| Autor: |
Mchiri C; Laboratoire de Physico-Chimie des Matériaux (LPCM), Faculté des Sciences de Monastir, Avenue de l'environnement, University of Monastir, Monastir 5019, Tunisia., Coetzee LC; Department of Chemistry, University of South Africa, Private Bag X6, Florida, Roodepoort, Johannesburg 1710, Gauteng, South Africa., Chandoul F; Faculty of Mathematical, Physical and Natural Sciences of Tunis, University of Tunis El Manar, Tunis 2092, Tunisia., Jedidi A; Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia., Adeyinka AS; Research Centre for Synthesis and Catalysis, Department of Chemical Sciences, University of Johannesburg, Auckland Park, Johannesburg 2006, Gauteng, South Africa., Magwa N; Department of Chemistry, University of South Africa, Private Bag X6, Florida, Roodepoort, Johannesburg 1710, Gauteng, South Africa., Roisnel T; Centre de Diffractométrie X, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes, France., Ben Moussa S; Faculty of Science and Arts, Mohail Asser, King Khalid University, Abha 61421, Saudi Arabia., Nasri H; Laboratoire de Physico-Chimie des Matériaux (LPCM), Faculté des Sciences de Monastir, Avenue de l'environnement, University of Monastir, Monastir 5019, Tunisia. |
| Abstrakt: |
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 Cd II 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 Φ f = 0.084, Φ f = 0.06 and Φ f = 0.03 for H 2 -TMPP free-base porphyrin, [Cd(TMPP)] and [Cd(TMPP)(Pyz)] ( 1 ) respectively. Singlet oxygen revealed that the H 2 -TMPP porphyrin produced the most efficient singlet oxygen quantum yield of (Φ Δ = 0.73) compared to [CdTMPP] (Φ Δ = 0.57) and [Cd(TMPP)(Pyz)] ( 1 ) (Φ Δ = 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%). |
