Linkage Isomers of 4‑Methylimidazolate Mn(II) Porphyrinates: Hindered or Unhindered?

Three different manganese­(II) porphyrins have been exploited to react with 4-methylimidazolate (4-MeIm^–), and the five-coordinate products are characterized by ultraviolet–visible, single-crystal X-ray, and electronic paramagnetic resonance spectroscopies. Interestingly, 4-MeIm^– is found to bond to the metal center through either of the two N atoms (N1 or N3), which yielded two linkage isomers with either an unhindered or a hindered ligand conformation, respectively. Investigations revealed it is the large metal out-of-plane displacements (Δ₂₄ and Δ₄ ≥ 0.59 Å) that have rendered the equivalence of two isomers with a small energy difference (5.2–8.3 kJ/mol). The nonbonded intra- and intermolecular interactions thus become crucial factors in the balance of linkage isomerization. All of the products in both solution and solid states show the same characteristic resonances of high-spin Mn­(II) (S = ⁵/₂) with g_⊥ ≈ 5.9 and g_∥ ≈ 2.0 at 4 K, consistent with the weak effects of the axial ligand on core conformation and metal electronic configurations. Zero-field splitting parameters obtained through simulations are also reported.