Investigation of excited state, reductive quenching, and intramolecular electron transfer of Ru( ii )–Re( i ) supramolecular photocatalysts for CO 2 reduction using time-resolved IR measurements
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 showmore »
- Authors:
-
[2];
[2];
[3]
- National Institute of Advanced Industrial Science and Technology, Tsukuba, Japan
- Chemistry Division, Brookhaven National Laboratory, Upton, USA
- Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Japan
- Department of Chemistry, Kyushu University, Fukuoka 819-0395, Japan
- Publication Date:
- Research Org.:
- National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan); Kyushu Univ., Fukuoka (Japan); Tokyo Institute of Technology (Japan); Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Economy, Trade and Industry (METI) (Japan); Japan Science and Technology Agency (JST); Japan Society for the Promotion of Science (JSPS)
- OSTI Identifier:
- 1422239
- Alternate Identifier(s):
- OSTI ID: 1425101
- Report Number(s):
- BNL-203320-2018-JAAM
Journal ID: ISSN 2041-6520; CSHCBM
- Grant/Contract Number:
- SC0012704; JPMJCR13L1; JP17H06375
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 47 OTHER INSTRUMENTATION
Citation Formats
Koike, Kazuhide, Grills, David C., Tamaki, Yusuke, Fujita, Etsuko, Okubo, Kei, Yamazaki, Yasuomi, Saigo, Masaki, Mukuta, Tatsuhiko, Onda, Ken, and Ishitani, Osamu. Investigation of excited state, reductive quenching, and intramolecular electron transfer of Ru( ii )–Re( i ) supramolecular photocatalysts for CO 2 reduction using time-resolved IR measurements. United Kingdom: N. p., 2018.
Web. doi:10.1039/C7SC05338J.
Koike, Kazuhide, Grills, David C., 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 CO 2 reduction using time-resolved IR measurements. United Kingdom. https://doi.org/10.1039/C7SC05338J
Koike, Kazuhide, Grills, David C., Tamaki, Yusuke, Fujita, Etsuko, Okubo, Kei, Yamazaki, Yasuomi, Saigo, Masaki, Mukuta, Tatsuhiko, Onda, Ken, and Ishitani, Osamu. Mon .
"Investigation of excited state, reductive quenching, and intramolecular electron transfer of Ru( ii )–Re( i ) supramolecular photocatalysts for CO 2 reduction using time-resolved IR measurements". United Kingdom. https://doi.org/10.1039/C7SC05338J.
@article{osti_1422239,
title = {Investigation of excited state, reductive quenching, and intramolecular electron transfer of Ru( ii )–Re( i ) supramolecular photocatalysts for CO 2 reduction using time-resolved IR measurements},
author = {Koike, Kazuhide and Grills, David C. and Tamaki, Yusuke and Fujita, Etsuko and Okubo, Kei and Yamazaki, Yasuomi and Saigo, Masaki and Mukuta, Tatsuhiko and Onda, Ken and Ishitani, Osamu},
abstractNote = {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.},
doi = {10.1039/C7SC05338J},
journal = {Chemical Science},
number = ,
volume = ,
place = {United Kingdom},
year = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}
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Works referenced in this record:
Photophysics of Singlet and Triplet Intraligand Excited States in [ReCl(CO) 3 (1-(2-pyridyl)-imidazo[1,5-α]pyridine)] Complexes
journal, April 2014
- Blanco-Rodríguez, Ana María; Kvapilová, Hana; Sýkora, Jan
- Journal of the American Chemical Society, Vol. 136, Issue 16
Excited-state properties and reactivity of [ReCL(CO) 3 (2,2′-bipy)](2,2′-bipy = 2,2′-bipyridyl) studied by time-resolved infrared spectroscopy
journal, January 1993
- George, Michael W.; Johnson, Frank P. A.; Westwell, Jeremy R.
- J. Chem. Soc., Dalton Trans., Issue 19
Interligand electron transfer and transition state dynamics in Ru(II)trisbipyridine
journal, December 1991
- Malone, R. A.; Kelley, D. F.
- The Journal of Chemical Physics, Vol. 95, Issue 12
Synthesis and Characterization of a Metal-to-Polyoxometalate Charge Transfer Molecular Chromophore
journal, December 2011
- Zhao, Chongchao; Huang, Zhuangqun; Rodríguez-Córdoba, William
- Journal of the American Chemical Society, Vol. 133, Issue 50
Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements
journal, February 2017
- Mukuta, Tatsuhiko; Simpson, Peter V.; Vaughan, Jamila G.
- Inorganic Chemistry, Vol. 56, Issue 6
Application of Time-Resolved, Step-Scan Fourier Transform Infrared Spectroscopy to Excited-State Electronic Structure in Polypyridyl Complexes of Rhenium(I)
journal, January 1996
- Schoonover, Jon R.; Strouse, Geoffrey F.; Dyer, R. Brian
- Inorganic Chemistry, Vol. 35, Issue 2
Electron transfers in chemistry and biology
journal, August 1985
- Marcus, R. A.; Sutin, Norman
- Biochimica et Biophysica Acta (BBA) - Reviews on Bioenergetics, Vol. 811, Issue 3
Intramolecular energy transfer in covalently linked polypyridine rhenium(I)/ruthenium(II) complexes
journal, December 1991
- Furue, M.; Naiki, M.; Kanematsu, Y.
- Coordination Chemistry Reviews, Vol. 111
Probing the Excited States of d 6 Metal Complexes Containing the 2,2‘-Bipyrimidine Ligand Using Time-Resolved Infrared Spectroscopy. 1. Mononuclear and Homodinuclear Systems
journal, April 2007
- Alsindi, Wassim Z.; Easun, Timothy L.; Sun, X. -Z.
- Inorganic Chemistry, Vol. 46, Issue 9
Femtosecond Dynamics of Excited-State Evolution in [Ru(bpy)3]2+
journal, January 1997
- Damrauer, N. H.
- Science, Vol. 275, Issue 5296
Development of efficient photocatalytic systems for CO2 reduction using mononuclear and multinuclear metal complexes based on mechanistic studies
journal, February 2010
- Takeda, Hiroyuki; Ishitani, Osamu
- Coordination Chemistry Reviews, Vol. 254, Issue 3-4
CO2 photoreduction with long-wavelength light: dyads and monomers of zinc porphyrin and rhenium bipyridine
journal, January 2012
- Windle, Christopher D.; Câmpian, Marius V.; Duhme-Klair, Anne-K.
- Chemical Communications, Vol. 48, Issue 66
Ultrafast Charge Separation in a Photoreactive Rhenium-Appended Porphyrin Assembly Monitored by Picosecond Transient Infrared Spectroscopy
journal, April 2006
- Gabrielsson, Anders; Hartl, František; Zhang, Hong
- Journal of the American Chemical Society, Vol. 128, Issue 13
A Visible-Light Harvesting System for CO 2 Reduction Using a Ru II -Re I Photocatalyst Adsorbed in Mesoporous Organosilica
journal, December 2014
- Ueda, Yutaro; Takeda, Hiroyuki; Yui, Tatsuto
- ChemSusChem, Vol. 8, Issue 3
An Inorganic Chromophore Based on a Molecular Oxide Supported Metal Carbonyl Cluster: [P 2 W 17 O 61 {Re(CO) 3 } 3 {ORb(H 2 O)}(μ 3 -OH)] 9–
journal, November 2013
- Zhao, Chongchao; Rodríguez-Córdoba, William; Kaledin, Alexey L.
- Inorganic Chemistry, Vol. 52, Issue 23
Enhanced Photocatalysis of Rhenium(I) Complex by Light-Harvesting Periodic Mesoporous Organosilica
journal, May 2010
- Takeda, Hiroyuki; Ohashi, Masataka; Tani, Takao
- Inorganic Chemistry, Vol. 49, Issue 10
Excited states of transition metal complexes studied by time-resolved infrared spectroscopy
journal, October 1998
- George, M.
- Coordination Chemistry Reviews, Vol. 177, Issue 1
Time-resolved infrared spectroscopy of excited states of transition metal species
journal, May 1993
- Turner, J. J.; George, M. W.; Johnson, F. P. A.
- Coordination Chemistry Reviews, Vol. 125, Issue 1-2
1-Benzyldihydronicotinamide—A Model for Reduced DPN
journal, April 1955
- Mauzerall, David; Westheimer, F. H.
- Journal of the American Chemical Society, Vol. 77, Issue 8
Pinpointing the Extent of Electronic Delocalization in the Re(I)-to-Tetrazine Charge-Separated Excited State Using Time-Resolved Infrared Spectroscopy
journal, August 2009
- Li, Guifeng; Parimal, Kumar; Vyas, Shubham
- Journal of the American Chemical Society, Vol. 131, Issue 33
Architecture of Supramolecular Metal Complexes for Photocatalytic CO 2 Reduction: Ruthenium−Rhenium Bi- and Tetranuclear Complexes
journal, April 2005
- Gholamkhass, Bobak; Mametsuka, Hiroaki; Koike, Kazuhide
- Inorganic Chemistry, Vol. 44, Issue 7
Luminescence and Time-Resolved Infrared Study of Dyads Containing (Diimine)Ru(4,4′-diethylamido-2,2′-bipyridine) 2 and (Diimine)Ru(CN) 4 Moieties: Solvent-Induced Reversal of the Direction of Photoinduced Energy-Transfer
journal, September 2009
- Easun, Timothy L.; Alsindi, Wassim Z.; Deppermann, Nina
- Inorganic Chemistry, Vol. 48, Issue 18
Molecular and electronic structure in the metal-to-ligand charge-transfer excited states of d6 transition-metal complexes in solution
journal, June 1984
- Caspar, Jonathan V.; Westmoreland, T. David; Allen, George H.
- Journal of the American Chemical Society, Vol. 106, Issue 12
Advances in molecular photocatalytic and electrocatalytic CO2 reduction
journal, November 2012
- Windle, Christopher D.; Perutz, Robin N.
- Coordination Chemistry Reviews, Vol. 256, Issue 21-22
New Series of Multifunctionalized Nickel(II)-Cyclam (Cyclam = 1,4,8,11-Tetraazacyclotetradecane) Complexes. Application to the Photoreduction of Carbon Dioxide
journal, February 1994
- Kimura, Eiichi; Wada, Senji; Shionoya, Mitsuhiko
- Inorganic Chemistry, Vol. 33, Issue 4
Femtosecond Transient Absorption Anisotropy Study on [Ru(bpy) 3 ] 2+ and [Ru(bpy)(py) 4 ] 2+ . Ultrafast Interligand Randomization of the MLCT State
journal, June 2005
- Wallin, Staffan; Davidsson, Jan; Modin, Judit
- The Journal of Physical Chemistry A, Vol. 109, Issue 21
Kinetics of Fluorescence Quenching by Electron and H-Atom Transfer
journal, January 1970
- Rehm, Dieter; Weller, Albert
- Israel Journal of Chemistry, Vol. 8, Issue 2
Time-Resolved Infrared Studies on Two Isomeric Ruthenium(II)/Rhenium(I) Complexes Containing a Nonsymmetric Quaterpyridine Bridging Ligand
journal, May 1998
- Schoonover, Jon R.; Shreve, Andrew P.; Dyer, R. Brian
- Inorganic Chemistry, Vol. 37, Issue 10
Supramolecular Photocatalysts for the Reduction of CO 2
journal, April 2017
- Tamaki, Yusuke; Ishitani, Osamu
- ACS Catalysis, Vol. 7, Issue 5
Photocatalytic reduction of CO2 using metal complexes
journal, December 2015
- Yamazaki, Yasuomi; Takeda, Hiroyuki; Ishitani, Osamu
- Journal of Photochemistry and Photobiology C: Photochemistry Reviews, Vol. 25
Electron-Transfer Acceleration Investigated by Time Resolved Infrared Spectroscopy
journal, February 2015
- Vlček, Antonín; Kvapilová, Hana; Towrie, Michael
- Accounts of Chemical Research, Vol. 48, Issue 3
Photo-driven electron transfer from the highly reducing excited state of naphthalene diimide radical anion to a CO 2 reduction catalyst within a molecular triad
journal, January 2017
- Martinez, Jose F.; La Porte, Nathan T.; Mauck, Catherine M.
- Faraday Discussions, Vol. 198
Photoreduction of indigo dyes by electron donors. One- and two-electron-transfer reactions as a consequence of excited-state quenching
journal, May 1986
- Schanze, Kirk S.; Lee, Lester Y. C.; Giannotti, Charles.
- Journal of the American Chemical Society, Vol. 108, Issue 10
Photoinduced Intramolecular Tryptophan Oxidation and Excited-State Behavior of [Re(L-AA)(CO) 3 (α-diimine)] + (L = Pyridine or Imidazole, AA = Tryptophan, Tyrosine, Phenylalanine)
journal, July 2011
- Blanco-Rodríguez, Ana María; Towrie, Mike; Sýkora, J.
- Inorganic Chemistry, Vol. 50, Issue 13
Development of highly efficient supramolecular CO 2 reduction photocatalysts with high turnover frequency and durability
journal, January 2012
- Tamaki, Yusuke; Watanabe, Katsuhiro; Koike, Kazuhide
- Faraday Discuss., Vol. 155
Photoelectrochemical Reduction of CO 2 Coupled to Water Oxidation Using a Photocathode with a Ru(II)–Re(I) Complex Photocatalyst and a CoO x /TaON Photoanode
journal, October 2016
- Sahara, Go; Kumagai, Hiromu; Maeda, Kazuhiko
- Journal of the American Chemical Society, Vol. 138, Issue 42
Proton-Coupled Electron Flow in Protein Redox Machines
journal, December 2010
- Dempsey, Jillian L.; Winkler, Jay R.; Gray, Harry B.
- Chemical Reviews, Vol. 110, Issue 12
Comparison of rhenium–porphyrin dyads for CO 2 photoreduction: photocatalytic studies and charge separation dynamics studied by time-resolved IR spectroscopy
journal, January 2015
- Windle, Christopher D.; George, Michael W.; Perutz, Robin N.
- Chemical Science, Vol. 6, Issue 12
Involvement of a Binuclear Species with the Re−C(O)O−Re Moiety in CO 2 Reduction Catalyzed by Tricarbonyl Rhenium(I) Complexes with Diimine Ligands: Strikingly Slow Formation of the Re−Re and Re−C(O)O−Re Species from Re(dmb)(CO) 3 S (dmb = 4,4‘-Dimethyl-2,2‘-bipyridine, S = Solvent)
journal, October 2003
- Hayashi, Yukiko; Kita, Shouichi; Brunschwig, Bruce S.
- Journal of the American Chemical Society, Vol. 125, Issue 39
Photophysical Behavior of a New CO2 Reduction Catalyst, Re(CO)2(bpy){P(OEt)3}2+
journal, October 1994
- Ishitani, Osamu; George, Michael W.; Ibusuki, Takashi
- Inorganic Chemistry, Vol. 33, Issue 21
Structural deformation of a ring-shaped Re(I) diimine dinuclear complex in the excited state
journal, October 2016
- Tanaka, Sei’ichi; Matsubara, Yoshitaka; Asatani, Tsuyoshi
- Chemical Physics Letters, Vol. 662
Photoelectrochemical CO 2 reduction using a Ru( ii )–Re( i ) multinuclear metal complex on a p-type semiconducting NiO electrode
journal, January 2015
- Sahara, Go; Abe, Ryu; Higashi, Masanobu
- Chemical Communications, Vol. 51, Issue 53
Photophysical properties of polypyridyl carbonyl complexes of rhenium(I)
journal, January 1991
- Worl, Laura A.; Duesing, Rich; Chen, Pingyun
- Journal of the Chemical Society, Dalton Transactions, Issue S
Energetic comparison between photoinduced electron-transfer reactions from NADH model compounds to organic and inorganic oxidants and hydride-transfer reactions from NADH model compounds to p-benzoquinone derivatives
journal, January 1987
- Fukuzumi, Shunichi; Koumitsu, Shintaro; Hironaka, Katsuhiko
- Journal of the American Chemical Society, Vol. 109, Issue 2
Photocatalyses of Ru(II)–Re(I) binuclear complexes connected through two ethylene chains for CO2 reduction
journal, November 2016
- Ohkubo, Kei; Yamazaki, Yasuomi; Nakashima, Takuya
- Journal of Catalysis, Vol. 343
Hydride, Hydrogen Atom, Proton, and Electron Transfer Driving Forces of Various Five-Membered Heterocyclic Organic Hydrides and Their Reaction Intermediates in Acetonitrile
journal, February 2008
- Zhu, Xiao-Qing; Zhang, Ming-Tian; Yu, Ao
- Journal of the American Chemical Society, Vol. 130, Issue 8
Photocatalytic reduction of CO2 using cis,trans-[Re(dmbpy)(CO)2(PR3)(PR’3)]+ (dmbpy=4,4′-dimethyl-2,2′-bipyridine)
journal, January 2007
- Tsubaki, Hideaki; Sugawara, Atsushi; Takeda, Hiroyuki
- Research on Chemical Intermediates, Vol. 33, Issue 1-2
Photochemistry and Photophysics of a Pd(II) Metalloporphyrin: Re(I) Tricarbonyl Bipyridine Molecular Dyad and its Activity Toward the Photoreduction of CO 2 to CO
journal, December 2011
- Schneider, Jacob; Vuong, Khuong Q.; Calladine, James A.
- Inorganic Chemistry, Vol. 50, Issue 23
Contrastive Photoreduction Pathways of Benzophenones Governed by Regiospecific Deprotonation of Imidazoline Radical Cations and Additive Effects
journal, November 2005
- Hasegawa, Eietsu; Seida, Takayuki; Chiba, Naoki
- The Journal of Organic Chemistry, Vol. 70, Issue 23
Application of transient infrared and near infrared spectroscopy to transition metal complex excited states and intermediates
journal, February 2007
- Butler, Jennifer M.; George, Michael W.; Schoonover, Jon R.
- Coordination Chemistry Reviews, Vol. 251, Issue 3-4
Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility
journal, April 2015
- Grills, David C.; Farrington, Jaime A.; Layne, Bobby H.
- Review of Scientific Instruments, Vol. 86, Issue 4
Substantial improvement in the efficiency and durability of a photocatalyst for carbon dioxide reduction using a benzoimidazole derivative as an electron donor
journal, August 2013
- Tamaki, Yusuke; Koike, Kazuhide; Morimoto, Tatsuki
- Journal of Catalysis, Vol. 304
Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels
journal, December 2009
- Morris, Amanda J.; Meyer, Gerald J.; Fujita, Etsuko
- Accounts of Chemical Research, Vol. 42, Issue 12
Electrons, Photons, Protons and Earth-Abundant Metal Complexes for Molecular Catalysis of CO 2 Reduction
journal, November 2016
- Takeda, Hiroyuki; Cometto, Claudio; Ishitani, Osamu
- ACS Catalysis, Vol. 7, Issue 1
Photoinduced Singlet Charge Transfer in a Ruthenium(II) Perylene-3,4:9,10-bis(dicarboximide) Complex
journal, June 2011
- Gunderson, Victoria L.; Krieg, Elisha; Vagnini, Michael T.
- The Journal of Physical Chemistry B, Vol. 115, Issue 23
Key Process of the Photocatalytic Reduction of CO 2 Using [Re(4,4‘-X 2 -bipyridine)(CO) 3 PR 3 ] + (X = CH 3 , H, CF 3 ; PR 3 = Phosphorus Ligands): Dark Reaction of the One-Electron-Reduced Complexes with CO 2
journal, December 1997
- Koike, Kazuhide; Hori, Hisao; Ishizuka, Masakazu
- Organometallics, Vol. 16, Issue 26