Investigation of excited state, reductive quenching, and intramolecular electron transfer of Ru(II)-Re(i) supramolecular photocatalysts for CO2 reduction using time-resolved IR measurements

Kazuhide Koike, David Grills, Yusuke Tamaki, Etsuko Fujita, Kei Okubo, Yasuomi Yamazaki, Masaki Saigo, Tatsuhiko Mukuta, Ken Onda, Osamu Ishitani

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Abstract

Supramolecular photocatalysts in which Ru(ii) photosensitizer and Re(i) catalyst units are connected to each other by an ethylene linker are among the best known, most effective and durable photocatalytic systems for CO2 reduction. In this paper we report, for the first time, time-resolved infrared (TRIR) spectra of three of these binuclear complexes to uncover why the catalysts function so efficiently. Selective excitation of the Ru unit with a 532 nm laser pulse induces slow intramolecular electron transfer from the 3MLCT excited state of the Ru unit to the Re unit, with rate constants of (1.0-1.1) × 104 s-1 as a major component and (3.5-4.3) × 106 s-1 as a minor component, in acetonitrile. The produced charge-separated state has a long lifetime, with charge recombination rate constants of only (6.5-8.4) × 104 s-1. Thus, although it has a large driving force (-ΔG0CR ∼ 2.6 eV), this process is in the Marcus inverted region. On the other hand, in the presence of 1-benzyl-1,4-dihydronicotinamide (BNAH), reductive quenching of the excited Ru unit proceeds much faster (kq[BNAH (0.2 M)] = (3.5-3.8) × 106 s-1) than the abovementioned intramolecular oxidative quenching, producing the one-electron-reduced species (OERS) of the Ru unit. Nanosecond TRIR data clearly show that intramolecular electron transfer from the OERS of the Ru unit to the Re unit (kET > 2 × 107 s-1) is much faster than from the excited state of the Ru unit, and that it is also faster than the reductive quenching process of the excited Ru unit by BNAH. To measure the exact value of kET, picosecond TRIR spectroscopy and a stronger reductant were used. Thus, in the case of the binuclear complex with tri(p-fluorophenyl)phosphine ligands (RuRe(FPh)), for which intramolecular electron transfer is expected to be the fastest among the three binuclear complexes, in the presence of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH), kET was measured as kET = (1.4 ± 0.1) × 109 s-1. This clearly shows that intramolecular electron transfer in these RuRe binuclear supramolecular photocatalysts is not the rate-determining process in the photocatalytic reduction of CO2, which is one of the main reasons why they work so efficiently.

Original languageEnglish
Pages (from-to)2961-2974
Number of pages14
JournalChemical Science
Volume9
Issue number11
DOIs
Publication statusPublished - Jan 1 2018

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Photocatalysts
Excited states
Quenching
Electrons
phosphine
Rate constants
Infrared radiation
Catalysts
Photosensitizing Agents
Reducing Agents
Infrared spectroscopy
Laser pulses
Ligands

ASJC Scopus subject areas

  • Chemistry(all)

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Investigation of excited state, reductive quenching, and intramolecular electron transfer of Ru(II)-Re(i) supramolecular photocatalysts for CO2 reduction using time-resolved IR measurements. / Koike, Kazuhide; Grills, David; Tamaki, Yusuke; Fujita, Etsuko; Okubo, Kei; Yamazaki, Yasuomi; Saigo, Masaki; Mukuta, Tatsuhiko; Onda, Ken; Ishitani, Osamu.

In: Chemical Science, Vol. 9, No. 11, 01.01.2018, p. 2961-2974.

Research output: Contribution to journalArticle

Koike, Kazuhide ; Grills, David ; Tamaki, Yusuke ; Fujita, Etsuko ; Okubo, Kei ; Yamazaki, Yasuomi ; Saigo, Masaki ; Mukuta, Tatsuhiko ; Onda, Ken ; Ishitani, Osamu. / Investigation of excited state, reductive quenching, and intramolecular electron transfer of Ru(II)-Re(i) supramolecular photocatalysts for CO2 reduction using time-resolved IR measurements. In: Chemical Science. 2018 ; Vol. 9, No. 11. pp. 2961-2974.
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AU - Koike, Kazuhide

AU - Grills, David

AU - Tamaki, Yusuke

AU - Fujita, Etsuko

AU - Okubo, Kei

AU - Yamazaki, Yasuomi

AU - Saigo, Masaki

AU - Mukuta, Tatsuhiko

AU - Onda, Ken

AU - Ishitani, Osamu

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N2 - Supramolecular photocatalysts in which Ru(ii) photosensitizer and Re(i) catalyst units are connected to each other by an ethylene linker are among the best known, most effective and durable photocatalytic systems for CO2 reduction. In this paper we report, for the first time, time-resolved infrared (TRIR) spectra of three of these binuclear complexes to uncover why the catalysts function so efficiently. Selective excitation of the Ru unit with a 532 nm laser pulse induces slow intramolecular electron transfer from the 3MLCT excited state of the Ru unit to the Re unit, with rate constants of (1.0-1.1) × 104 s-1 as a major component and (3.5-4.3) × 106 s-1 as a minor component, in acetonitrile. The produced charge-separated state has a long lifetime, with charge recombination rate constants of only (6.5-8.4) × 104 s-1. Thus, although it has a large driving force (-ΔG0CR ∼ 2.6 eV), this process is in the Marcus inverted region. On the other hand, in the presence of 1-benzyl-1,4-dihydronicotinamide (BNAH), reductive quenching of the excited Ru unit proceeds much faster (kq[BNAH (0.2 M)] = (3.5-3.8) × 106 s-1) than the abovementioned intramolecular oxidative quenching, producing the one-electron-reduced species (OERS) of the Ru unit. Nanosecond TRIR data clearly show that intramolecular electron transfer from the OERS of the Ru unit to the Re unit (kET > 2 × 107 s-1) is much faster than from the excited state of the Ru unit, and that it is also faster than the reductive quenching process of the excited Ru unit by BNAH. To measure the exact value of kET, picosecond TRIR spectroscopy and a stronger reductant were used. Thus, in the case of the binuclear complex with tri(p-fluorophenyl)phosphine ligands (RuRe(FPh)), for which intramolecular electron transfer is expected to be the fastest among the three binuclear complexes, in the presence of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH), kET was measured as kET = (1.4 ± 0.1) × 109 s-1. This clearly shows that intramolecular electron transfer in these RuRe binuclear supramolecular photocatalysts is not the rate-determining process in the photocatalytic reduction of CO2, which is one of the main reasons why they work so efficiently.

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