Photocatalytic turnover of CO2 under visible light by [Re(CO)3(1-(1,10) phenanthroline-5-(4-nitro-naphthalimide))Cl] in tandem with the sacrificial donor BIH
“…This temperature dependence suggests that this latter emissive band is associated with a 3 MLCT transition, as previously observed for similar Re complexes. 54 Computational studies revealed that upon the introduction of spin-orbit coupling (SOC) via the spin-orbit mean field (SOMF) 55 approach the character of the second band becomes more convoluted. Scalar roots S8 and S9 are quasi-degenerate and exhibit oscillator strength values of 0.128 and 0.342, respectively.…”
The photocatalytic efficacy of a novel mononuclear rhenium(I) complex in CO2 reduction is remarkable, with a turnover number (TONCO) of 1517 in three hours, significantly outperforming previous Re(I) catalysts. This complex, synthesized via a substitution reaction on an aromatic ring to form a bromo-bipyridine derivative, L1 = 2-Bromo-6-(1H-pyrazol-1-yl)pyridine, and further reacting with [Re(CO)5Cl], results in the facial-tricarbonyl complex [ReL1(CO)3Cl] (1). The light green solid was obtained with an 80% yield and thoroughly characterized using cyclic voltammetry, NMR, FTIR and UV-vis spectroscopy. Cyclic voltammetry under CO2 atmosphere revealed three distinct redox processes, suggesting the formation of new electroactive compounds. The studies on photoreduction highlighted the ability of the catalyst to reduce CO2, while NMR, FTIR, and ESI mass spectrometry provided insights into the mechanism, revealing the formation of solvent-coordinated complexes and new species under varying conditions. Additionally, computational studies (DFT) were undertaken to better understand the electronic structure and reactivity patterns of 1, focusing on the role of the ligand, spectroscopic features, and redox behavior. This comprehensive approach provides insights on the intricate dynamics of CO2 photoreduction, showcasing the potential of Re(I) complexes in catalysis.
“…This temperature dependence suggests that this latter emissive band is associated with a 3 MLCT transition, as previously observed for similar Re complexes. 54 Computational studies revealed that upon the introduction of spin-orbit coupling (SOC) via the spin-orbit mean field (SOMF) 55 approach the character of the second band becomes more convoluted. Scalar roots S8 and S9 are quasi-degenerate and exhibit oscillator strength values of 0.128 and 0.342, respectively.…”
The photocatalytic efficacy of a novel mononuclear rhenium(I) complex in CO2 reduction is remarkable, with a turnover number (TONCO) of 1517 in three hours, significantly outperforming previous Re(I) catalysts. This complex, synthesized via a substitution reaction on an aromatic ring to form a bromo-bipyridine derivative, L1 = 2-Bromo-6-(1H-pyrazol-1-yl)pyridine, and further reacting with [Re(CO)5Cl], results in the facial-tricarbonyl complex [ReL1(CO)3Cl] (1). The light green solid was obtained with an 80% yield and thoroughly characterized using cyclic voltammetry, NMR, FTIR and UV-vis spectroscopy. Cyclic voltammetry under CO2 atmosphere revealed three distinct redox processes, suggesting the formation of new electroactive compounds. The studies on photoreduction highlighted the ability of the catalyst to reduce CO2, while NMR, FTIR, and ESI mass spectrometry provided insights into the mechanism, revealing the formation of solvent-coordinated complexes and new species under varying conditions. Additionally, computational studies (DFT) were undertaken to better understand the electronic structure and reactivity patterns of 1, focusing on the role of the ligand, spectroscopic features, and redox behavior. This comprehensive approach provides insights on the intricate dynamics of CO2 photoreduction, showcasing the potential of Re(I) complexes in catalysis.
“…Transition-metal complexes as a kind of molecular catalysts for homogeneous systems have attracted enormous attention due to their clear molecular structures and catalytic active sites, which facilitates the exploration of the relationship between structure and catalytic performance . In recent years, various precious metal (such as Re, − Ir, Au, , and Ru , ) complexes have been employed as molecular catalysts for photocatalytic reduction of CO 2 . Although these kind of complexes usually display excellent photocatalytic performance for CO 2 reduction, − the development of nonprecious metal (such as Co, − Mn, − Ni, , and Fe − ) complex catalysts has become a hot spot due to the high cost of precious metal complexes.…”
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