Synthesis and structural characterization of [2, 3-naphtho-12-nitro-5, 10, 15, 20-tetrakis (pentafluorophenyl)‎ porphyrinato] nickel (II)‎

Abstract EN

The title compound was obtained by complexation of the corresponding nitro-chlorin with Ni (OAc) 2×4H2O.

During this process at 100°C the spontaneous oxidation of chlorin to porphyrin was observed.

The product, Ni (II) C52H11F20N5O2⋅H2O⋅CH2Cl2, crystallizes in the triclinic system, space group P1, with cell constants a = 7.5855 (2) Å, b = 15.5580 (4) Å, c = 21.1029 (5) Å, α = 91.675 (2) ° , β = 96.294 (2)°, γ = 96.212 (2)°, V = 2458.79 (11) Å3, and Z = 2.

The nickel (II) atom is coordinated by four N-atoms from porphyrin core and the NiN4 unit adopts a square-planar geometry.

The Ni–N bond lengths are within the range 1.887 (4)–1.931(4) Å, while the average N–Ni–N angles are 178.83 and 90.01°.

The porphyrin core 20-membered ring adopts non-planar saddle conformation and the four pentafluorophenyl substituents are oriented nearly perpendicular to the macrocyclic porphyrin system.

The molecular packing in the crystal is influenced by π⋅⋅⋅π interactions of the naphthalene rings and weak intermolecular C–H⋅⋅⋅F dipole–dipole attractions linking the Ni(II)-porphyrin complex and dichloromethane molecules.