Author Scopus IDs: 57200559482
Author Affiliations: Osterloh, W.R., Department of Chemistry, University of Houston, Houston, TX 77204-5003, United States
Fang, Y., Department of Chemistry, University of Houston, Houston, TX 77204-5003, United States
Chaudhri, N., Department of Chemistry, Indian Insti
Funding Details: E-680 Welch Foundation Science and Engineering Research Board, SERB: EMR/2016/4016 Bangladesh Council of Scientific and Industrial Research, BCSIR.We are grateful for financial support provided by the Robert A Welch Foundation (KMK Grant No. E-680), and the Science and Engineering Research Board (No. EMR/2016/4016). N.C. thanks the Council of Scientific and Industrial Research (CSIR).
Corresponding Author: Kadish, K.M.; Department of Chemistry, United States; email:
Appears in Collections:Journal Publications [CY]

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