Distorted five-coordinate square pyramidal geometry of a cadmium(II) complex containing a 2-methylimidazole ligand: Crystal structure and axial ligand effect on spectroscopic properties

Mchiri, Chadlia; Nasri, Habib; Frochot, Céline; Acherar, Samir

doi:10.1016/j.poly.2019.114107

Cited by 10 publications

(1 citation statement)

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“…Thus, metalation of H 2 -TMPP with Cd(II) metal and the axial coordination of the pyrazine led to a reduction in the Φ ∆ value compared to that observed for H 2 -TMPP. Previous investigations into Cd(II)-porphyrins have determined that the Cd(II) metal ion is larger than the central hole of the porphyrinato core, which generates an important deformation on the macrocycle [22,33]. Additionally, as reported before, the coordination of axial ligands with a metalloporphyrin can generate a deformation on the macrocycle.…”

Section: Fluorescence and Singlet Oxygen Studiesmentioning

confidence: 67%

Synthesis, Characterization, DFT and Photocatalytic Studies of a New Pyrazine Cadmium(II) Tetrakis(4-methoxy-phenyl)-porphyrin Compound

et al. 2022

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This study describes the synthesis, theoretical investigations, and photocatalytic degradational properties of a new (pyrazine)(meso-tetrakis(4-tert-methoxyphenyl)-porphyrinato)-cadmium (II) ([Cd(TMPP)-Pyz] complex (1). The new penta-coordinated CdII porphyrin complex (1) was characterized by various spectroscopic techniques, including FT-IR, NMR, UV-visible absorption, fluorescence emission, and singlet oxygen, while its molecular structure was studied using single crystal X-ray diffraction. The UV–Vis spectroscopic study highlighted the redshift of the absorption bands after the insertion of the Cd(II) metal ion into the TMPP ring. The co-coordination of the pyrazine axial ligand enhanced this effect. A fluorescence emission spectroscopic study showed a significant blueshift in the Q bands, accompanied by a decrease in the fluorescence emission intensity and quantum yields of Φf = 0.084, Φf = 0.06 and Φf = 0.03 for H2-TMPP free-base porphyrin, [Cd(TMPP)] and [Cd(TMPP)(Pyz)] (1) respectively. Singlet oxygen revealed that the H2-TMPP porphyrin produced the most efficient singlet oxygen quantum yield of (ΦΔ = 0.73) compared to [CdTMPP] (ΦΔ = 0.57) and [Cd(TMPP)(Pyz)] (1) (ΦΔ = 0.13). In the crystal lattice, the [Cd(TMPP)Pyz]) was stabilized through non-covalent intermolecular interactions (NCI), such as the hydrogen bonds C-H···N and C-H···Cg. Additionally, crystal explorer software was then utilized to measure the quantitative analysis of the intermolecular interactions in the unit cell of the crystal structure and established that the C-H···π interaction dominated. The Natural bond orbital (NBO) analysis revealed that each molecule is stabilized by hyperconjugation and charge delocalization. As a photocatalyst, the coordination complex 1 showed excellent photocatalytic activity toward the degradation of Levafix Blue CA reactive dye (i.e., dye photo-degradation of 80%).

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Section: Fluorescence and Singlet Oxygen Studiesmentioning

confidence: 67%