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<p>Our current study establishes the synthesis and the spectroscopic attributes of a two five-coordinated iron(II) picket fence porphyrin with the formula [Na(2,2,2-crypt)][Fe<sup>II</sup>(TpivPP)(NCO)] (<b>Fe2NCO</b>) and [K(2,2,2-crypt)][Fe<sup>II</sup>(TpivPP)(NCS)] (<b>Fe2NCS</b>) where TpivPP is the (α,α,α,α-terakis(<i>o</i>-pivalamidophenyl)(porphinato) anion and (2,2,2-crypt) is the cryptand-222). The two complexes are characterized in solution by UV-visible and IR spectroscopies. The molecular structures of the two compounds are determined and described using single-crystal X-ray diffraction analysis and Hirshfeld surface area derivations. Our complexes crystallize in the monoclinic system with space group C2 and P2<sub>1</sub>/n, respectively. The average distance between the central Fe(II) ion and the nitrogen atoms in the equatorial position is 2.120(2) Å and 2.104(2) Å, respectively, while the Fe<sup>II</sup>–N(axial ligand) distances from the cyanate and thiocyanate ligand are 2.005(3) Å and 2.042(2) Å, respectively. In each compound, the crystal packing cohesion is stabilized by unconventional intramolecular C–H<sup>…</sup>O and C–H<sup>…</sup>N hydrogen bonds. Furthermore, several important physical attributes were numerically examined to deliver an in-depth analysis of the electron charge migration pathways of the iron(II) porphyrin complex using Density Functional Theory (DFT) at the B3LYP-D3/LanL2DZ level. This includes the analysis of frontier molecular orbitals (FMOs) and associated reactivity descriptors, molecular electrostatic potential (MEP), non-covalent interaction (NCI) analysis through reduced density gradient (RDG) surfaces, and bond critical points (BCPs), as well as electron localization function (ELF), localized orbital locator (LOL), and Hirshfeld surface characterization.</p>

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Spectroscopic investigations, hirshfeld surface analysis, and computational modeling (DFT, QTAIM-NCI/ELF) of two penta-coordinate complexes with pseudohalide ligands

  • 期刊论文

  • 发表日期：

    2026年5月18日

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  • Mondher Dhifet,
  • Amin Naifar,
  • Houcine Ghalla,
  • Habib Nasri

摘要

Our current study establishes the synthesis and the spectroscopic attributes of a two five-coordinated iron(II) picket fence porphyrin with the formula [Na(2,2,2-crypt)][FeII(TpivPP)(NCO)] (Fe2NCO) and [K(2,2,2-crypt)][FeII(TpivPP)(NCS)] (Fe2NCS) where TpivPP is the (α,α,α,α-terakis(o-pivalamidophenyl)(porphinato) anion and (2,2,2-crypt) is the cryptand-222). The two complexes are characterized in solution by UV-visible and IR spectroscopies. The molecular structures of the two compounds are determined and described using single-crystal X-ray diffraction analysis and Hirshfeld surface area derivations. Our complexes crystallize in the monoclinic system with space group C2 and P21/n, respectively. The average distance between the central Fe(II) ion and the nitrogen atoms in the equatorial position is 2.120(2) Å and 2.104(2) Å, respectively, while the FeII–N(axial ligand) distances from the cyanate and thiocyanate ligand are 2.005(3) Å and 2.042(2) Å, respectively. In each compound, the crystal packing cohesion is stabilized by unconventional intramolecular C–H…O and C–H…N hydrogen bonds. Furthermore, several important physical attributes were numerically examined to deliver an in-depth analysis of the electron charge migration pathways of the iron(II) porphyrin complex using Density Functional Theory (DFT) at the B3LYP-D3/LanL2DZ level. This includes the analysis of frontier molecular orbitals (FMOs) and associated reactivity descriptors, molecular electrostatic potential (MEP), non-covalent interaction (NCI) analysis through reduced density gradient (RDG) surfaces, and bond critical points (BCPs), as well as electron localization function (ELF), localized orbital locator (LOL), and Hirshfeld surface characterization.