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

Chadlia Mchiri; Louis-Charl C. Coetzee; Faycal Chandoul; Abdesslem Jedidi; Adedapo S. Adeyinka; Nomampondo Magwa; Thierry Roisnel; Sana Ben Moussa; Habib Nasri

doi:10.3390/molecules27123833

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

Chadlia Mchiri, Louis-Charl C. Coetzee, Faycal Chandoul, Abdesslem Jedidi, Adedapo S. Adeyinka, Nomampondo Magwa, Thierry Roisnel, Sana Ben Moussa, Habib Nasri

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Abstract

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%).

Original language	English (US)
Pages (from-to)	3833
Journal	Molecules
Volume	27
Issue number	12
DOIs	https://doi.org/10.3390/molecules27123833
State	Published - Jun 14 2022

Bibliographical note

KAUST Repository Item: Exported on 2022-06-21
Acknowledgements: The authors extend their appreciation to the Deanship of Scientific Research at King Khalid University, Abha, KSA, for funding this work through the Research Group under grant number (R.G.P-1/3/43). The authors would like to acknowledge the center for high-performance computing (CHPC), South Africa, for providing computational resources for this research project. A. Jedidi acknowledges King Abdulaziz University’s High-Performance Computing Center (Aziz Supercomputer) (http://hpc.kau.edu.sa, accessed on 11 March 2021) for supporting the computational work and KAUST Supercomputing Laboratory (Shaheen II) for the provided resources.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

ASJC Scopus subject areas

Organic Chemistry

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@article{9f59ad1c8e00429691d021fb39c81712,

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

abstract = "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%).",

author = "Chadlia Mchiri and Coetzee, {Louis-Charl C.} and Faycal Chandoul and Abdesslem Jedidi and Adeyinka, {Adedapo S.} and Nomampondo Magwa and Thierry Roisnel and {Ben Moussa}, Sana and Habib Nasri",

note = "KAUST Repository Item: Exported on 2022-06-21 Acknowledgements: The authors extend their appreciation to the Deanship of Scientific Research at King Khalid University, Abha, KSA, for funding this work through the Research Group under grant number (R.G.P-1/3/43). The authors would like to acknowledge the center for high-performance computing (CHPC), South Africa, for providing computational resources for this research project. A. Jedidi acknowledges King Abdulaziz University{\textquoteright}s High-Performance Computing Center (Aziz Supercomputer) (http://hpc.kau.edu.sa, accessed on 11 March 2021) for supporting the computational work and KAUST Supercomputing Laboratory (Shaheen II) for the provided resources. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2022",

month = jun,

day = "14",

doi = "10.3390/molecules27123833",

language = "English (US)",

volume = "27",

pages = "3833",

journal = "Molecules",

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number = "12",

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TY - JOUR

T1 - Synthesis, Characterization, DFT and Photocatalytic Studies of a New Pyrazine Cadmium(II) Tetrakis(4-methoxy-phenyl)-porphyrin Compound

AU - Mchiri, Chadlia

AU - Coetzee, Louis-Charl C.

AU - Chandoul, Faycal

AU - Jedidi, Abdesslem

AU - Adeyinka, Adedapo S.

AU - Magwa, Nomampondo

AU - Roisnel, Thierry

AU - Ben Moussa, Sana

AU - Nasri, Habib

N1 - KAUST Repository Item: Exported on 2022-06-21 Acknowledgements: The authors extend their appreciation to the Deanship of Scientific Research at King Khalid University, Abha, KSA, for funding this work through the Research Group under grant number (R.G.P-1/3/43). The authors would like to acknowledge the center for high-performance computing (CHPC), South Africa, for providing computational resources for this research project. A. Jedidi acknowledges King Abdulaziz University’s High-Performance Computing Center (Aziz Supercomputer) (http://hpc.kau.edu.sa, accessed on 11 March 2021) for supporting the computational work and KAUST Supercomputing Laboratory (Shaheen II) for the provided resources. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2022/6/14

Y1 - 2022/6/14

N2 - 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%).

AB - 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%).

UR - http://hdl.handle.net/10754/679182

UR - https://www.mdpi.com/1420-3049/27/12/3833

U2 - 10.3390/molecules27123833

DO - 10.3390/molecules27123833

M3 - Article

C2 - 35744951

SN - 1420-3049

VL - 27

SP - 3833

JO - Molecules

JF - Molecules

IS - 12

ER -

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

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