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Novel octa-phenotiazine, octa-benzoazepine and octa-carbazole substituted magnesium(II) (MgPz-I-III) and zinc(II) (ZnPz-I-III) porphyrazines were synthesized from 2,3-bis[6-(4a,10a-dihydro-phenothiazin-10-yl)-hexylsulfanyl]-but-2-enedinitrile (5), 2,3-bis [6-(4a,11a-dihydro-dibenzo[b,f]azepin-5-yl)-hexysulfan-yl]-but-2-enedinitrile (8) and 2,3-bis(6-carbazol-9-yl-hexylsulfanyl)-but-2-enedinitrile (10), respectively. These dinitrile derivatives 5, 8 and 10 were also prepared by the reaction of 1,2-dicyano-1,2-ethylenedithiolate di-sodium salt (4) with 10-(6-bromohexyl)-10H-phenothiazine (3), 5-(6-bromohexyl)-5H-diben-zo[b,f]azepine (7) and 9-(6-bromo-hexyl)-9H-carbazole (9), respectively. Porphyrazino-zinc(II) complexes were synthesized by one-step reaction using Zn(BuO)${}_{\mathrm{\text{2}}}$ as a template agent. All the novel compounds were characterized by elemental analysis and different spectroscopic methods such as ${}^{\mathrm{\text{1}}}$H NMR, ${}^{\mathrm{\text{13}}}$C NMR, FT-IR, UV-Vis and mass. The photochemical properties including photodegradation and singlet oxygen generation for magnesium(II) and zinc (II) porphyrazine complexes were studied in dimethylsulfoxide solutions for determination of their photosensitizer behaviors.

The aggregation behavior of unsubstituted magnesium porphyrazine (MgPz) was studied in layers at the water–air interface and in Langmuir–Schaefer films. Regions of existence and characteristics of the structure and properties of stable nanostructured monolayers of MgPz were determined with the method of quantitative analysis of compression isotherms of floating layers in a wide range of initial surface coverage degrees (ISCD). MgPz on the water surface forms monolayers of three types: a face-on type and two edge-on types that differ in the structure. The specific feature of the monolayers of the second type is the independence of the structure of two-dimensional MgPz nanoparticles formed on water on the ISCD. A mathematical model and a state diagram of the monolayer were constructed and a passport of MgPz monolayers was compiled. For the first time, the state diagram contains boundary isotherms based on data obtained from the model. Langmuir–Schaefer films of MgPz formed from layers of various types were prepared and studied by UV-vis absorption spectroscopy.