SYNTHESIS, ELECTRONIC STRUCTURE AND STUDY OF YTTERBIUM TETRAPHENYLPORPHYRIN COMPLEXES STABILITY BY PHOTOELECTRON SPECTROSCOPY AND THERMOGRAVIMETRY

Metalloorganic complexes of rare earth elements with porphyrins have attracted attention over the past years in view of potential applications as templates for biology, nanotechnology and medicine. For deeper understanding and studying of their properties the knowledge of electronic structure and bonding in these compounds is required and should be investigated essentially by a photoelectron spectroscopy. In present work the electronic structure and stability of tetrakis-porphyrins and its ytterbium complexes were studied experimentally by X-ray (XPS) photoemission spectroscopy. The X-ray photoemission data show the different atomic constituents in accordance with its states in molecules which can be related to the peaks of N1s, C1s, O1s, Yb4d appearing in the electronic spectra. In the tetraphenylporphyrin free base spectrum of the N1s state core levels there are two peaks of N1s which were assigned to sp3 and sp2 nitrogen respectively (pyrrol- and azastates). In Yb metalloporphyrin charge distribution is more uniform for N1s spectra and thus wide single peak of N1s states reflects small difference between pyrol- and aza-nitrogen. The analysis of Yb4d electronic states shows that spectra do not consist of the spin-orbit split doublet, but instead is composed of asymmetric peak with multiplet splitting. Divalent Yb has a filled 4f shell, i.e. a 4f14 configuration, and the 4d spectra shows the doublet with 3:2 ratio, while for trivalent Yb, 4f13, the 4d peaks consist of a multiplet. The spectrum analysis demonstrated the multiplet splitting of Yb 4d and trivalent state in Yb(acac)-5,10,15,20-tetrakis-porphyrins. The research of thermal stability of tetraphenylporphyrin, octabrominetetraphenylporphyrin, ytterbium acetylacetonate octabrominetetraphenylporphyrin by X-ray photoelectron spectroscopy and thermogravimetry measurements in the range of temperatures of 30-450°C (when heating in ultrahigh vacuum) has shown destruction of the octabrominetetraphenylporphyrin and ytterbium acetylacetonate octabrominetetraphenylporphyrin after warming up higher than 150ºС while free base porphyrines (tetraphenylporphyrines) have shown thermal stability under vacuum conditions.

tetraphenylporphyrin, ytterbium, octabrominetetraphenylporphyrin, thermogravimetric, photoelectron spectroscopy, thermal evaporation

1. Rosa A., Ricciardi G., Baerends E.J., Zimin M., Rodgers M.A.J., Matsumoto S., Ono N., Chimica D., Sauro V.N. Inorg. Chem. 2005. V. 44. № 19. P. 6609-6622.

2. Ray P.C., Leszczynski J. Chem. Phys. Lett. 2006. V. 419. № 4. P. 578-583.

3. Balzani V., Credi A., Venturi M. Chem. Eur. J. 2008. V. 14. № 1. P. 26-39.

4. Li C., Ly J., Lei B., Fan W., Zhang D., Han J., Meyyappan M., Thompson M., Zhou C. J. Phys. Chem. B. 2004. V. 108. № 28. P. 9646-9649.

5. Lovett J.E., Hoffmann M., Cnossen A., Shutter A.T.J., Hogben H.J., Warren J.E., Pascu S.I., Kay C.W.M., Timmel C.R., Anderson H.L. J. Am. Chem. Soc. 2009. V. 131. № 38. P. 13852-13859.

6. Sedghi G., Sawada K., Esdaile L.J., Hoffmann M., Anderson H.L., Bethell D., Haiss W., Higgins S.J., Nichols R.J. J. Am. Chem. Soc. 2008. V. 13. № 27. P. 8582-8583.

7. Enikolopyan N.S. Porphyrins: Structure, properties and synthesis. M.: Nauka, 1985. 333 p. (in Russ.).

8. Gorshkova A.S., Gorbachev S.V., Kopylova E.V., Rumyantseva V.D., Mozhchil R.N., Ionov A.M. / In: Chemical and Biochemical Technology: Materials, Processing and Reliability, Ch. 10 (Varfolomeev S.D., Ed.). Toronto; New Jersey: Apple Academic Press, 2014. P. 129-152.

9. Nishimura N., Ooi M., Shimazu K., Fujii H., Uosaki K. J. Electroanalyt. Chem. 1999. V. 473 P. 75-84.

10. Ghosh A., Moulder J., Bröring M., Vogel E. Angew Chem. Int. Ed. 2001. V. 40. № 2. P. 431-434.

11. Mozhchil R.N., Menushenkov A.P., Ionov A.M., Mironov A.F., Rumyantseva V.D. Macroheterocycles. 2015. V. 8 (3). P. 252-258. (in Russ.). https://doi.org/10.6060/mhc141244m

12. Peisert H., Knupfer M., Fink J. Surface Sci. 2002. V. 515. P. 491-498.

13. Kenneth T.P., Miller A., Klier K., Opila R. L., Rowe J. E. Surface Sci. 2003. V. 529. P. L285-L292.

14. Mozhchil R.N., Menushenkov A.P. Ionov A.M., Bozhko S.I., Rumyantseva V.D. Electronic structure of rare-earth metalloporphyrins by electron spectroscopy / X Int. Conf. "Spectroscopy of coordination compounds": The book of abstracts. September 2013. Tuapse, Russia. P. 63-64.