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

The formation of μ-oxo and μ-fluoro dimers based on aluminum tetra-15-crown-5-phthalocyanine Al[(15C5)4PcX], X = OH, OCH3 (I) was studied by UV-Vis and 1H NMR spectroscopy. It is established that the formation of μ-oxo dimer (μ-O)[(15C5)4PcAl]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)4PcAl(OH)] with tetrabutylammonium fluoride in chloroform results in the formation of stable μ-fluoro dimer of (μ-F)[(15C5)4PcAl]2+, structure of which identified based on UV-Vis, 1H NMR, and MALDI-TOF mass spectral data. Conditions for preparation of complex [(15C5)4PcAlF2]− in solutions are found, and the possibility of sequential transformations in the series of complexes [(15C5)4PcAl](OH) → [(15C5)4PcAlF2]− → (μ-F)[(15C5)4Pcal]2+ is shown.