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

Autor:	Jia X; The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States., Nedzbala HS; The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States., Bottum SR; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States., Cahoon JF; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States., Concepcion JJ; Chemistry Division, Energy & Photon Sciences Directorate, Brookhaven National Laboratory, Upton, New York 11973, United States., Donley CL; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States., Gang A; The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States., Han Q; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States., Hazari N; The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States., Kessinger MC; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States., Lockett MR; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States., Mayer JM; The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States., Mercado BQ; The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States., Meyer GJ; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States., Pearce AJ; The Department of Chemistry, Yale University, P. O. Box 208107, New Haven, Connecticut 06520, United States., Rooney CL; 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., Sampaio RN; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States., Shang B; 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., Wang H; 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.
Jazyk:	angličtina
Zdroj:	Inorganic chemistry [Inorg Chem] 2023 Feb 06; Vol. 62 (5), pp. 2359-2375. Date of Electronic Publication: 2023 Jan 24.
DOI:	10.1021/acs.inorgchem.2c04137
Abstrakt:	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) 5 Cl to form complexes of the type Re(bpy)(CO) 3 Cl, which are related to known catalysts for CO 2 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 TiO 2 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 CO 2 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.
Databáze:	MEDLINE
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