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Synthesis and Surface Attachment of Molecular Re(I) Complexes Supported by Functionalized Bipyridyl Ligands

  • Xiaofan Jia
    Xiaofan Jia
    The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States
    More by Xiaofan Jia
  • Hannah S. Nedzbala
    Hannah S. Nedzbala
    The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States
  • Samuel R. Bottum
    Samuel R. Bottum
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States
  • James F. Cahoon
    James F. Cahoon
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States
  • Javier J. Concepcion*
    Javier J. Concepcion
    Chemistry Division, Energy & Photon Sciences Directorate, Brookhaven National Laboratory, Upton, New York 11973, United States
    *Email: [email protected]
  • Carrie L. Donley
    Carrie L. Donley
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States
  • Albert Gang
    Albert Gang
    The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States
    More by Albert Gang
  • Qi Han
    Qi Han
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States
    More by Qi Han
  • Nilay Hazari*
    Nilay Hazari
    The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States
    *Email: [email protected]
    More by Nilay Hazari
  • Matthew C. Kessinger
    Matthew C. Kessinger
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States
  • Matthew R. Lockett
    Matthew R. Lockett
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States
  • James M. Mayer*
    James M. Mayer
    The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States
    *Email: [email protected]
  • Brandon Q. Mercado
    Brandon Q. Mercado
    The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States
  • Gerald J. Meyer
    Gerald J. Meyer
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States
  • Adam J. Pearce
    Adam J. Pearce
    The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States
  • Conor L. Rooney
    Conor L. Rooney
    The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States
    Energy Sciences Institute, Yale University, West Haven, Connecticut 06516, United States
  • Renato N. Sampaio
    Renato N. Sampaio
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States
  • Bo Shang
    Bo Shang
    The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States
    Energy Sciences Institute, Yale University, West Haven, Connecticut 06516, United States
    More by Bo Shang
  • , and 
  • Hailiang Wang
    Hailiang Wang
    The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States
    Energy Sciences Institute, Yale University, West Haven, Connecticut 06516, United States
Cite this: Inorg. Chem. 2023, 62, 5, 2359–2375
Publication Date (Web):January 24, 2023
https://doi.org/10.1021/acs.inorgchem.2c04137
Copyright © 2023 American Chemical Society

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    Abstract

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    Eleven 2,2′-bipyridine (bpy) ligands functionalized with attachment groups for covalent immobilization on silicon surfaces were prepared. Five of the ligands feature silatrane functional groups for attachment to metal oxide coatings on the silicon surfaces, while six contain either alkene or alkyne functional groups for attachment to hydrogen-terminated silicon surfaces. The bpy ligands were coordinated to Re(CO)5Cl to form complexes of the type Re(bpy)(CO)3Cl, which are related to known catalysts for CO2 reduction. Six of the new complexes were characterized using X-ray crystallography. As proof of principle, four molecular Re complexes were immobilized on either a thin layer of TiO2 on silicon or hydrogen-terminated silicon. The surface-immobilized complexes were characterized using X-ray photoelectron spectroscopy, IR spectroscopy, and cyclic voltammetry (CV) in the dark and for one representative example in the light. The CO stretching frequencies of the attached complexes were similar to those of the pure molecular complexes, but the CVs were less analogous. For two of the complexes, comparison of the electrocatalytic CO2 reduction performance showed lower CO Faradaic efficiencies for the immobilized complexes than the same complex in solution under similar conditions. In particular, a complex containing a silatrane linked to bpy with an amide linker showed poor catalytic performance and control experiments suggest that amide linkers in conjugation with a redox-active ligand are not stable under highly reducing conditions and alkyl linkers are more stable. A conclusion of this work is that understanding the behavior of molecular Re catalysts attached to semiconducting silicon is more complicated than related complexes, which have previously been immobilized on metallic electrodes.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c04137.

    • Experimental details; synthesis and characterization of compounds; cyclic voltammetry with complexes 2ak; surface functionalization procedures; comparison of molecular and surface-bound characterization; characterization of hybrid electrodes; IR spectra of complexes 2ak; NMR spectra of new compounds; and X-ray diffraction data (PDF)

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    CCDC 21729942172999 contain 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.

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    Cited By

    This article is cited by 5 publications.

    1. Hannah S. Nedzbala, Dalaney Westbroek, Hannah R. M. Margavio, Hyuenwoo Yang, Hyunho Noh, Samantha V. Magpantay, Carrie L. Donley, Amar S. Kumbhar, Gregory N. Parsons, James M. Mayer. Photoelectrochemical Proton-Coupled Electron Transfer of TiO2 Thin Films on Silicon. Journal of the American Chemical Society 2024, 146 (15) , 10559-10572. https://doi.org/10.1021/jacs.4c00014
    2. Xiaofan Jia, Eleanor Stewart-Jones, Jose L. Alvarez-Hernandez, Gabriella P. Bein, Jillian L. Dempsey, Carrie L. Donley, Nilay Hazari, Madison N. Houck, Min Li, James M. Mayer, Hannah S. Nedzbala, Rebecca E. Powers. Photoelectrochemical CO2 Reduction to CO Enabled by a Molecular Catalyst Attached to High-Surface-Area Porous Silicon. Journal of the American Chemical Society 2024, 146 (12) , 7998-8004. https://doi.org/10.1021/jacs.3c10837
    3. Xiaofan Jia, Kai Cui, Jose L. Alvarez-Hernandez, Carrie L. Donley, Albert Gang, Sharon Hammes-Schiffer, Nilay Hazari, Sungho Jeon, James M. Mayer, Hannah S. Nedzbala, Bo Shang, Eric A. Stach, Eleanor Stewart-Jones, Hailiang Wang, Alexa Williams. Synthesis and Surface Attachment of Molecular Re(I) Hydride Species with Silatrane Functionalized Bipyridyl Ligands. Organometallics 2023, 42 (16) , 2238-2250. https://doi.org/10.1021/acs.organomet.3c00235
    4. James V. Coe, Walter J. Dressick, Claudia Turro. Etalon-Assisted Study of the Strong CO Ligand Vibrations of the fac-[Re(CO)3(bpy)(CH3CN)]+ Octahedral Complex. The Journal of Physical Chemistry B 2023, 127 (29) , 6516-6531. https://doi.org/10.1021/acs.jpcb.3c02496
    5. Hitoshi Izu, Hiroyasu Tabe, Yuji Namiki, Hiroki Yamada, Satoshi Horike. Heterogenous CO2 Reduction Photocatalysis of Transparent Coordination Polymer Glass Membranes Containing Metalloporphyrins. Inorganic Chemistry 2023, 62 (29) , 11342-11349. https://doi.org/10.1021/acs.inorgchem.3c00700