N-heterocyclic carbenes (NHCs) have been established as powerful modifiers to functionalize metal surfaces for a wide variety of energy and nanoelectronic applications. To fundamentally understand and harness NHC modification, it is essential to identify suitable methods to interrogate NHC surface chemistry at the spatial limit. Here, we demonstrate tip-enhanced Raman spectroscopy (TERS) as a promising tool for chemically probing the surface properties of NHCs at the single-molecule scale. We show that with subnanometer resolution, TERS measurements are capable of not only unambiguously identifying the chemical structure of individual NHCs by their vibrational fingerprints but also definitively determining the binding mode of NHCs on metal surfaces. In particular, by investigating low-temperature NHC adsorption on Ag(111), our TERS studies provide insights into the temperature dependence of the adsorption properties of NHCs. This work suggests the potential of single-molecule vibrational spectroscopy for investigations of NHC surface modification at the most fundamental level.
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http://dx.doi.org/10.1021/acsnano.4c10942 | DOI Listing |
J Am Chem Soc
January 2025
The State Key Laboratory of Molecular Engineering of Polymers and Department of Macromolecular Science, Fudan University, Shanghai 200438, P. R China.
Designing artificial enzymes for in vivo catalysis presents a great challenge due to biomacromolecule contamination, poor biodistribution, and insufficient substrate interaction. Herein, we developed single-chain polymeric nanoparticles with Cu/N-heterocyclic carbene active sites (SCNP-Cu) to function as peroxidase mimics for in vivo catalysis and chemo-dynamic therapy (CDT). Compared with the enzyme mimics based on unfolded linear polymer scaffold and multichain cross-linked scaffold, SCNP-Cu exhibits improved tumor accumulation and CDT efficiency both in vitro and in vivo.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Advanced Computational Chemistry Centre, Cotton University, Guwahati 781001, India.
The complete conversion of dinitrogen to ammonia mediated by a side-on N-bound carbene-beryllium complex, [NHC-Be(η-N)] has been studied considering both the symmetric and unsymmetric pathways. -heterocyclic carbenes complexed with Be(η-N) moieties were considered substrates in our study. We found that two mechanistic pathways were possible for the reduction of dinitrogen to form ammonia.
View Article and Find Full Text PDFChem Asian J
January 2025
Northwest University, College of Chemistry and Materials Science, 1 Xuefu Ave., Guodu Education and Hi-Tech Industries Zone, Chang'an District, 710127, Xi'an, CHINA.
The reversible photoisomerization of azobenzene (AZB) and its derivatives has been applied across various fields. Developing discrete AZB-functionalized organometallic cages is essential for manufacturing functional materials. In this work, we designed and fabricated a series of three-dimensional, hexaazobenzene-terminated poly-NHC-based (NHC = N-heterocyclic carbene) complexes [M3(A)2](BF4)3 and [M3(B)2](BF4)3 (M = Ag, Au).
View Article and Find Full Text PDFPharmaceuticals (Basel)
December 2024
Department of Life, Health and Environmental Sciences, University of L'Aquila, Piazzale Salvatore Tommasi 1, Blocco 11, Coppito, 67010 L'Aquila, Italy.
Background/objectives: Infectious diseases represent a serious threat due to rising antimicrobial resistance, particularly among multidrug-resistant bacteria and influenza viruses. Metal-based complexes, such as -heterocyclic carbene-gold (NHC-gold) complexes, show promising therapeutic potential due to their ability to inhibit various pathogens.
Methods: Eight NHC-gold complexes were synthesized and tested for antibacterial activity against , , and for anti-influenza activity in lung and bronchial epithelial cells infected with influenza virus A/H1N1.
Molecules
December 2024
Centre for AMR and One Health Research, Technological University Dublin, TU Dublin, Tallaght Campus, D24 FKT9 Dublin, Ireland.
Heteroleptic coumarin-based silver(I) complexes with improved solubility profiles were synthesised using either triphenylphosphine or an -heterocyclic carbene as adduct ligands, and were fully characterised using IR and NMR spectroscopy, elemental analysis, and, where possible, X-ray crystallography. The triphenylphosphine adducts formed well-resolved structures, where the oxyacetate ligands asymmetrically chelated the silver(I) ion in a bidentate chelating mode, and the silver(I) ion was also bound to two triphenylphosphine ligands. The solubility profile and photostability of the adducts were considerably improved compared to those of previously isolated simple coumarin silver(I) complexes.
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