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Related Concept Videos

¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

2.0K
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...
2.0K
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

1.1K
Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...
1.1K
Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

1.1K
Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...
1.1K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

1.2K
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
1.2K
NMR Spectroscopy: Spin–Spin Coupling01:08

NMR Spectroscopy: Spin–Spin Coupling

1.7K
The spin state of an NMR-active nucleus can have a slight effect on its immediate electronic environment. This effect propagates through the intervening bonds and affects the electronic environments of NMR-active nuclei up to three bonds away; occasionally, even farther. This phenomenon is called spin–spin coupling or J-coupling. Coupling interactions are mutual and result in small changes in the absorption frequencies of both nuclei involved. While nuclei of the same element are involved...
1.7K
Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

1.0K
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...
1.0K

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Accessing a Hidden Pathway to Supramolecular Toroid through Vibrational Strong Coupling.

Shunsuke Imai1,2, Takumi Hamada3,4, Misa Nozaki5

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Vibrational strong coupling (VSC) enables the creation of unique molecular structures. This study demonstrates VSC

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Area of Science:

  • Supramolecular Chemistry
  • Materials Science
  • Physical Chemistry

Background:

  • Control over intermolecular interactions is key for designing supramolecular assemblies.
  • Vibrational strong coupling (VSC) is an emerging technique for manipulating molecular interactions.
  • VSC has the potential to control molecular assembly but has not yet created inaccessible structures.

Purpose of the Study:

  • To investigate the use of VSC to control the transformation of naphthalenediimide supramolecular polymers.
  • To explore if VSC can direct molecular assembly toward structures not achievable through conventional methods.

Main Methods:

  • Utilized vibrational strong coupling (VSC) targeting the C-H stretch.
  • Induction of supramolecular polymer transformation via an amino-yne click reaction.
  • Employed theoretical simulations to understand structural changes and intermolecular interactions.

Main Results:

  • VSC accelerated the click reaction within supramolecular polymers, unlike in individual monomers.
  • VSC uniquely altered the morphological transformation, yielding metastable toroids instead of thick fibers.
  • Toroidal structures were exclusively formed under VSC, indicating a novel assembly pathway.

Conclusions:

  • VSC modifies intermolecular interactions in naphthalenediimide assemblies, promoting slipped packing.
  • This VSC-induced modulation leads to the formation of unique toroidal structures.
  • VSC offers a powerful tool for directing molecular assembly beyond conventional limitations.