Ruthenium complexes with tetra-15-crown-5-phtalocyanine and N-donor axial ligands: synthesis, structure and supramolecular chemistry studies | A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences

Yulia Yu. Enakieva, Yulia G. Gorbunova, Sergey G. Sakharov, Sergey E. Nefedov and Aslan Yu. Tsivadze

We have previously developed and used the method of synthesis of crown-substituted Ru phthalocyaninate complexes with various N-donor ligands (py, iqnl, Et3N) [1]. The preparation technique involves the interaction of (R4Pc)Ru(CO)(CH3OH) [2] (R = 15-crown-5) with selective decarbonilation agent – trimethylamine oxide in N-donor solvent.

Using this method in present work, we have synthesized complexes (R4Pc)RuL2 (L = Me3N, pyz, TED). Purification was performed by column chromatography on neutral alumina (CHCl 3/MeOH 99.5 : 0.5 vol.%). In order to identify the synthesized crown-substituted Ru phthalocyaninate complexes we have used various methods – UV-vis, FT-IR, ‘H-NMR-spectroscopies and ESI mass-spectrometry. 13C-NMR-spectra were obtained for complex (R4Pc)Ru(TED)2 using DEPT-135 and selective INEPT methods. 2D-spectroscopy COSY-’H, 13C was used to set correlations in ‘H and 13C NMR spectra The structure of (R4Pc)Ru(TED)2 was also investigated by means of X-ray analysis firstly .

We have also studied the processes of supramolecular cation-induced aggregation of (R4Pc)RuL2 ( L = py, TED). It was demonstrated, that interaction of these complexes with KSCN leads to formation of framework-shape aggregates n(R4Pc)RuL2×2nKSCN. Interaction of (R4Pc)RuLj with NaSCN leads to (R4Pc)RuL2*4NaSCN, where Na cations are incapsulated into crown-ether voids.


  1. Gorbunova, Y.G.; Enakieva, Y.Y.; Sakharov, S.G.; Tsivadze, A.Yu. J.Porphyrins Phtalocyanines 2004, in print.
  2. Enakieva, Y.Y.; Gorbunova, Y.G.; Sakharov, S.G.; Tsivadze, A.Yu. Russ.J.Inorg.Chem.2002, 47,1973-1979
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