Cerium(IV) tetra-15-crown-5-phtalocyaninate: synthesis and investigation | 2017 ИФХЭ РАН

Kirill P. Birin, Yulia G. Gorbunova, Aslan Yu. Tsivadze

It was previously shown that cerium complexes with porphyrins and their analogues posses interesting electrochemical properties in the series of other lanthanides complexes[1]. In contrast to other lanthanides the quadrivalent state of cerium is stable in complexes. Depending on the nature of porphyrin ligand in the complex cerium can be tervalent or quadrivalent. In some porphyrin complexes the equilibrium between tervalent and quadrivalent states of cerium is possible [2]. In order to investigate the difference between ter- and quadrivalent lanthanides crown-substituted phtalocyaninates we synthesed Ce(IV) bis-tetra-15-crown-5-phtalocyaninate. The structure of the complex and the valent state of Ce in the obtained substance was proved by a number of spectral methods.

A variety of synthetic methods was employed in order to optimize the preparation procedure of the complex. The best found method is reflux of the mixture of cerium (III) acetate, tetra-15-crown-5-phtalocyanine and 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU) in 1-chloronaphtalene for 1.5 hours.

It is proved that Ce(IV) double-decker phtalocyaninate was synthesed although Ce(III) acetate was employed.

The complex was purified by column chromatography on basic alumina with a mixture of MeOH/CHCl3 as eluent. The structure of cerium phtalocyaninate was proved by UV-Vis, IR, H NMR, MALDI TOF MS methods.

The cation-induced aggregation of the product was investigated with Na+, K+, Rb+, Cs+ cations. The formation of face-to-face aggregates was observed.


  1. Jiang,J.; Liu,W.; Poon, K.W.; Du,D; Arnold,D.P.; Ng, D.K.P Eur.J.Inorg.Chem.2000, 205-209
  2. Sun, X.; Bao, M.; Pan,N.;Cui,X.;Arnold,D.P.;Jiang,J. Aust.J. Chem.2002,55,1-9.
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