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Ring-Oxidized Zinc(II) Phthalocyanine Cations: Structure, Spectroscopy, and Decomposition Behavior

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journal contribution
posted on 16.07.2018 by Declan McKearney, Sylvie Choua, Wen Zhou, Yumeela Ganga-Sah, Romain Ruppert, Jennifer A. Wytko, Jean Weiss, Daniel B. Leznoff
A bromonium oxidizing agent was used to produce a ring-oxidized zinc phthalocyanine (PcZn), [PcZn­(solvent)]2[BArF4]2 (1·solvent), in good yield. This material is dimeric in the solid state with one axially coordinated solvent [tetrahydrofuran (THF) or 1,2-dimethoxyethane (DME)] and close intradimer ring–ring distances of 3.18 and 3.136 Å (THF and DME respectively); this proximity facilitates strong antiferromagnetic coupling to yield diamagnetic dimers. 1·THF is present in solution as a monomer and a dimer. In CH2Cl2, the dimer is favored above 0.1 mM, and it is almost exclusively present in solvents with a high dielectric constant such as acetonitrile. The material 1·THF/DME decomposes in DME to a meso-nitrogen-protonated species, [HPcZn­(DME)2]­[BArF4] (2), which was isolated and represents the first example of such a structurally characterized, protonated, unsubstituted PcM complex. A partially oxidized dimer or “pimer” [(PcZn­(DME))2][BArF4] (3) was also structurally characterized and has a intradimer ring–ring distance of 3.192 Å, similar to 1·THF/DME. Dimer 3 also represents the first isolated PcM-based pimer. Electron paramagnetic resonance analysis of a 1.0 mM solution of 1·DME in DME showed the production of 3 over hours by the combination of 1·DME and 2 in solution.

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