Photooxidation of 2,2′-(Ethyne-1,2-diyl)dianilines: An Enhanced Photocatalytic Properties of New Salophen-Based Zn(II) Complexes
Abstract
:1. Introduction
2. Materials and Methods
2.1. Synthesis of N2, O2—Donor-Based Schiff’s Base Ligands
2.2. Synthesis of Zn(II) Complexes
3. Results and Discussion
3.1. Molar Conductance and Thermal Analysis
3.2. Absorption and Emission Studies
3.3. Photocatalysis
3.3.1. Optimization of Catalysis (Ligands and Zn(II) Complexes
3.3.2. Identifying the Active Species and Optimization of Oxidant for Photooxidation Process
Effect of Visible Light Intensity
Effect of Solvent
Recyclability and Stability of the Catalytic System
3.3.3. The Efficiency of the Photocatalyst System
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Complex | ν (Ar-OH) | ν (-C=N-) | ν (Zn-O) | ν (Zn-N) | λonset (nm) | Eg (eV) | Eg (eV) (Solid State) | Surface Area (m2/g) |
---|---|---|---|---|---|---|---|---|
CPAMN) | 3295 | 1645 | - | - | 503.66 | 2.46 | 2.75 | 65 |
FPAMN | 3306 | 1652 | - | - | 512.39 | 2.42 | 2.72 | 59 |
MPAMN | 3345 | 1660 | - | - | 514.52 | 2.41 | 2.87 | 57 |
[Zn(CPAMN)] | - | 1628 | 516 | 428 | 596.15 | 2.08 | 2.18 | 208 |
[Zn(FPAMN)] | - | 1634 | 522 | 436 | 553.57 | 2.24 | 2.15 | 184 |
[Zn(MPAMN)] | - | 1642 | 518 | 419 | 568.80 | 2.18 | 2.24 | 169 |
S.No. | Intensity of the Visible Light (Tungsten) | Time (h) | % Yield Compound 5a |
---|---|---|---|
1 | CPAMN | 24 | -- |
2 | FPAMN | 24 | -- |
3 | MPAMN | 24 | -- |
4 | [Zn(CPAMN)] | 24 | 84 |
5 | [Zn(FPAMN)] | 24 | 62 |
6 | [Zn(MPAMN)] | 24 | 40 |
Oxidant | Scavenger | Time (min) | Conversion Rate |
---|---|---|---|
Tert-butyl peroxide | t-butyl alcohol | 24 | 10 |
Pyridine N-oxide | t-butyl alcohol | 24 | 16 |
4-Methylpyridine N-oxide | t-butyl alcohol | 24 | 22 |
(Diacetoxyiodo)benzene | t-butyl alcohol | 24 | 84 |
Bis(tert-butylcarbonyloxy) iodobenzene | t-butyl alcohol | 24 | 69 |
[Bis(trifluoroacetoxy)iodo]benzene | t-butyl alcohol | 24 | 74 |
Tert-butyl peroxide | Benzoquinone | 24 | 5 |
Pyridine N-oxide | Benzoquinone | 24 | 2 |
4-Methylpyridine N-oxide | Benzoquinone | 24 | trace |
(Diacetoxyiodo)benzene | Benzoquinone | 24 | 15 |
Bis(tert-butylcarbonyloxy) iodobenzene | Benzoquinone | 24 | 8 |
[Bis(trifluoroacetoxy)iodo]benzene | Benzoquinone | 24 | 5 |
S.No. | Intensity of the Visible Light (Tungsten) | Time (h) | % Yield Compound 5 a |
---|---|---|---|
1 | 300 Watts | 46 | 40 |
2 | 400 Watts | 38 | 62 |
3 | 500 Watts | 24 | 84 |
S.No. | Solvent and H2O | Time (h) | Yield (%) Compound 2a |
---|---|---|---|
1 | Toluene | 24 | 32 |
2 | Dichloroethane | 24 | 58 |
3 | THF | 24 | 35 |
4 | 1,4-Dioxane | 24 | 18 |
5 | Acetone | 24 | 21 |
6 | Methanol | 24 | 30 |
7 | Ethanol | 24 | 42 |
8 | CH3CN | 24 | 84 |
9 | DMF | 24 | 13 |
10 | DMSO | 24 | 9 |
11 | Pure H2O | 24 | 65 |
Diamine Compound | Product | Complexes | Yield % |
---|---|---|---|
1a | 2a | [Zn(CPAMN)] | 84 |
[Zn(FPAMN)] | 59 | ||
[Zn(MPAMN)] | 48 | ||
1b | 2b | Zn(CPAMN)] | 90 |
[Zn(FPAMN)] | 61 | ||
[Zn(MPAMN)] | 39 | ||
1c | 2c | Zn(CPAMN)] | 79 |
[Zn(FPAMN)] | 55 | ||
[Zn(MPAMN)] | 42 | ||
1d | 2d | Zn(CPAMN)] | 81 |
[Zn(FPAMN)] | 49 | ||
[Zn(MPAMN)] | 31 | ||
1e | 2e | Zn(CPAMN)] | 85 |
[Zn(FPAMN)] | 51 | ||
[Zn(MPAMN)] | 43 | ||
1f | 2f | Zn(CPAMN)] | 86 |
[Zn(FPAMN)] | 49 | ||
[Zn(MPAMN)] | 37 | ||
1g | 2g | Zn(CPAMN)] | 69 |
[Zn(FPAMN)] | 50 | ||
[Zn(MPAMN)] | 41 | ||
1h | 2h | Zn(CPAMN)] | 74 |
[Zn(FPAMN)] | 38 | ||
[Zn(MPAMN)] | 21 | ||
1i | 2i | Zn(CPAMN)] | 87 |
[Zn(FPAMN)] | 56 | ||
[Zn(MPAMN)] | 32 | ||
1j | 2j | Zn(CPAMN)] | 64 |
[Zn(FPAMN)] | 35 | ||
[Zn(MPAMN)] | 19 |
S.No. | Photocatalyst | Time (h) | Yield (%) a |
---|---|---|---|
PC-1 | Dichloro(N,N,N′,N′-tetramethylethylenediamine)zinc (28308-00-1) | 24 | -- |
PC-2 | Zinc bis[bis(trimethylsilyl)amide] (14760-26-0) | 24 | 5 |
PC-3 | Zinc di[bis(trifluoromethylsulfonyl)imide] (168106-25-0) | 24 | 8 |
PC-4 | Ziram (CAS No. 137-30-4) | 24 | 10 |
PC-5 | Zinc phthalocyanine (14320-04-8) | 24 | -- |
PC-6 | [Zn(CPAMN)] | 24 | 84 |
PC-7 | [Zn(FPAMN)] | 24 | 59 |
PC-8 | [Zn(MPAMN)] | 24 | 48 |
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Subburu, M.; Gade, R.; Chetti, P.; Pola, S. Photooxidation of 2,2′-(Ethyne-1,2-diyl)dianilines: An Enhanced Photocatalytic Properties of New Salophen-Based Zn(II) Complexes. Photochem 2022, 2, 358-375. https://doi.org/10.3390/photochem2020025
Subburu M, Gade R, Chetti P, Pola S. Photooxidation of 2,2′-(Ethyne-1,2-diyl)dianilines: An Enhanced Photocatalytic Properties of New Salophen-Based Zn(II) Complexes. Photochem. 2022; 2(2):358-375. https://doi.org/10.3390/photochem2020025
Chicago/Turabian StyleSubburu, Mahesh, Ramesh Gade, Prabhakar Chetti, and Someshwar Pola. 2022. "Photooxidation of 2,2′-(Ethyne-1,2-diyl)dianilines: An Enhanced Photocatalytic Properties of New Salophen-Based Zn(II) Complexes" Photochem 2, no. 2: 358-375. https://doi.org/10.3390/photochem2020025