Add time:09/07/2019         Source:sciencedirect.com

Reactivity of magnesium phthalocyanine (MgPc) in the dry 3,4-lutidine (3,4-lut), in the 3,4-lut/DMSO, in DMSO and in 3,4-lut/acetylacetone (acacH) systems has been investigated. Reaction of MgPc with dry 3,4-lut leads to formation of MgPc(3,4-lut) compound (1), in which the Mg atom is characterised by rarely encountering in magnesium phtalocyanines 4 + 1 N-type of coordination. In presence of the water tracer, depending on the reaction conditions and the 3,4-lut quantity in the MgPc/3,4-lut/DMSO system the solvothermal reaction leads to formation of three complexes in the crystalline form: MgPc(H2O)·2(3,4-lut) – (2), [MgPc(3,4-lut)][MgPc(H2O)·2(3,4-lut)]·½(3,4-lut) – (3) and [MgPc(H2O)·(3,4-lut)][MgPc(DMSO)]·½(DMSO) – (4). Reaction of MgPc with DMSO yields crystalline MgPc(DMSO) complex (5). In these complexes in the solid-state the central Mg atom of MgPc exhibits 4 + 1 coordination. The reaction of MgPc in the case of 3,4-lut/acacH system leads to demetallation of MgPc and formation of crystalline Mg(acac)2(H2O)2 compound (6) that after several days at ambient air in the mother liquor transforms into organic crystalline compound of C10H12O2 (7). The structure of 1–7 has been determined by X-ray single crystal diffraction. All MgPc-derivatives (1–5) were characterised by thermogravimetric analysis. Partial MO energy diagrams and the calculated absorption spectra of the MgPc-derivatives were compared with the experimental electronic absorption spectra in 3,4-lutidine and DMSO solutions. These results point that the axial ligation of MgPc by O- and N-donor ligands do not change significantly the energy gap of the HOMO-LUMO levels which is compared with that of the parent MgPc pigment.

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