Mn(II)-β-octabromo-5,10,15,20-tetrakis-(2,6-difluorophenyl)porphyrin, Mn(II)-β-octachloro-5,10,15,20-tetrakis-(2,6-difluorophenyl)porphyrin, Mn(II)-β-octachloro-5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrin and Mn(II)-β-octachloro-5,10,15,20-tetrakis-(2,6-dichlorophenyl)porphyrin were obtained by interaction of the corresponding porphyrins with manganese chloride in N,N-dimethylformamide at room temperature. Mn(III)-5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrin was synthesized using the complexation reaction of 5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrin and the metal exchange of its Cd(II)-complex with MnCl2 in N,N-dimethylformamide. It was shown that chlorination of Mn(III)-5,10,15,20-tetrakis-(2,6-difluorophenyl)porphyrin and Mn(III)-5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrin using N-chlorosuccinimide in N,N-dimethylfolmamide led to the formation of the corresponding β-octachloro substituted manganese(II) complexes. Obtained Mn(II, III)-porphyrins were identified by UV–Vis, 1H NMR spectroscopy and mass spectrometry methods. The spectral and photochemical properties of the synthesized compounds have been studied. Quantum chemical calculations were also carried out on a number of compounds to substantiate the photostability data obtained. It was reviled that the formation and stability of reduced forms of Mn-porphyrins are significantly influenced by the electronegativity of the introduced substituents, their amount and the nature of the solvent. The electrochemical properties for a number of manganese complexes were studied by the cyclic voltammetry method. It was established that halogenation of phenyl and pyrrole rings of manganese-porphyrins leads to a positive shift of Ered/ox potentials and an increase in their reducing capacity compared to the unsubstituted complexes. The influence of the nature of the solvent on the oxidation state of the manganese cation in the coordination center of the obtained halogen-substituted tetrapyrrole macrocycles was revealed and described in detail. The results of the studies will certainly be in demand in the prediction of spectral, photochemical and electrochemical properties of new tetrapyrrolic macrocyclic compounds and designing on their base of redox-controlled optoelectronic devices.
