SYNTHESIS AND OPTICAL PROPERTIES OF CAMPHOR-SABSTITUTED TETRAPYRAZINOPORPHYRAZINES

  • Grigoriy V. Kuvshinov Ivanovo State University of Chemistry and Technology
  • Tatyana M. Ziyadova Ivanovo State University of Chemistry and Technology
  • Sofya A. Kuvshinova Ivanovo State University of Chemistry and Technology
  • Oscar I. Koifman Ivanovo State University of Chemistry and Technology, G.A. Krestov Institute of Solution Chemistry of RAS
Keywords: camphorquinone, 2, 3-dicyanopyrazine, phthalocyanines, spectral properties, fluorescence

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.

References

Braun A., Tscherniac Tcherniac J. Uber die Produkte der Einwirkung von Acetanhydrid auf Phtalamid. J. Ber. 1907. V. 40. P. 2709-2714.

Linstead R.P. Phthalocyanines. Part I. A New Type of Synthetic Colouring. J. Chem. Soc. (Resumed). 1934. P. 1016-1017.

Byrne G.T., Linstead R.P. Love A.R. Phthalocyanines. Part II. The Preparation of Phthalocyanineand some Metallic Derivatives from o-Cyanobenzamide and Phthaiimide. J. Chem. Soc. (Resumed). 1934. P. 1017-1022.

Lenzoff C.C., Lever A.B.P. Phthalocyanines – Properties and Applications. V. 1-4. Weinheim: VCH Publisher, Inc. 1989. 1993. 1996.

Hanack M., Igbal Z., Lyubimtsev A., Özcesmeci I., Özcesmeci M., Ziegles T. Synthesis of unusual phthalocyanines and naph-thalocyanines. J. Porphyrins Phthalocyanines. 2009. V. 13. N 3. P. 312-321.

Zhang Z., Lim J.M., Ishida M., Roznyatovskiy V.V., Lynch V.M., Gong H.-Y., Yang X., Kim D., Sessler J.L. Cy-clo[m]pyridine[n]pyrroles: hybrid macrocycles that display expanded ñ-conjugation upon protonation. J. Am. Chem. Soc. 2012. V. 134. P. 4076-4079.

Trukhina O.N., Zhabanov Y.A., Krasnov A.V., Danilova E.A., Islyaikin M.K. Synthesis and thermal behavior of unsubsti-tuted [30]trithia-2,3,5,10,12,13,15,20,22,23,25,30-dodecaazahexaphyrin. J. Porphyrins Phthalocyanines. 2011. V. 15. N 11. P. 1287-1291.

Znoiko S.A., Akopova O.B., Bumbina N.V., Maizlish V.E., Shaposhnikov G.P. Synthesis and Properties of Sulfo and Alkyl-sulfamoyl Substituted CuII and NiII Phthalocyanines Bearing 1-Benzotryazolyl and 4-(1-Methyl-1-phenylethyl)phenoxy Groups. Macroheterocycles. 2014. V. 7. N 3. P. 287-295.

Wang A., Long L., Zhang C. Synthesis of unsymmetrical phthalocyanines: a brief overview. Tetrahedron. 2012. V. 68. N1. P. 2433-2451.

Chun Keun Jang, Song Hak Kim, Jae-Yun Jaung. Synthesis and optical properties of tetrapyrazinoporphyrazines containing asymmetrical alkyl chains and t-butylphenyl groups. J. Porph. Phthal. 2010. V. 14. P. 531-539.

Stuzhin P.A., Erkolani C. Porphyrazines with Annulated Heterocycles. The Porphyrin Handbook. Ed. K.M. Kadish, K.M. Smith, R. Guilard. Amsterdam: Academic Press. 2002. V. 15. Chap. 101. P. 263-364.

Shaposhnikov G.P., Kulinich V.P., Maizlish V.E. Modified phthalocyanines and their structural analogies. Ed. O.I. Koifmana. M.: KRASAND. 2012. Chap. 9. P. 333-376 (in Russian).

Kobayashi N. Optically active phthalocyanines. Coord. Chem. Rev. 2001. V. 219-221. P. 99-123.

Kobayashi N., Nevin W.A. Optically active tetrapyrazinoporphyrazines and their circular dichroism in monomeric and dimeric forms. Chem. Lett. 1998. V. 8. P. 851-852.

Jang Ch.K., Kim S.H., Lee D.K., Jaung J.J. Synthesis of organo-soluble tetrapyrazinoporphyrazines and their visible spectra properties. Bull. Korean Chem. Soc. 2008. V. 29 N 9. P. 1665-1666.

Chun Keun Jang, Seung Hwan Byun, Song Hak Kim, Do Kyung Lee, Jae-Yun Jaung. Synthesis and optical properties of tetrapyrazinoporphyrazines containing camphorquinone group. J. Porph. Phthal. 2009. V. 13. P. 794-797.

Filatov M.S., Trukhina O.N., Efimova S.V., Koifman O.I., Islyaikin M.K. Synthesis and X-Ray Crystal Structure of 1’,7’,7’-Trimethylbicyclo[2.2.1]­heptane[2’,3’-b]-2,3-dicyanopyrazine. Macroheterocycles. 2013. V. 6. P. 82-85.

Filatov M.S., Trukhina O.N., Rodriguez-Morgade M.S., Islyaikin M.K., Koifman O.I., Torres T. Synthesis and spectro-scopic properties of chiral bornane[2,3-b]pyrazino-fused [30]trithiadodecaazahexaphyrins. J. Porph. Phthal. 2014. V. 18. P. 1014-1020.

Efimova S.V., Koifman O.I., Usol’tseva N.V., Bykova V.V., Anan’eva G.A. Synthesis, spectral and mesomorphic properties of camphor-substituted pyrazinoporphyrazines. Liquid crystals and their practical application. 2012. V. 28. N 2. P. 78-88.

Published
2017-05-12
How to Cite
Kuvshinov, G. V., Ziyadova, T. M., Kuvshinova, S. A., & Koifman, O. I. (2017). SYNTHESIS AND OPTICAL PROPERTIES OF CAMPHOR-SABSTITUTED TETRAPYRAZINOPORPHYRAZINES. ChemChemTech, 60(4), 60-67. https://doi.org/10.6060/tcct.2017604.5505
Section
CHEMISTRY (inorganic, organic, analytical, physical, colloid and high-molecular compounds)