ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Photochemical Properties of Re(CO)3 Complexes with and without a Local Proton Source and Implications for CO2 Reduction Catalysis

  • Lucas A. Paul
    Lucas A. Paul
    Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, 37077 Göttingen, Germany
  • Nico C. Röttcher
    Nico C. Röttcher
    Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, 37077 Göttingen, Germany
  • Jennifer Zimara
    Jennifer Zimara
    Max-Planck-Institute for Biophysical Chemistry, Am Fassberg 11, 37077 Göttingen, Germany
  • Jan-Hendrik Borter
    Jan-Hendrik Borter
    Max-Planck-Institute for Biophysical Chemistry, Am Fassberg 11, 37077 Göttingen, Germany
  • Jia-Pei Du
    Jia-Pei Du
    Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, 37077 Göttingen, Germany
    More by Jia-Pei Du
  • Dirk Schwarzer*
    Dirk Schwarzer
    Max-Planck-Institute for Biophysical Chemistry, Am Fassberg 11, 37077 Göttingen, Germany
    *Email: [email protected]
  • Ricardo A. Mata*
    Ricardo A. Mata
    Universität Göttingen, Institut für Physikalische Chemie, Tammannstrasse 6, 37077 Göttingen, Germany
    *Email: [email protected]
  • , and 
  • Inke Siewert*
    Inke Siewert
    Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, 37077 Göttingen, Germany
    *Email: [email protected]
    More by Inke Siewert
Cite this: Organometallics 2020, 39, 13, 2405–2414
Publication Date (Web):June 18, 2020
https://doi.org/10.1021/acs.organomet.0c00240
Copyright © 2020 American Chemical Society

    Article Views

    1264

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (2)»

    Abstract

    Abstract Image

    Herein, we present a detailed study on the photophysical properties and the excited state reactivity of two mononuclear Re(CO)3 complexes with imdazol-pyridine ligands equipped with and without a local proton source, [Re(CO)3LCl], where for 1: L = 2,4-ditert-butyl-6-(6-(1-methyl-1H-imidazol-2-yl)pyridin-2-yl)phenol and 2: L = 2-(3,5-ditert-butyl-2-methoxyphenyl)-6-(1-methyl-1H-imidazol-2-yl)pyridine. Time-resolved IR and UV/vis spectroscopy revealed that excitation of 1 and 2 is followed by population of the triplet excited state within <100 fs, where structural and vibrational relaxation to the T1 equilibrium structure is observed on the picosecond time scale. The T1 state can be viewed as a MLCT state as all ν(CO) features in the transient infrared (TRIR) spectra are shifted to higher wavenumbers upon excitation, which is indicative for a decreasing Re → CO π-backdonation. The T1 states have considerably long lifetimes at room temperature of 160 ns for 1 and 430 ns for 2 in dmf and they can be successfully quenched by the sacrificial electron donors triethanolamine (TEOA) and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH). The quenching rates are 2 orders of magnitude larger for BIH than for TEOA, as the latter reaction is endergonic. However, both species are not active in the photochemical CO2-to-CO conversion. We rationalize this for 2 by the low steady-state concentration of the initial reduction product, [Re(CO)3LCl], which ejects chloride rather fast. Thus, the second, homogeneous electron transfer process between [Re(CO)3LCl] and [Re(CO)3L(solvent)] forming the active species [Re(CO)3L], has a very low probability and decomposition pathways come to the fore. 1 decomposes under irradiation in the presence of BIH or TEOA forming the initial photoproduct 3. We tentatively assume that the ligand in 3 is deprotonated and switches from a N,N- to a N,O-coordination mode. This indicates that in the excited state the Re–N bond is cleaved quite easily, as this decomposition pathway has not been observed under electrochemical conditions.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.organomet.0c00240.

    • Experimental details, X-ray crystallography, transient spectroscopy, luminescence data, IR and NMR spectra, CV data (PDF)

    • Cartesian coordinates for singlet and triplet forms of compounds 1 and 2 (XYZ)

    Accession Codes

    CCDC 1994870 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 8 publications.

    1. Mona Christin Maaß, Alexander Tasch, Christian Jooss, Thomas Waitz. Photocatalytic Hydrogen Evolution Using ZnS Particles and LEDs. Journal of Chemical Education 2022, 99 (5) , 2086-2092. https://doi.org/10.1021/acs.jchemed.1c01157
    2. Inke Siewert. Electrochemical CO2 Reduction Catalyzed by Binuclear LRe2(CO)6Cl2 and LMn2(CO)6Br2 Complexes with an Internal Proton Source. Accounts of Chemical Research 2022, 55 (4) , 473-483. https://doi.org/10.1021/acs.accounts.1c00609
    3. Shao-An Hua, Lucas A. Paul, Manuel Oelschlegel, Sebastian Dechert, Franc Meyer, Inke Siewert. A Bioinspired Disulfide/Dithiol Redox Switch in a Rhenium Complex as Proton, H Atom, and Hydride Transfer Reagent. Journal of the American Chemical Society 2021, 143 (16) , 6238-6247. https://doi.org/10.1021/jacs.1c01763
    4. Marcus Mkhatshwa, Frederick P. Malan, Katlego Makgopa, Amanda-Lee E. Manicum. The crystal structure of fac -tricarbonyl(6-bromo-2,2-bipyridine-κ 2 N,N )-(nitrato-κ O )rhenium(I), C 13 H 7 BrN 3 O 6 Re. Zeitschrift für Kristallographie - New Crystal Structures 2023, 238 (4) , 667-669. https://doi.org/10.1515/ncrs-2023-0141
    5. Jimin Kwak, Junhyeok Woo, Seongmin Park, Mi Hee Lim. Rational design of photoactivatable metal complexes to target and modulate amyloid-β peptides. Journal of Inorganic Biochemistry 2023, 238 , 112053. https://doi.org/10.1016/j.jinorgbio.2022.112053
    6. Li‐Qi Qiu, Kai‐Hong Chen, Zhi‐Wen Yang, Fang‐Yu Ren, Liang‐Nian He. Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole‐Pyridine Framework for Efficient CO 2 Photoreduction. Chemistry – A European Journal 2021, 27 (62) , 15536-15544. https://doi.org/10.1002/chem.202102837
    7. P. A. Abramov. SYNTHESIS AND CRYSTAL STRUCTURE OF [LRe(CO)3(O2CC3F7)]. Journal of Structural Chemistry 2021, 62 (9) , 1416-1424. https://doi.org/10.1134/S0022476621090109
    8. Mohammed Bakir, Mark A.W. Lawrence, Junior Johnson, Colin McMillen. Physicochemical and X-ray crystallographic properties of the first rhenium compound of benzophenone thiosemicarbazone (bptsc), fac-[Re(CO)3(κ2-Nim,S-bptsc)Cl]. Journal of Molecular Structure 2021, 1235 , 130135. https://doi.org/10.1016/j.molstruc.2021.130135

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect