Irina V. Biryukova. Yulia G. Gorbunova and Aslan Yu. Tsivadze
Owing to their unique physical and chemical properties associated with the inter-ring л-л interactions, sandwich-type phthalocyaninates have been intensively studied as prospective molecular electronic conductors, molecular magnetic, electrochromic display and non-linear optical materials, etc. Besides, triple-decker phthalocyaninates complexes possess quite interesting magnetic properties because of the f-f interaction between metal ions in the molecule .
Numerous homoleptic triple-decker phthalocyaninates complexes have been reported, but heteroleptic analogues containing different metal ions are still relatively rare. We choose terbium and yttrium as the subjects of our investigation.
The homoleptic triple-decker complexes were prepared by the direct reaction between terra-15-crown-5-phthalocyanine (H2R4Pc, R=15-crown-5) and terbium or yttrium acetylacetanate in high boiling solvent – 1,2,4-trichlorobenzene (TCB). The terbium triple-decker complex was also prepared by the reaction between H2R4Pc and terbium acetate in the presence of DBU in refluxing 1-chloronaphthalene. But in this case we obtained the mixture of several products, namely: mono-, double- and triple-decker terbium crownphthalocyaninates.
The interaction between double-decker terbium tetra-15-crown-5-phthalocyaninate Tb(R4Pc)2, H2R4Pc and yttrium acetylacetanate in the boiling TCB yielded heteroleptic triple-decker complex.
The UV-vis electronic absorption spectroscopy, MALDI-TOF mass spectrometry, ‘H-NMR and IR-spectroscopy were used to confirm the composition and structure of obtained compounds.
Ishikawa,N; Iino,T.;Kaizu,Y.J.Am.Chem.Soc.2002, 124,11440-11447