Diiron(III)-μ-Fluoro Bisporphyrins: Effect of Bridging Ligand on the Metal Spin State.

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 (1) H 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.