SYNTHESIS AND OPTICAL PROPERTIES OF CAMPHOR-SABSTITUTED TETRAPYRAZINOPORPHYRAZINES

Abstract

The synthesis of the complexes of Cu, Ni, Co, Pd, Sn, Hg of 1',7',7'-trimethylbicyclo[2.2.1]heptano-[2',3'-b]-2,3-pyrazinoporphyrazine for new materials for variety of potential applications is described. Metallic complexes were synthesized by the template cyclotetramerization of dicarbonitrile with metal chlorides at temperature 140-150 ºС for 20 min. Ammonium molybdate tetrahydrate was used as a catalyst. The products were purificated by chromatography on silica gel (eluent -chloroform). Complexes of Pd, Sn and Hg were synthesized for the first time. The metallocomplexes of camphor-substituted tetrapyrazinoporphyrazine are crystalline substances of dark blue color, not fusible up to 300 ° C, which have good solubility in chloroform, toluene, ethanol, acetone, DMF, acetic and trifluoroacetic acids. The chemical structures of the complexes of Cu, Ni, Co, Pd, Sn, Hg of 1',7',7'-trimethylbicyclo[2.2.1]heptano-[2’,3’-b]-2,3-pyrazinoporphyrazine obtained in this study were characterized by proton nuclear magnetic resonance and mass spectrometry. The absence of impurity signals in the 1H NMR spectra indicates a high degree of purity of the compounds obtained. For copper, nickel and cobalt complexes, a good correlation was found between the experimental and literature data on the chemical shifts of protons in 1H NMR spectra. Optical properties of the synthesized complexes were studied. The electronic absorption spectra of the complexes in their chloroform, DMF, acetic acid and sulfuric acid solutions were obtained. In organic solvents the typical B band (Soret band, around 400 nm) and Q band (in 600-700 nm region) of phthalocyanines were identified in this study. Complexes of Pd, Sn and Hg in their sulfuric acid solutions are non-stable. The influence of the chemical structure of metalic complexes and solvents on the optical properties was studied. Emission properties of the synthesized complexes of Pd and Hg in their chloroform and DMF solutions were analyzed. Hg-porphyrazine has very intensive fluorescence. The solution has blue color and red fluorescence at common condition.Forcitation:Kuvshinov G.V., Ziyadova T.M., Kuvshinova S.A., Koifman O.I. Synthesis and optical properties of camphor-sabstituted tetrapyrazinoporphyrazines. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 4. P. 60-67.