Mechanistic study of photocatalytic CO<sub>2</sub> reduction using a Ru(<scp>ii</scp>)–Re(<scp>i</scp>) supramolecular photocatalyst

Kamogawa, Kei; Shimoda, Yudai; Miyata, Kiyoshi; Onda, Ken; Yamazaki, Yasuomi; Tamaki, Yusuke; Ishitani, Osamu

doi:10.1039/d1sc02213j

Cited by 32 publications

(57 citation statements)

References 41 publications

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“…Based on previous work [17,18,[43][44][45][46] and the above experimental investigations, we propose the mechanism for all these photocatalytic systems shown in Figure 11. At first, the Re complex is photochemically excited to generate the 1 Re* species, and then the species could rapidly undergo ISC, forming 3 Re* states in order to participate in the photocatalytic electron transfer process.…”

Section: Mechanistic Discussionmentioning

confidence: 85%

Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole‐Pyridine Framework for Efficient CO₂ Photoreduction

Qiu

Chen

Yang

et al. 2021

Chemistry A European J

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The photocatalytic reduction of CO 2 into fuels offers the prospect for creating a new CO 2 economy. Harnessing visible light-driven CO 2 -to-CO reduction mediated by the long-lived triplet excited state of rhenium(I) tricarbonyl complexes is a challenging approach. We here develop a series of new mononuclear rhenium(I) tricarbonyl complexes (Re-1À Re-4) based on the imidazole-pyridine skeleton for photo-driven CO 2 reduction. These catalysts are featured by combining pyridyl-imidazole with the aromatic ring and different pendant organic groups onto the N1 position of 1,3imidazole unit, which display phosphorescence under Arsaturated solution even at ambient conditions. By contrast, {Re[9-(pyren-1-yl)-10-(pyridin-2-yl)-9H-pyreno[4,5-d] imidazole)](CO) 3 Cl} (Re-4) by introducing pyrene ring at the N1 position of pyrene-fused imidazole unit exhibits superior catalytic performance with a higher turnover number for CO (TON CO = 124) and > 99.9 % selectivity, primarily ascribed to the strong visible light-harvesting ability, long-lived triplet lifetimes (164.2 μs) and large reductive quenching constant. Moreover, the rhenium(I) tricarbonyl complexes derived from π-extended pyrene chromophore exhibit a long lifetime corresponding to its ligand-localized triplet state ( 3 IL) evidenced from spectroscopic investigations and DFT calculations.

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Section: Mechanistic Discussionmentioning

confidence: 85%

Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole‐Pyridine Framework for Efficient CO₂ Photoreduction

Qiu

Chen

Yang

et al. 2021

Chemistry A European J

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“…Here, DMSO is a suitable solvent for the photocatalytic CO 2 reduction using a Re diimine tricarbonyl complex in the presence of BIH and TEOA. 38 Under micromolar-order concentration conditions, ReDRe dissociated into the corresponding monomer (Figure 9). The first oxidation and reduction potentials of the porphyrin dimer D' and monomer D (Scheme 3) were almost same in DMSO in differential pulse voltammetry (DPV) (Figure S95) and the potentials of ReD'Re were similar to those in DMA.…”

Section: Scheme 3 Synthesis Of the Heterodimer Red'mentioning

confidence: 99%

Photocatalytic CO₂reduction sensitized by a special-pair mimic porphyrin connected with a rhenium(i) tricarbonyl complex

et al. 2022

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“…They demonstrated that the triethanolamine ligand on the catalyst moiety reacts with CO 2 to produce a carbonate ester complex, which then subsequently gets reduced to CO. This phenomenon was found beneficial in the sense that even lower concentrations of CO 2 (10%) could get reduced efficiently …”

Section: Resultsmentioning

confidence: 99%

“…This phenomenon was found beneficial in the sense that even lower concentrations of CO 2 (10%) could get reduced efficiently. 192 2.7. Selection of the Semiconductor Component.…”

Section: Table 1 Continuedmentioning

confidence: 99%

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO₂ Reduction

et al. 2021

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Photocatalytic CO2 reduction into C1 products is one of the most trending research subjects of current times as sustainable energy generation is the utmost need of the hour. In this review, we have tried to comprehensively summarize the potential of supramolecule-based photocatalysts for CO2 reduction into C1 compounds. At the outset, we have thrown light on the inert nature of gaseous CO2 and the various challenges researchers are facing in its reduction. The evolution of photocatalysts used for CO2 reduction, from heterogeneous catalysis to supramolecule-based molecular catalysis, and subsequent semiconductor–supramolecule hybrid catalysis has been thoroughly discussed. Since CO2 is thermodynamically a very stable molecule, a huge reduction potential is required to undergo its one- or multielectron reduction. For this reason, various supramolecule photocatalysts were designed involving a photosensitizer unit and a catalyst unit connected by a linker. Later on, solid semiconductor support was also introduced in this supramolecule system to achieve enhanced durability, structural compactness, enhanced charge mobility, and extra overpotential for CO2 reduction. Reticular chemistry is seen to play a pivotal role as it allows bringing all of the positive features together from various components of this hybrid semiconductor–supramolecule photocatalyst system. Thus, here in this review, we have discussed the selection and role of various components, viz. the photosensitizer component, the catalyst component, the linker, the semiconductor support, the anchoring ligands, and the peripheral ligands for the design of highly performing CO2 reduction photocatalysts. The selection and role of various sacrificial electron donors have also been highlighted. This review is aimed to help researchers reach an understanding that may translate into the development of excellent CO2 reduction photocatalysts that are operational under visible light and possess superior activity, efficiency, and selectivity.

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Mechanistic study of photocatalytic CO₂ reduction using a Ru(ii)–Re(i) supramolecular photocatalyst

Abstract: Supramolecular photocatalysts comprising [Ru(diimine)3]2+ photosensitiser and fac-[Re(diimine)(CO)3{OC(O)OC2H4NR2}] catalyst units can be used to reduce CO2 to CO with high selectivity, durability and efficiency. In the presence of triethanolamine, the Re...

Cited by 32 publications

References 41 publications

Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole‐Pyridine Framework for Efficient CO₂ Photoreduction

Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole‐Pyridine Framework for Efficient CO₂ Photoreduction

Photocatalytic CO₂reduction sensitized by a special-pair mimic porphyrin connected with a rhenium(i) tricarbonyl complex

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO₂ Reduction

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Mechanistic study of photocatalytic CO2 reduction using a Ru(ii)–Re(i) supramolecular photocatalyst

Abstract: Supramolecular photocatalysts comprising [Ru(diimine)3]2+ photosensitiser and fac-[Re(diimine)(CO)3{OC(O)OC2H4NR2}] catalyst units can be used to reduce CO2 to CO with high selectivity, durability and efficiency. In the presence of triethanolamine, the Re...

Cited by 32 publications

References 41 publications

Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole‐Pyridine Framework for Efficient CO2 Photoreduction

Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole‐Pyridine Framework for Efficient CO2 Photoreduction

Photocatalytic CO2reduction sensitized by a special-pair mimic porphyrin connected with a rhenium(i) tricarbonyl complex

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO2 Reduction

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Product

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Mechanistic study of photocatalytic CO₂ reduction using a Ru(ii)–Re(i) supramolecular photocatalyst

Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole‐Pyridine Framework for Efficient CO₂ Photoreduction

Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole‐Pyridine Framework for Efficient CO₂ Photoreduction

Photocatalytic CO₂reduction sensitized by a special-pair mimic porphyrin connected with a rhenium(i) tricarbonyl complex

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO₂ Reduction