Spectroscopic, structural characterization, along with DFT calculation, of a new cadmium(II) acetato meso-arylporphyrin: Theoretical study on NO2, CO2, N2, NO2, and SO2 gas-sensing and analysis of electrical conductance and dielectric properties

• Published in: Journal of molecular structure 2025-02, Vol.1322 (Part 1), p.140343, Article 140343
• Main Authors: Dardouri, N.E., Amor, F. Ben, Bouzid, G., Mkacher, H., Hamdaoui, N., Nasri, S., Ghalla, H., Roisnel, Thierry, Turowska-Tyrk, Ilona, Nasri, H.
• Format: Article
• Language: English
• Subjects: Cadmium(II) porphyrin complex; Chemical Sciences; DFT calculation, QTAIM and NCI-RDG analyses; Electrical conductance and dielectric properties; UV–Vis spectroscopy; X-ray molecular structure
• ISSN: 0022-2860; 0022-2860
• DOI: 10.1016/j.molstruc.2024.140343

•Synthesis of the (acetato)‑meso-tetra(para-methoxyphenyl)porphyrin ion complex [Cd(TMPP)(OAc)]- (complex 1).•IR, UV/Vis, IR and 1H MNR spectroscopy investigations on complex 1.•Single crystal X-ray molecular structure and Hirshfeld surface analysis of 1 are reported.•DFT, FMOs, MEP calculations and QTAIM and NCI-RDG analyses on complex 1.•The impedance and dielectric spectroscopy of the InGa/[Cd(TMPP)(OAc)]/InGa device. The paper presents a combined experimental and computational investigation of the cadmium(II) (acetato)‑meso-tetra(para-methoxyphenyl)porphyrin ion complex [Cd(TMPP)(OAc)]- (complex 1), which was prepared by the reaction of [Cd(TMPP)] with an excess of NaOAc and crysptand-222 in chloroform. This new Cd(II) meso‑arylporphyrin was characterized by elementary analysis and UV–Vis, IR, and 1H NMR spectroscopic techniques along with single crystal X-ray diffraction. This later study shows that the Cd2+center ion adopts a distorted square pyramidal geometry and is coordinated by the four nitrogens of the TMPP porphyrinate and the oxygen atom of the acetato axial ligand. The intermolecular interactions in the crystal lattice of [Cd(TMPP)(OAc)]-, determined using the PLATON program and Hirshfeld surfaces analysis, are of types O__H…O, C__H…H, C__H…Cl, C__H…Cg and C__Cl…Cg (Cg is the centroid of a phenyl or a pyrrole ring) involving the [Cd(TMPP)(OAc)]- ion complex, the [Na(crypt-222)]+ counterion, and the chloroform and water molecules found in the crystal lattice of complex 1. Using DFT calculations at the DFT/B3LYP-D3/lanL2DZ level of theory HOMO–LUMO orbitals of 1 and several global reactive parameters of this compound were calculated. The 3D-MEP plots of [Cd(TMPP)(OAc)]- were also determined. This theoretical study includes the sensing properties of complex 1 and the NO2, CO2, N2, and SO2 gas molecules. Furthermore, experimental tests have been carried out concerning the impedance and dielectric spectroscopy of the InGa/[Cd(TMPP)(OAc)]/InGa device. The paper presents a combined experimental and computational investigation of the cadmium(II) (acetato)‑meso-tetra(para-methoxyphenyl)porphyrin ion complex [Cd(TMPP)(OAc)]- (complex 1), which was prepared by the reaction of [Cd(TMPP)] with an excess of NaOAc and crysptand-222 in chloroform. This new Cd(II) meso‑arylporphyrin was characterized by elementary analysis and UV/Vis, IR, and 1H NMR spectroscopic techniques along with single crystal X-ray diffraction. The intermolecular interactions in the c