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Ring-Oxidized Zinc(II) Phthalocyanine Cations: Structure, Spectroscopy, and Decomposition Behavior.
- Source :
-
Inorganic chemistry [Inorg Chem] 2018 Aug 20; Vol. 57 (16), pp. 9644-9655. Date of Electronic Publication: 2018 Jul 16. - Publication Year :
- 2018
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Abstract
- A bromonium oxidizing agent was used to produce a ring-oxidized zinc phthalocyanine (PcZn), [PcZn(solvent)] <superscript>•</superscript> <subscript>2</subscript> [BAr <superscript>F</superscript> <subscript>4</subscript> ] <subscript>2</subscript> (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 CH <subscript>2</subscript> Cl <subscript>2</subscript> , 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) <subscript>2</subscript> ][BAr <superscript>F</superscript> <subscript>4</subscript> ] (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)) <subscript>2</subscript> ] <superscript>•</superscript> [BAr <superscript>F</superscript> <subscript>4</subscript> ] (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.
Details
- Language :
- English
- ISSN :
- 1520-510X
- Volume :
- 57
- Issue :
- 16
- Database :
- MEDLINE
- Journal :
- Inorganic chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 30009596
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.8b01579