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Related Concept Videos

¹H NMR of Conformationally Flexible Molecules: Temporal Resolution00:52

¹H NMR of Conformationally Flexible Molecules: Temporal Resolution

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At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the...
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Raman Spectroscopy: Overview01:20

Raman Spectroscopy: Overview

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The underlying principle of Raman spectroscopy is based on the interaction between light and matter, specifically molecules' inelastic scattering of photons. When a monochromatic beam of light, typically from a laser source, interacts with a sample, most scattered light has the same frequency as the incident light. This is known as Rayleigh scattering.
However, a small fraction of the scattered light exhibits a frequency shift due to the exchange of energy between the incident photons and...
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¹³C NMR: Distortionless Enhancement by Polarization Transfer (DEPT)01:20

¹³C NMR: Distortionless Enhancement by Polarization Transfer (DEPT)

1.0K
When proton-coupled carbon-13 spectra are simplified by a broadband proton decoupling technique, structural information about the coupled protons is lost. Distortionless enhancement by polarization transfer (DEPT) is a technique that provides information on the number of hydrogens attached to each carbon in a molecule. While the DEPT experiment utilizes complex pulse sequences, the pulse delay and flip angle are specifically manipulated. The resulting signals have different phases depending on...
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NMR Spectroscopy of Aromatic Compounds01:14

NMR Spectroscopy of Aromatic Compounds

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Aromatic compounds can be identified or analyzed using proton NMR and carbon‐13 NMR. Typically, aromatic hydrogens or hydrogens directly bonded to the aromatic rings are strongly deshielded by the aromatic ring current. Therefore, they absorb in the range of 6.5–8.0 ppm in proton NMR spectra. For instance, aromatic hydrogens directly bonded to the benzene ring absorb at 7.3 ppm. However, aromatic hydrogens of larger rings absorb farther upfield or downfield than the ideal range.
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¹H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR01:15

¹H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR

1.1K
The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one proton, the remaining eleven protons are replaced by deuterium. The deuterium substitution avoids the possible peak splitting caused by the spin-spin coupling between the adjacent protons. The remaining proton flips between the axial and equatorial positions.
1.1K
¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

1.7K
The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
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Chemically Interrogating N-Heterocyclic Carbenes at the Single-Molecule Level Using Tip-Enhanced Raman Spectroscopy.

Linfei Li1, Sayantan Mahapatra1, Jeremy F Schultz1

  • 1Department of Chemistry, University of Illinois Chicago, Chicago, Illinois 60607, United States.

ACS Nano
|November 11, 2024
PubMed
Summary

Tip-enhanced Raman spectroscopy (TERS) probes N-heterocyclic carbene (NHC) surface chemistry at the single-molecule level. This technique identifies NHC structure and binding modes on metal surfaces, advancing nanoelectronic applications.

Keywords:
Ag(111)N-heterocyclic carbenesRaman spectroscopySTMTERS

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Area of Science:

  • Surface Science
  • Nanotechnology
  • Spectroscopy

Background:

  • N-heterocyclic carbenes (NHCs) are vital for functionalizing metal surfaces in energy and nanoelectronic applications.
  • Understanding NHC surface chemistry at the nanoscale is crucial for harnessing their potential.

Purpose of the Study:

  • To demonstrate tip-enhanced Raman spectroscopy (TERS) as a tool for probing NHC surface properties at the single-molecule scale.
  • To investigate the chemical structure and binding modes of NHCs on metal surfaces.

Main Methods:

  • Utilized tip-enhanced Raman spectroscopy (TERS) with subnanometer resolution.
  • Studied low-temperature N-heterocyclic carbene adsorption on Ag(111) surfaces.

Main Results:

  • TERS unambiguously identified individual NHC chemical structures via vibrational fingerprints.
  • TERS definitively determined NHC binding modes on metal surfaces.
  • Investigated temperature-dependent adsorption properties of NHCs.

Conclusions:

  • TERS is a powerful technique for single-molecule vibrational spectroscopy of NHCs.
  • This method offers fundamental insights into NHC surface modification for advanced applications.