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

Journal Article · · Inorganic Chemistry
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  1. Yale University, New Haven, CT (United States)
  2. University of North Carolina, Chapel Hill, NC (United States)
  3. Brookhaven National Laboratory (BNL), Upton, NY (United States). Chemistry Div.
+ Show Author Affiliations
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. So 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.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); University of North Carolina, Chapel Hill, NC (United States)
Sponsoring Organization:
National Institutes of Health (NIH); National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704; SC0021173
OSTI ID:
1963579
Alternate ID(s):
OSTI ID: 2377748
Report Number(s):
BNL--224180-2023-JAAM
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 5 Vol. 62; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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