A new Ni(II) metalloporphyrin: characterization, theoretical sensing calculations and catalytic degradation of methylene blue and methyl orange dyes.

With the aim of studying the electronic and structural properties of metalloporphyrins, we first prepared the 4-acetoxy-3-methoxy benzaldehyde (1) then by reaction this aldehyde with pyrrole the meso-arylporphyrin, namely the meso-tetrakis(4-acetoxy-3-methoxyphenyl)porphyrin (H2TAMPP) (2) was synthesized. We have also prepared a nickel(II) meso-tetra(aryl)porphyrin with the formula [Ni(TAMPP)] (3). Both two porphyrinic compounds 2–3 have been characterized by UV/Vis, fluorescence, 1H and 13C NMR and IR spectroscopies as well as by MALDI and ESI-HRMS mass spectrometry. Density functional Theory (DFT) calculations at the DFT/B3LYP-D3/6–311 G (d, p) level of theory have been carried out to investigate the HOMO–LUMO orbitals of 2–3 and several global reactive parameters of these two compounds such as the chemical potential, the global hardness, the Mulliken electronegativity, the global softness (S) and the global electrophilicity index. The stability and charge delocalization of 2–3 were studied by natural bond orbital (NBO) analysis. On the other hand, our two porphyrinic species 2–3 were theoretically studied for the adsorption of NO2 and H2S gases using the B3LYP/6-31G (d) bases method. Furthermore, H2TAMPP (2) and its corresponding Ni(II) complex (3) were tested as catalysts of the degradation of the methylene blue (MB) and the methyl orange (MO) dyes using an aqueous solution of hydrogen peroxide. [ABSTRACT FROM AUTHOR]