Remarkable Anion‐Dependent Spin‐State Switching in Diiron(III) μ‐Hydroxo Bisporphyrins: What Role Do Counterions Play?

Abstract

Addition of 2,4,6-trinitrophenol (HTNP) to an ethene-bridged diiron(III) μ-oxo bisporphyrin (1) in CH₂ Cl₂ initially leads to the formation of diiron(III) μ-hydroxo bisporphyrin (2⋅TNP) with a phenolate counterion that, after further addition of HTNP or dissolution in a nonpolar solvent, converts to a diiron(III) complex with axial phenoxide coordination (3⋅(TNP)₂ ). The progress of the reaction from μ-oxo to μ-hydroxo to axially ligated complex has been monitored in solution by using ¹ H NMR spectroscopy because their signals appear in three different and distinct spectral regions. The X-ray structure of 2⋅TNP revealed that the nearly planar TNP counterion fits perfectly within the bisporphyrin cavity to form a strong hydrogen bond with the μ-hydroxo group, which thus stabilizes the two equivalent iron centers. In contrast, such counterions as I₅ , I₃ , BF₄ , SbF₆ , and PF₆ are found to be tightly associated with one of the porphyrin rings and, therefore, stabilize two different spin states of iron in one molecule. A spectroscopic investigation of 2⋅TNP has revealed the presence of two equivalent iron centers with a high-spin state (S=5/2) in the solid state that converts to intermediate spin (S=3/2) in solution. An extensive computational study by using a range of DFT methods was performed on 2⋅TNP and 2⁺ , and clearly supports the experimentally observed spin flip triggered by hydrogen-bonding interactions. The counterion is shown to perturb the spin-state ordering through, for example, hydrogen-bonding interactions, switched positions between counterion and axial ligand, ion-pair interactions, and charge polarization. The present investigation thus provides a clear rationalization of the unusual counterion-specific spin states observed in the μ-hydroxo bisporphyrins that have so far remained the most outstanding issue.