The reaction of the starting materials [ Co II ( Porph )] (Porph = α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrin (TpivPP) and the meso-tetraphenylporphyrin (TPP)) with an excess of 4,4′-bipyridine in chlorobenzene leads to the creation of two cobalt(II) derivatives: [ Co II (α,β,α,β- TpivPP )(4,4′- bpy )2]· C 6 H 5 Cl · C 6 H 14(1) and [ Co II ( TPP )(4,4′- bpy )2]·2 bpy (2). These compounds have been characterized by UV-vis, IR, 1 H NMR and MALDI-TOF spectroscopy. The proton NMR spectra of (1) and (2) clearly indicated that these derivatives are paramagnetic while the UV-vis data confirmed creation of a new six-coordinated or penta-coordinated Co ( II )-meso-porphyrin complexes by displaying red shifted Soret bands. The determined X-ray structures of (1) and (2) show that in the solid state these species are considered as coordination polymers which consist of 1D chains of alternating [ Co II ( Porph )] and 4,4′-bipyridine molecules located at the axial positions of the cobalt(II) coordination sphere. The coordination geometry of Co ( II ) in (1) and (2) is octahedral; the porphyrin (TpivPP or TPP) acts as a tetradentate chelating ligand with four nitrogen atoms from the pyrrole moieties occupying the equatorial positions along the porphyrin core. The N -donor atoms of the 4,4′-bipyridine create the axial ligands. It is noteworthy that for complex (1) the starting porphyrin is the α,α,α,α-TpivPP atropisomer but the final coordination polymer contains the α,β,α,β-TpivPP conformer.

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The asymmetric unit of the title compound, [Co(C44H28N4)]·C12H24O6, contains one half of a CoII(TPP) (TPP is tetra­phenyl­porphyrin) complex and one half of an 18-crown-6 mol­ecule of crystallization, both lying on inversion centers. The CoII(TPP) complex exhibits a nearly planar conformation of the porphyrinate core [maximum deviation = 0.069 (2) Å] with an average Co—N distance of 1.971 (4) Å. The distance between the Co atom and the closest O atom of the 18-crown-6 mol­ecule is 2.533 (2) Å, indicating a short non-bonded contact between the Co atom and the crown ether mol­ecule. An ethyl­ene group of the 18-crown-6 mol­ecule is disordered over two sites with occupancies of 0.565 (7) and 0.435 (7).

The reaction of the cobalt(II) meso-tetraphenylporphyrin (TPP) starting material with an excess of 2-aminophenol (Hon) in organic solvents, yields the cobalt(II) porphyrin species [Co II (TPP)(Hon) 2 ] (1). This compound has been characterized by UV-vis, IR, MSI MS and 1 H NMR spectroscopy. The UV-vis data and especially the proton NMR results, for the isolated product, indicated that complex 1 is a Co(II) mesoporphyrin derivative. The X-ray molecular structure of the title compound bis(2-aminophenol) (tetraphenyl-porphyrinato) cobalt(II) has been determined. This structure is the first one reported of a metalloporphyrin with a 2-aminophenol axial ligand species. The central metal is hexacoordinated by the four nitrogen atoms of the pyrrole rings and the nitrogen atoms of the two Hon trans axial ligands.

The asymmetric unit of the title compound, [Co(C36H44N4)]·2C7H5NO3, is composed of one half of the complex, arranged about an inversion center, and a complete 2-nitro­benzaldehyde (NBA) mol­ecule. The structure consists of columns that contain inter­leaved mol­ecules of NBA and [CoII(OEP)] (OEP is 2,3,7,8,12,13,17,18-octa­ethyl­porphyrin), which are stacked along the a axis. The CoII atom is involved in a π inter­action with the ring of the NBA mol­ecule with a centroid–metal distance of 3.508 (6) Å. There is an intra­molecular C—H⋯O hydrogen bond in the NBA mol­ecule.