Tetranuclear supramolecular structures containing phthalocyanine cores

A metal-free phthalocyanine with four pyridyl donor groups, bound through ethylthio ester bridges on the periphery, have been prepared. The pyridine donors were quaternized with iodomethane to a water-soluble tetracationic phthalocyanine. The tetranuclear supramolecular phthalocyanine was prepared by the coordination of peripheral pyridine donors with VO(acac)₂. The paramagnetic tetranuclear structure was studied in powder and solution forms by the electron paramagnetic resonance (EPR) technique. Electron paramagnetic resonance studies, together with the other spectral data confirmed the presence of identical pyridine-coordinated VO(acac)₂ paramagnetic centers attached to the peripheral positions of the phthalocyanine core. The X-band EPR signals recorded from powder and solution forms of supramolecules have a characteristic line shape that proves the presence of axial symmetry around the paramagnetic vanadium ions. The anisotropic Lande splitting factors were calculated as g_∥ < g_⊥ < g_c = 2.0023. Orbital energy levels for magnetic electrons were determined from theoretically fitted Spin Hamiltonian parameters.