Sil, Debangsu ; Kumar, Amit ; Rath, Sankar Prasad (2016) Diiron(III)-μ-Fluoro Bisporphyrins: Effect of Bridging Ligand on the Metal Spin State Chemistry - A European Journal, 22 (32). pp. 11214-11223. ISSN 0947-6539
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Official URL: http://doi.org/10.1002/chem.201600786
Related URL: http://dx.doi.org/10.1002/chem.201600786
Abstract
A hitherto unknown family of diiron(III)–μ-fluoro bisporphyrins has been synthesized and structurally characterized. Fluoride abstraction from SbF6− and BF4− resulted in the synthesis of the μ-fluoro complexes of ethane- and ethene-bridged diiron(III) bisporphyrins. Two such complexes were structurally characterized, which revealed a single fluoro bridge between two iron centers with a remarkably bent Fe-F-Fe unit. Although isoelectronic with the μ-hydroxo complexes, the μ-fluoro species are quite divergent in terms of the electronic structure and properties. UV/Vis spectroscopy of the μ-fluoro complex exhibits a large redshift (ca. 18 nm) of the Soret band in comparison to their μ-hydroxo analog. Combined analysis by single crystal X-ray structure determination and Mössbauer and 1H NMR spectroscopy revealed the presence of two equivalent iron(III) centers in the μ-fluoro complexes in both solid and solution phases. In contrast, the iron(III) centers of the μ-hydroxo complexes are known to be inequivalent. Variable-temperature magnetic studies show a weak antiferromagnetic interaction between the iron(III) centers of the μ-fluoro complexes with coupling constants (J) ranging from −33 to −40 cm−1. The experimental results were further supported by DFT calculations.
Item Type: | Article |
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Source: | Copyright of this article belongs to John Wiley and Sons, Inc. |
ID Code: | 120852 |
Deposited On: | 06 Jul 2021 07:23 |
Last Modified: | 06 Jul 2021 07:23 |
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