Single crystals of the title zinc porphyrinato complex, [Zn(C44H8F20N4)]·2C6H6, were obtained by the solvent evaporation method. The molecular complex exhibits point group symmetry \overline1 with the central ZnII atom located on an inversion centre. The porphyrinato core is approximately planar, and the cation has no other ligating atoms than the four porphyrinato N atoms. π–π interactions between benzene solvent molecules and [Zn(TFPP)] units lead to multilayer packing structures. In addition, intermolecular C—H...F hydrogen bonding is observed between [Zn(TFPP)] molecules.

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 (Δ 24 and Δ 4 ≥ 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.