Bridged dimeric aluminum(III) tetra-15-crown-5-phthalocyanines as precursors for creation of highly ordered polymer materials

摘要

The formation of mu-oxo and mu-fluoro dimers based on aluminum tetra-15-crown-5-phthalocyanine Al[(15C5)(4)PcX], X = OH, OCH3 (I) was studied by UV-Vis and H-1 NMR spectroscopy. It is established that the formation of mu-oxo dimer (mu-O)[(15C5)(4)PcAl](2) in chloroform solution occurs upon titration of I with methanol, ethanol, and dimethylsulfoxide, as well as at the Al2O3-eluent interphase, upon an increase of the methanol concentration in chloroform and upon storage of I in the solid state. It is shown for the first time that the interaction of [(15C5)(4)PcAl(OH)] with tetrabutylammonium fluoride in chloroform results in the formation of stable mu-fluoro dimer of (mu-F)[(15C5)(4)PcAl] (2) (+) , structure of which identified based on UV-Vis, H-1 NMR, and MALDI-TOF mass spectral data. Conditions for preparation of complex [(15C5)(4)PcAlF2](-) in solutions are found, and the possibility of sequential transformations in the series of complexes [(15C5)(4)PcAl](OH) -> [(15C5)(4)PcAlF2](-) -> (mu-F)[(15C5)(4)Pcal] (2) (+) is shown.