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Electrosynthesis, electrochemistry, and crystal structure of the tetracationic Zn-meso-tetrapyridiniumyl-β-octaethylporphyrin

Laboratoire d'Electrochimie et de Chimie Physique du Corps Solide, U.M.R. au C.N.R.S. no. 7512, Université Louis Pasteur, 4 rue Blaise Pascal, F-67000 Strasbourg, France

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S. LOBSTEIN

Laboratoire d'Electrochimie et de Chimie Physique du Corps Solide, U.M.R. au C.N.R.S. no. 7512, Université Louis Pasteur, 4 rue Blaise Pascal, F-67000 Strasbourg, France

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L. RUHLMANN

Laboratoire d'Electrochimie et de Chimie Physique du Corps Solide, U.M.R. au C.N.R.S. no. 7512, Université Louis Pasteur, 4 rue Blaise Pascal, F-67000 Strasbourg, France

Laboratoire de Chimie Physique, Equipe d'Electrochimie et de Photoélectrochimie, Groupe TEMiC, U.M.R. au C.N.R.S. no. 8000, Université Paris-Sud, Bâtiment 420, F-91405 Orsay, France

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D. MELAMED

Energy Sciences and Technology Department, Brookhaven National Laboratory, Upton, NY 11973, USA

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K. M. BARKIGIA

Energy Sciences and Technology Department, Brookhaven National Laboratory, Upton, NY 11973, USA

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, and

J. FAJER

Laboratoire d'Electrochimie et de Chimie Physique du Corps Solide, U.M.R. au C.N.R.S. no. 7512, Université Louis Pasteur, 4 rue Blaise Pascal, F-67000 Strasbourg, France

Energy Sciences and Technology Department, Brookhaven National Laboratory, Upton, NY 11973, USA

Corresponding author, Bldg 555, Brookhaven National Laboratory, Upton, NY 11973, USA.

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https://doi.org/10.1002/jpp.547Cited by:28 (Source: Crossref)

Abstract

Exhaustive electro-oxidation of ZnOEP in the presence of pyridine and Et₄NPF₆ affords in high yield the new tetracationic porphyrin in which the four meso protons of ZnOEP are replaced by four pyridinium groups linked via their nitrogens: [Zn-5,10,15,20-tetrakis(N-pyridiniumyl)-2,3,7,8,12,13,17,18-octaethylporphyrin]⁴⁺, 1. The compound has been characterized by elemental analysis, ¹H NMR, and crystallography. The latter confirms the preparative electrosynthetic methodology and molecular structure of 1, and shows the porphyrin skeleton to adopt a severely nonplanar saddle conformation which minimizes steric crowding between the 12 peripheral substituents. As a consequence of the nonplanarity (and the high charge) of the complex, 1 exhibits significant red-shifts of the visible and Soret bands as well as a considerable broadening and loss of intensity of the latter. 1 first undergoes four one-electron reduction steps at the four pyridinium sites before the normal one-electron reduction of the porphyrin π-system.

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