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              <p>We hereby report the synthesis of a new hexacoordinated magnesium(II) metalloporphyrin with the formula [Mg(TBrPP)(4-pypo-κO)2] (1) where TBrPP is the meso-tetra(para-bromophenyl)porphyrinate and (4-pypo-κO) is the O-bonded 4-pyrrolidinopyridine axial ligand. This Mg(II) coordination is considered the linking isomer of the already known N-bonded 4-pyrrolidinopyridine (4-pypo-κN) with the formula [Mg(TTP)(4-pypo-κN)2] where TTP is the meso-tetra(p-tolyl)porphyrinate. Complex 1 was characterized by elemental analysis, IR, 1H NMR, UV/Vis and fluorescence spectrometric techniques, cyclic voltammetry measurements as well as single-crystal X-ray diffraction analysis. The Wingx supported program PLATON and the Hirshfeld surface analysis were both used to elucidate the intermolecular interactions in the crystal lattice of complex 1. Computational studies at DFI/B3LYP-D3/6-31G(d,p)-LanL2DZ level of DFT were used to elucidate the minimum energy geometry, the HOMO and LUMO molecular orbitals characteristics and the reactivity of complex 1. The molecular electrostatic potential (MEP) calculations on complex 1 have been made to determine the electrophilic-nucleophilic character of our new Mg(II) metalloporphyrin. Furthermore, the quantum theory atom in molecule (QTAIM) calculations were performed to get more insights into the type of interactions between the [Mg(TBrPP)] moiety and the two 4-pyrrolidinopyridine axial ligands of complex 1. © 2023 Elsevier B.V.</p>
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