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Related Concept Videos

¹H NMR: Complex Splitting01:13

¹H NMR: Complex Splitting

A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
2D NMR: Heteronuclear Single-Quantum Correlation Spectroscopy (HSQC)01:19

2D NMR: Heteronuclear Single-Quantum Correlation Spectroscopy (HSQC)

Heteronuclear single-quantum correlation spectroscopy (HSQC) is a 2D NMR technique that reveals one-bond correlations between hydrogen and a heteronucleus. The HSQC experiment is similar to the heteronuclear correlation experiment (HETCOR) but is more sensitive. In the HSQC spectrum, the proton chemical shift is plotted on the horizontal F2 axis, while the 13C chemical shift is plotted on the vertical F1 axis. The corresponding proton and 13C spectra are also shown. The HSQC contour plot does...
2D NMR: Overview of Heteronuclear Correlation Techniques01:18

2D NMR: Overview of Heteronuclear Correlation Techniques

Heteronuclear correlation spectroscopy is an analytical technique that investigates the coupling between different types of nuclei, often a proton and an X-nucleus, such as carbon-13 or nitrogen-15. This method is commonly used in nuclear magnetic resonance (NMR) spectroscopy to gain insights into complex chemical compounds' structural and compositional aspects. A typical heteronuclear correlation spectrum displays X-nucleus chemical shifts on one axis and a proton spectrum on the other axis.
¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

Spin systems where the difference in chemical shifts of the coupled nuclei is greater than ten times J are called first-order spin systems. These nuclei are weakly coupled, and their chemical shifts and coupling constant can generally be estimated from the well-separated signals in the spectrum.
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are slanted or...
UV–Vis Spectroscopy: Molecular Electronic Transitions01:16

UV–Vis Spectroscopy: Molecular Electronic Transitions

In Ultraviolet–Visible (UV–Vis) spectroscopy, the absorption of electromagnetic radiation is used to probe the electronic structure of molecules. This technique provides insights into molecular electronic transitions, particularly the movement of electrons between different molecular orbitals. Radiation is absorbed if the energy of the electromagnetic radiation passing through the molecule is precisely equal to the energy difference between the excited and ground states. During this process,...
Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

In bromoethane, the three methyl protons are coupled to the two methylene protons that are three bonds away. In accordance with the n+1 rule, the signal from the methyl protons is split into three peaks with 1:2:1 relative intensities. The methylene protons appear as a quartet, with the relative intensities of 1:3:3:1.
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must have a...

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A Technical Guide for Performing Spectroscopic Measurements on Metal-Organic Frameworks
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Spectroscopic study of the benchmark Mn+-H2 complex.

Viktoras Dryza1, Berwyck L J Poad, Evan J Bieske

  • 1School of Chemistry, The University of Melbourne, Victoria, Australia 3010.

The Journal of Physical Chemistry. A
|May 2, 2009
PubMed
Summary

We recorded the infrared spectrum of manganese cation-dihydrogen (Mn+-H2) complex. Spectroscopic data reveal a T-shaped configuration, crucial for understanding noncovalent interactions and potential hydrogen storage applications.

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Area of Science:

  • Physical Chemistry
  • Spectroscopy
  • Quantum Chemistry

Background:

  • Transition metal cation-dihydrogen complexes are vital for understanding noncovalent interactions.
  • Characterizing these complexes aids in developing hydrogen storage solutions.
  • Previous studies have initiated the characterization of such systems.

Purpose of the Study:

  • To record and analyze the rotationally resolved infrared spectrum of the Mn+-H2 complex.
  • To determine the structural and energetic properties of the Mn+-H2 complex.
  • To establish Mn+-H2 as a benchmark for quantum chemical calculations.

Main Methods:

  • Rotationally resolved infrared spectroscopy was employed.
  • The H-H stretch region (4022-4078 cm(-1)) was investigated.
  • Mn+ photodissociation products were monitored.

Main Results:

  • The H-H stretch transition in Mn+-H2 is shifted by -111.8 cm(-1) from free H2.
  • The complex adopts a T-shaped configuration with an intermolecular separation of 2.73 A.
  • A binding energy of 7.9 kJ/mol was previously measured.

Conclusions:

  • Mn+-H2 is the most thoroughly characterized transition-metal cation-dihydrogen complex to date.
  • The findings provide a benchmark for calibrating quantum chemical calculations.
  • These systems show potential for hydrogen storage applications.