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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

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C7SC05338J· OSTI ID:1422239
 [1]; ORCiD logo [2];  [3]; ORCiD logo [2];  [3];  [3];  [4];  [3];  [4]; ORCiD logo [3]
  1. National Institute of Advanced Industrial Science and Technology, Tsukuba, Japan
  2. Chemistry Division, Brookhaven National Laboratory, Upton, USA
  3. Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Japan
  4. Department of Chemistry, Kyushu University, Fukuoka 819-0395, Japan
+ Show Author Affiliations

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.

Research Organization:
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 Organization:
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)
Grant/Contract Number:
SC0012704; JPMJCR13L1; JP17H06375
OSTI ID:
1422239
Alternate ID(s):
OSTI ID: 1425101
Report Number(s):
BNL-203320-2018-JAAM; CSHCBM
Journal Information:
Chemical Science, Journal Name: Chemical Science; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United Kingdom
Language:
English
Citation Metrics:
Cited by: 45 works
Citation information provided by
Web of Science

References (56)

Photophysics of Singlet and Triplet Intraligand Excited States in [ReCl(CO) 3 (1-(2-pyridyl)-imidazo[1,5-α]pyridine)] Complexes journal April 2014
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
Interligand electron transfer and transition state dynamics in Ru(II)trisbipyridine journal December 1991
Synthesis and Characterization of a Metal-to-Polyoxometalate Charge Transfer Molecular Chromophore journal December 2011
Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements journal February 2017
Application of Time-Resolved, Step-Scan Fourier Transform Infrared Spectroscopy to Excited-State Electronic Structure in Polypyridyl Complexes of Rhenium(I) journal January 1996
Electron transfers in chemistry and biology journal August 1985
Intramolecular energy transfer in covalently linked polypyridine rhenium(I)/ruthenium(II) complexes journal December 1991
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
Femtosecond Dynamics of Excited-State Evolution in [Ru(bpy)3]2+ journal January 1997
Development of efficient photocatalytic systems for CO2 reduction using mononuclear and multinuclear metal complexes based on mechanistic studies journal February 2010
CO2 photoreduction with long-wavelength light: dyads and monomers of zinc porphyrin and rhenium bipyridine journal January 2012
Ultrafast Charge Separation in a Photoreactive Rhenium-Appended Porphyrin Assembly Monitored by Picosecond Transient Infrared Spectroscopy journal April 2006
A Visible-Light Harvesting System for CO 2 Reduction Using a Ru II -Re I Photocatalyst Adsorbed in Mesoporous Organosilica journal December 2014
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
Enhanced Photocatalysis of Rhenium(I) Complex by Light-Harvesting Periodic Mesoporous Organosilica journal May 2010
Excited states of transition metal complexes studied by time-resolved infrared spectroscopy journal October 1998
Time-resolved infrared spectroscopy of excited states of transition metal species journal May 1993
1-Benzyldihydronicotinamide—A Model for Reduced DPN journal April 1955
Pinpointing the Extent of Electronic Delocalization in the Re(I)-to-Tetrazine Charge-Separated Excited State Using Time-Resolved Infrared Spectroscopy journal August 2009
Architecture of Supramolecular Metal Complexes for Photocatalytic CO 2 Reduction:  Ruthenium−Rhenium Bi- and Tetranuclear Complexes journal April 2005
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
Molecular and electronic structure in the metal-to-ligand charge-transfer excited states of d6 transition-metal complexes in solution journal June 1984
Advances in molecular photocatalytic and electrocatalytic CO2 reduction journal November 2012
New Series of Multifunctionalized Nickel(II)-Cyclam (Cyclam = 1,4,8,11-Tetraazacyclotetradecane) Complexes. Application to the Photoreduction of Carbon Dioxide journal February 1994
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
Kinetics of Fluorescence Quenching by Electron and H-Atom Transfer journal January 1970
Time-Resolved Infrared Studies on Two Isomeric Ruthenium(II)/Rhenium(I) Complexes Containing a Nonsymmetric Quaterpyridine Bridging Ligand journal May 1998
Supramolecular Photocatalysts for the Reduction of CO 2 journal April 2017
Photocatalytic reduction of CO2 using metal complexes journal December 2015
Electron-Transfer Acceleration Investigated by Time Resolved Infrared Spectroscopy journal February 2015
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
Photoreduction of indigo dyes by electron donors. One- and two-electron-transfer reactions as a consequence of excited-state quenching journal May 1986
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
Development of highly efficient supramolecular CO 2 reduction photocatalysts with high turnover frequency and durability journal January 2012
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
Proton-Coupled Electron Flow in Protein Redox Machines journal December 2010
Comparison of rhenium–porphyrin dyads for CO 2 photoreduction: photocatalytic studies and charge separation dynamics studied by time-resolved IR spectroscopy journal January 2015
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
Photophysical Behavior of a New CO2 Reduction Catalyst, Re(CO)2(bpy){P(OEt)3}2+ journal October 1994
Structural deformation of a ring-shaped Re(I) diimine dinuclear complex in the excited state journal October 2016
Photoelectrochemical CO 2 reduction using a Ru( ii )–Re( i ) multinuclear metal complex on a p-type semiconducting NiO electrode journal January 2015
Photophysical properties of polypyridyl carbonyl complexes of rhenium(I) journal January 1991
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
Photocatalyses of Ru(II)–Re(I) binuclear complexes connected through two ethylene chains for CO2 reduction journal November 2016
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
Photocatalytic reduction of CO2 using cis,trans-[Re(dmbpy)(CO)2(PR3)(PR’3)]+ (dmbpy=4,4′-dimethyl-2,2′-bipyridine) journal January 2007
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
Contrastive Photoreduction Pathways of Benzophenones Governed by Regiospecific Deprotonation of Imidazoline Radical Cations and Additive Effects journal November 2005
Application of transient infrared and near infrared spectroscopy to transition metal complex excited states and intermediates journal February 2007
Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility journal April 2015
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
Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels journal December 2009
Electrons, Photons, Protons and Earth-Abundant Metal Complexes for Molecular Catalysis of CO 2 Reduction journal November 2016
Photoinduced Singlet Charge Transfer in a Ruthenium(II) Perylene-3,4:9,10-bis(dicarboximide) Complex journal June 2011
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

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